arXiv subjects

Rüdiger Klingeler

Publications and source records attributed to Rüdiger Klingeler.

At least 19 recordsLinked to original sources

arXiv2026

Sulfur-rich Spirofluorene-Bridged N Heterotriangulene Redox-Active Polymers

Sulfur-rich spirofluorene-bridged N-heterotriangulene (FTN) polymers featuring covalently linked oligosulfide units and a terthiophene-based analogue were synthesized via nucleophilic aromatic substitution and Stille cross-coupling polymerization. The resulting materials are amorphous, insoluble solids with high thermal stability and sulfur contents up to 25 wt%. Structural and compositional analyses by combustion analysis, ToF-SIMS, FT-IR, XPS, and solid-state NMR confirm the efficient incorporation of short oligosulfide to disulfide linkages and well-defined terthiophene units in the respective polymers. Electrochemical characterization in lithium half-cells reveals a reversible, high-voltage oxidation of the FTN unit at 3.8-4.0 V (vs. Li/Li+), accompanied by low-voltage sulfur- or terthiophene-based redox processes between 1.5-2.5 V (vs. Li/Li+). Sulfur incorporation markedly increases the theoretical and initial discharge capacities (up to 129 mA h g-1), while the sulfide conversion processes exhibit rapid fading and poor reversibility due to sulfide dissolution. In contrast, the terthiophene-linked polymer shows only transient low-voltage activity while maintaining high Coulombic efficiencies (ca. 99.7%) governed by the persistent FTN backbone redox event. Our results highlight how different redox-active linkers influence the electrochemical behavior of FTN-based polymers and provide insights into the design of functional organic cathode materials featuring multi-redox processes.

cond-mat.mtrl-sci↗

arXiv2026

Magnetism in antiperovskite (Li$_2$\textit{M})\textit{Ch}O (\textit{M} = Fe, Mn, Co; \textit{Ch} = S, Se) diluted magnets with fixed 1/3 filling: the key role of magnetic anisotropy

We report the magnetic properties of a series of lithium-rich antiperovskites (Li$_2M$)$Ch$O ($M$ = Fe, Co, Mn and $Ch$ = Se, S) where transition metal and lithium ions are randomly distributed on the X-sites of the X$_3$BA structure, thereby forming a strongly diluted magnetic sublattice. Our study hence enables us to investigate the evolution of magnetic order at fixed 1/3-filling -- which is in the vicinity but slightly above the percolation threshold -- upon variation of the spin size, the magnetic anisotropy, and the orbital configuration. The data imply the absence of a distinct Curie-Weiss behavior up to 350~K but show rather large and weakly temperature-dependent magnetic susceptibility. We observe clear signatures of long-range antiferromagnetic order evolving in the 1/3-filled and strongly diluted magnetic X-site lattice with increasing Néel temperatures from $T_{\rm{N}}\simeq 30$~K in (Li$_2$Mn)$Ch$O to $\simeq 50$~K in (Li$_2$Fe)$Ch$O and $70-90$~K in (Li$_2$Co)$Ch$O. Except for $M$ = Co, the chalcogenide has no sizable effect on $T_{\rm N}$. We conclude significant magnetic coupling and short-range magnetic correlations at well above $T_{\rm N}$ which is in line with the observation of a broad electron spin resonance signal at room temperature. The actual ordering temperatures are strongly diminished by magnetic dilution. While structural parameters such as the tolerance factor and bonding angles do not strongly affect $T_{\rm N}$, a key parameter is the magnetic anisotropy of the transition metals.

cond-mat.str-el↗

arXiv2025

Elucidating the origin of long-range ferromagnetic order in Fe$_3$GeTe$_2$ by low-energy magnon excitation studies

We report a detailed high-field/high-frequency ferromagnetic resonance (HF-FMR) study of low-energy magnon excitations in the van der Waals ferromagnet Fe$_3$GeTe$_2$. At 2 K, the field dependence of the magnon branches is well described by a semiclassical domain-based model, from which we extract key microscopic parameters including the anisotropy gap $Δ= 170\pm 4$ GHz, the anisotropy field $B_{\rm A} = 5.85\pm 0.08$ T, and the effective $g$-factor $g_{\rm ab}\simeq g_{\rm c} = 2.07(4)$. Furthermore the uniaxial anisotropy constant was determined to be $K = (10.5\pm 0.23) \times 10^{-6}$ erg/cm$^3$. Anisotropic short-range magnetic order persists above $T_{\rm C}$ up to approximately 270 K, as evidenced by a finite anisotropy gap and anisotropic shifts in the FMR resonance fields. Both results clearly show the presence of anisotropic local magnetic fields well above $T_{\rm C}$. Our findings underscore the crucial role of magneto-crystalline anisotropy in driving long-range magnetic order in Fe$_3$GeTe$_2$.

cond-mat.str-el↗

arXiv2025

Anomalous Charge Density Wave and Fermi Surface Reconstruction in Pressurized BaFe2Al9

The intermetallic compound BaFe2Al9 exhibits unusual physical properties associated with a charge density wave (CDW) transition. Unlike conventional CDW materials, which typically display subtle structural distortions or lattice modulations, BaFe2Al9 undergoes a first-order phase transition in which lattice strain plays a crucial role in the formation of the CDW state. To further explore this unique behavior, we conducted high-pressure studies, examining the electrical transport, magnetic, and structural properties to gain deeper insight into the underlying CDW mechanism. At ambient pressure, electrical resistivity and magnetization measurements confirm the presence of a CDW transition. Upon applying pressure, the CDW transition temperature (TCDW) shifts to higher values, reaching approximately 300 K near 3.2 GPa, and the electrical resistivity increases, suggesting that pressure modulates the charge carrier concentration. Furthermore, the initially sharp first-order transition becomes more gradual, and analysis of the temperature derivative of resistivity indicates a crossover from first-order to second-order like behavior under pressure. High-pressure magnetization measurements are consistent with the electrical transport data, showing an enhancement of TCDW with increasing pressure. The residual resistivity increases with pressure, while the Fermi liquid coefficient A decreases above 2 GPa, pointing to a possible Fermi surface reconstruction. High-pressure synchrotron powder X-ray diffraction (XRD) measurements at room temperature reveal a lattice anomaly near 3.8 GPa, marked by a distinct trend change in macrostrain, further supporting the existence of a pressure induced structural response. These findings provide valuable insight into the nature of CDW formation in BaFe2Al9 and highlight the critical role of lattice strain and external pressure in tuning its electronic ground state.

cond-mat.str-el↗

arXiv2025

Magnetic and thermodynamic studies on the distorted kagome magnet Pr$_3$BWO$_9$

We report specific heat, ac/dc magnetic susceptibility as well as static and pulsed field magnetization studies on the distorted kagome magnet Pr$_3$BWO$_9$ down to 0.4~K and up to high magnetic fields. The low-temperature thermodynamic properties are found to be governed by an electronic quasi-doublet ground state; the energy splitting of which amounts to $Δ_1\simeq 18$ K and exhibits a quadratic field dependence with $g_\mathrm{eff} = 2.6$. Fitting of the specific heat data implies that the next excited state is strongly gapped at $Δ_2=430$ K and three-fold degenerate in zero field. Our dc and ac susceptibility studies down to 0.4 K do not detect signatures of distinct spin glass behavior. Pulsed field magnetization measurements up to 60 T confirm the Ising-like paramagnetic nature of the magnetic ground state which is characterized by $m_J=\pm 4$ and the anisotropy energy $E_a\simeq 950$ K.

cond-mat.str-el↗

arXiv2025

Spin waves in Na$_2$Co$_2$TeO$_6$ studied by high-frequency/high-field ESR: Successes and failures of the triple-$\mathbf{q}$ model

The Kitaev candidate material Na$_2$Co$_2$TeO$_6$ is proposed to be proximate to a quantum spin liquid state but a suitable spin model and the nature of its ground states are still under debate. Our high-frequency/high-field electron spin resonance spectroscopy studies of Na$_2$Co$_2$TeO$_6$ single-crystals under in-plane and out-of-plane magnetic fields elucidate the ground state by investigating its low-energy spin wave excitations. Several excitation modes are observed in the low-field phase and in the phases induced by $B\parallel a^*$. In addition, the spectra exhibit a frequency-independent feature at the phase boundary connected to the putative quantum phase transition. For magnetic fields applied along the $c$ axis, the observation of three distinct spin wave modes in the antiferromagnetic (AFM) ground state reveals a previously unresolved splitting of the zero-field excitation gap into $Δ= 211\,$GHz and $Δ_2 = 237\,$GHz. The softening of one of these modes evidences a field-induced phase transition at $B_{\rm c1} = 4.7\,$T, which is corroborated by a clear anomaly in the isothermal magnetization. Spin wave calculations based on the extended Heisenberg-Kitaev model exclude a zigzag ground state of the AFM phase. A triple-q spin configuration correctly predicts two spin wave modes, but fails to reproduce the softening mode. Our analysis shows that the triple-q ground state model of Na$_2$Co$_2$TeO$_6$ is incomplete and suggests the relevance of interlayer interactions.

cond-mat.str-el↗

arXiv2025

Anisotropic magnetic phase diagrams, tricriticality, and spin-reorientation in high-pressure grown SmCrO$_3$ single crystals

SmCrO$_3$ single crystals were successfully grown utilizing the high-pressure optical floating-zone method and their crystal structure, magnetization behavior, and magnetic phase diagrams were thoroughly investigated. Magnetic studies were conducted for fields applied along all principal crystallographic directions, with measurements taken at temperatures as low as 0.4 K and magnetic fields up to 14 T. The single crystal growth parameters are reported and the orthorhombic structure with the centrosymmetric space group $Pbnm$ is confirmed. Long-range order of the Cr$^{3+}$ and Sm$^{3+}$ magnetic sublattices evolves at $T_{\rm N}$ = 192 K and $T_{\rm N2}$=3 K, respectively. In contrast to previous studies on polycrystals our single crystal data imply a discontinuous and one-step spin-reorientation (SR) of net magnetic moments $\tilde{M}$ from the $c$ axis into the $ab$ plane at zero magnetic field at $T_{\rm SR}$=33 K. Its discontinuous nature is maintained if $B$ is applied $||c$ axis but tricritical behavior and a triple point is found for $B||a$ axis. While our data are consistent with the magnetic representation $Γ_4$ for $T > T_{\mathrm {SR}}$, the size and in-plane direction of the observed net magnetic moment disagree to previously proposed spin configurations, i.e., $Γ_1$ and $Γ_2$, for the spin-reoriented phases. In general, our high-quality single crystals enable us to revisit the phase diagram and to clarify the complex magnetism in SmCrO3 arising from the interplay of anisotropic 3$d$ and 4$f$ magnetic sublattices.

cond-mat.str-el↗

arXiv2025

Two-stage evolution of magnetic correlations in spiral spin liquid material, Ca$_{10}$Cr$_{7}$O$_{28}$

We present an X-band and tunable high-frequency/high-field electron spin resonance (HF-ESR) study of single-crystalline Ca$_{10}$Cr$_{7}$O$_{28}$, which constitutes alternating antiferromagnetic and ferromagnetic kagome bilayers. At high temperatures, a phonon-assisted relaxation process is evoked to account for the pronounced increase of the linewidth in an exchange-narrowing regime ($k_{\rm B}T\gg J$). In contrast, at low temperatures ($k_{\rm B}T\lesssim J$), a power-law behavior in line narrowing is observed. Our data reveal two distinct power-law regimes for the linewidth which crossover at $T^*\approx 7.5$~K. Notably, the intriguing evolution of the ESR linewidth in this alternating kagome bilayer system with opposite sign of exchange interactions highlights distinct spin dynamics compared to those in a uniform kagome antiferromagnet.

cond-mat.str-el↗

arXiv2024

Separating cationic and anionic redox activity in antiperovskite Li$_2$Fe)SO

Lithium-rich antiperovskite promise to be a compelling high-capacity cathode material due to existence of both cationic and anionic redox activity. Little is however known about the effect of separating the electrochemical cationic from the anionic process and the associated implications on the electrochemical performance. In this context, we report the electrochemical properties of the illustrative example of three different Li$_2$Fe)SO materials with a focus on separating cationic from anionic effects. With the high voltage anionic process, an astonishing electrochemical capacity of around 400~mAh/g can initially be reached. Our results however identify the anionic process as the cause of poor cycling stability and demonstrate that fading reported in previous literature is avoided by restricting to only the cationic processes. Following this path, our Li$_2$Fe)SO-BM500 shows strongly improved performance indicated by constant electrochemical cycling over 100 cycles at a capacity of around 175~mAh/g at 1~C. Our approach also allows us to investigate the electrochemical performance of the bare antiperovskite phase excluding extrinsic activity from initial or cycling-induced impurity phases. Our results underscore that synthesis conditions are a critical determinant of electrochemical performance in lithium-rich antiperovskites, especially with regard to the amount of electrochemical secondary phases, while the particle size has not been found a crucial parameter. Overall, separating and understanding the effects of cationic from anionic redox activity in lithium-rich antiperovskites provides the route to further improve their performance in electrochemical energy storage.

cond-mat.mtrl-sci↗

arXiv2023

Magnetic phase diagram and magneto-elastic coupling of NdB$_4$ studied by high-resolution capacitance dilatometry up to 35~T

We report high-resolution dilatometry studies on single crystals of the Shastry-Sutherland-lattice magnet NdB$_4$ supported by specific heat and magnetometry data. Our dilatometric studies evidence pronounced anomalies at the phase boundaries which imply strong magneto-elastic coupling. The evolution of the three zero-field phase transitions separating distinct antiferromagnetic phases at $TN=17.2$~K, $TIT=6.8$~K and $TLT=4.8$~K can thus be traced in applied magnetic fields which provides the magnetic phase diagrams for $B\parallel c$ up to 15~T and for $B\parallel [110]$ up to 35~T. New in-field phases are discovered for both field directions and already known phases are confirmed. In particular, phase boundaries between different phases are unambiguously shown by sign changes of observed anomalies and corresponding changes in uniaxial pressure effects. For $B||c$, we find a 1/4-magnetization plateau in addition to a previously reported plateau at 1/5 of the saturation magnetization. TN increases for $B\parallel c$ in fields up to 15~T implying that magnetic moments of the all-in/all-out structure in the high temperature AFM ordered phase are driven towards the $c$ axis in high magnetic fields. Uniaxial pressure dependencies ${\partial}T_{\mathrm{crit}}/{\partial}p_{\mathrm{c}}$ of the phase transition temperatures for magnetic fields and pressure applied along the $c$ axis are derived from the data.

cond-mat.str-el↗

arXiv2023

High-pressure crystal growth and investigation of the metal-to-metal transition of Ruddlesden-Popper trilayer nickelates La$_4$Ni$_3$O$_{10}$

Single crystals of Ruddlesden-Popper nickelates La$_4$Ni$_3$O$_{10}$ were grown by means of the floating-zone technique at oxygen pressure of 20~bar. Our results reveal the effects of the annealing process under pressure on the crystal structure. We present the requirements for crystal growth and show how a reported ferromagnetic impurity phase can be avoided. The different growth and post-annealing processes result in two distinct phases $P2_1/a$ and {\it Bmab} in which the metal-to-metal transitions occur at 152~K and 136~K, respectively.

cond-mat.str-el↗

arXiv2023

1/3 plateau and 3/5 discontinuity in the magnetization and the magnetic phase diagram of hexagonal GdInO$_3$

We report the high-pressure optical floating-zone growth of GdInO$_3$ single crystals and show its magnetic phase diagram down to the mK-regime as determined by magnetization measurements. The centered-honeycomb lattice structure shows considerable magnetic frustration ($\lvertΘ\rvert /T_{\rm N}\simeq 5$) and develops long-range magnetic order below $T_{\rm N}$~=~2.1 K from a short-range ordered paramagnetic phase. Concomitantly, a small net magnetic moment evolves at $T_{\rm N}$ which points along the crystallographic $c$ direction. Upon cooling, the net moment reorients at $T^{**}\simeq 1.7$ K and $T^{*}\simeq 1$ K. A broad 1/3 plateau indicative of the up-up-down ($uud$) spin configuration appears for $B||c$ but is absent for $B||ab$, thereby suggesting easy axis anisotropy. At $T=0.4$ K, a jump in magnetization at $\simeq 3/5$ of the saturation magnetization signals a discontinuous transition to a high field phase and we find evidence for a possible tricritical point. Small energy and field scales in the accessible regimes render GdInO$_3$ a prime example to study the phase diagram of a semiclassical frustrated hexagonal lattice in the presence of weak easy axis anisotropy of mainly dipolar origin.

cond-mat.str-el↗

arXiv2021

Magneto-structural coupling in ilmenite-type NiTiO$_3$: a combined diffraction and dilatometry study

We report the ground state magnetic structure and in-field magnetostrictive effects of NiTiO$_3$ studied by means of zero field and in-field single-crystal neutron diffraction, magnetization, and high-resolution dilatometry experiments. Zero-field neutron diffraction on NiTiO$_3$ single crystals reveals an easy-plane antiferromagnet with a multidomain ground state. Upon application of external magnetic fields, neutron diffraction shows the evolution of domains with spins perpendicular to the applied field. The rotation of spins in the multidomain state exhibits pronounced lattice changes in the magnetostriction measurements. We see magnetization and magnetostriction measurements sale with each other in the multidomain state revealing the strong coupling of spins to the lattice.

cond-mat.str-el↗

arXiv2021

Structural and physical properties of trilayer nickelates $R_4$Ni$_3$O$_{10}$ ($R =$ La, Pr and Nd)

We investigate the low temperature structural and physical properties of the trilayer nickelates R4Ni3O10 (R = La, Pr and Nd) using resistivity, thermopower, thermal conductivity, specific heat, high-resolution synchrotron powder X-ray diffraction and thermal expansion experiments. We show that all three compounds crystallize with a monoclinic symmetry, and undergo a metal-to-metal (MMT) transition at 135 K (La), 156 K (Pr) and 160 K (Nd). At MMT, the lattice parameters show distinct anomalies; however, without any lowering of the lattice symmetry. Unambiguous signatures of MMT are also seen in magnetic and thermal measurements, which suggest a strong coupling between the electronic, magnetic and structural degrees of freedom in these nickelates. Analysis of thermal expansion yields hydrostatic pressure dependence of MMT in close agreement with experiments. We show that the 9-fold coordinated Pr ions in the rocksalt (RS) layers have a crystal field (CF) split doublet ground state with possible antiferromagnetic ordering at 5 K. The Pr ions located in the perovskite block (PB) layers with 12-fold coordination, however, exhibit a non-magnetic singlet ground state. The CF ground state of Nd in both RS and PB layers is a Kramers doublet. Heat capacity of R = Nd shows a Schottky-like anomaly near35 K, and an upturn below T = 10 K suggesting the presence of short-range correlations between the Nd moments. However, no signs of long-range ordering could be found down to 2 K despite a sizeable theta_p ~ -40 K. The strongly suppressed magnetic long-range ordering in both R = Pr and Nd suggests the presence of strong magnetic frustration in these compounds. The low-temperature resistivity shows a T^0.5 dependence. No evidence for the heavy fermion behavior could be found in any of the three compounds.

cond-mat.str-el↗

arXiv2021

Revisiting the phase diagram of LaFe$_{1-x}$Co$_x$AsO on single crystals by thermodynamic methods

In this work we revisit the phase diagram of Co-doped LaFeAsO using single crystals and thermodynamic methods. From magnetic susceptibility studies we track the doping evolution of the antiferromagnetic phase, revealing a continuous suppression of $T_\mathrm{N}$ up to 5$\%$ Co doping. In order to study the evolution of the so-called nematic phase, the temperature dependence of the lengths changes along the $a$ and $b$ orthorhombic directions, $ΔL/L_0$, was determined by high-resolution capacitance dilatometry. The results clearly show a gradual reduction of the orthorhombic distortion $δ$ and of $T_\mathrm{S}$ with increasing Co content up to 4.5$\%$, while it is completely suppressed for 7.5$\%$ Co. Bulk superconductivity was found in a small doping region around 6$\%$ Co content, while both $T_\mathrm{c}$ and the superconducting volume fraction rapidly drop in the neighbouring doping regime. Ultimately, no microscopic coexistence between the superconducting and magnetic phases can be assessed within our resolution limit, in sharp contrast with other iron-pnictide families, e.g., electron- and hole-doped BaFe$_2$As$_2$.

cond-mat.supr-con↗

arXiv2020

Challenges in the crystal growth of Li2FeSiO4

The high-pressure optical floating-zone method enables single crystal growth of the Pmnb high-temperature phase of Li2FeSiO4. The influence of growth conditions on crystal quality, phase homogeneity, and impurity formation in Li2FeSiO4 is studied. The use of different starting materials, i.e., either the P121/n1 or the Pmn21 polymorph, as well as optimization of various growth conditions is investigated. Several mm3-sized high-quality single crystals are obtained by the choice of the Pmn21 polymorph as the starting material. A general challenge of Li2FeSiO4 crystal growth is polymorph control during crystallization. While the temperature gradient at the solid-liquid interface seems to have significant impact on stabilizing the Pmnb high-temperature phase, growth velocity has no evident effect.

cond-mat.mtrl-sci↗

arXiv2020

Magnetoelastic coupling and Grüneisen scaling in NdB$_4$

We report high-resolution capacitance dilatometry studies on the uniaxial length changes in a NdB$_4$ single crystal. The evolution of magnetically ordered phases below $T_{\rm N}$= 17.2~K (commensurate antiferromagnetic phase, cAFM), $T_{\rm IT}$= 6.8~K (intermediate incommensurate phase, IT), and $T_{\rm LT}$= 4.8~K (low-temperature phase, LT) is associated with pronounced anomalies in the thermal expansion coefficients. The data imply significant magneto-elastic coupling and evidence of a structural phase transition at $T_{\rm LT}$ . While both cAFM and LT favor structural anisotropy $δ$ between in-plane and out-of-plane length changes, it competes with the IT-type of order, i.e., $δ$ is suppressed in that phase. Notably, finite anisotropy well above $T_{\rm N}$ indicates short-range correlations which are, however, of neither cAFM, IT, nor LT-type. Grüneisen analysis of the ratio of thermal expansion coefficient and specific heat enables the derivation of uniaxial as well as hydrostatic pressure dependencies. While $α$/$c_{\rm p}$ evidences a single dominant energy scale in LT, our data imply precursory fluctuations of a competing phase in IT and cAFM, respectively. Our results suggest the presence of orbital degrees of freedom competing with cAFM and successive evolution of a magnetically and orbitally ordered ground state.

cond-mat.str-el↗

arXiv2020

Filled Carbon Nanotubes as Anode Materials for Lithium-Ion Batteries

Downsizing well-established materials to the nanoscale is a key route to novel functionalities, in particular if different functionalities are merged in hybrid nanomaterials. Hybrid carbon-based hierarchical nanostructures are particularly promising for electrochemical energy storage since they combine benefits of nanosize effects, enhanced electrical conductivity and integrity of bulk materials. We show that endohedral multiwalled carbon nanotubes (CNT) encapsulating high-capacity (here: conversion and alloying) electrode materials have a high potential for use in anode materials for lithium-ion batteries (LIB). There are two essential characteristics of filled CNT relevant for application in electrochemical energy storage: (1) rigid hollow cavities of the CNT provide upper limits for nanoparticles in their inner cavities which are both separated from the fillings of other CNT and protected against degradation. In particular, the CNT shells resist strong volume changes of encapsulates in response to electrochemical cycling, which in conventional conversion and alloying materials hinders application in energy storage devices. (2) Carbon mantles ensure electrical contact to the active material as they are unaffected by potential cracks of the encapsulate and form a stable conductive network in the electrode compound. Our studies confirm that encapsulates are electrochemically active and can achieve full theoretical reversible capacity. The results imply that encapsulating nanostructures inside CNT can provide a route to new high-performance nanocomposite anode materials for LIB.

physics.app-ph↗