arXiv subjects

Rüdiger Klingeler

Publications and source records attributed to Rüdiger Klingeler.

36 records · Page 2Linked to original sources

arXiv2020

Magnetic phase diagram and magneto-elastic coupling of NiTiO3

We report high-resolution dilatometry on high-quality single crystals of NiTiO3 grown by means of the optical floating-zone technique. The anisotropic magnetic phase diagram is constructed from thermal expansion and magnetostriction studies up to B=15T and magnetization studies in static (15T) and pulsed (60T) magnetic fields. Our data allow to quantitatively study magneto-elastic coupling and to determine uniaxial pressure dependencies. While the entropy changes are found to be of magnetic nature, Grüneisen analysis implies only one relevant energy scale in the whole low-temperature regime. Thereby, our data suggest that the observed structural changes due to magneto-elastic coupling and previously reported magnetodielectric coupling[1] are driven by the same $magnetic$ degrees of freedom that lead to long-range magnetic order in NiTiO3, which in turn, establishes a linear magnetodielectric coupling in this compound.

cond-mat.str-el↗

arXiv2019

Anisotropic ionic conductivity of LiMn$_{1-x}$Fe$_x$PO$_4$ ($0\leq x \leq 1$) single crystals

We report AC-impedance studies on a series of high-quality LiMn$_{1-x}$Fe$_x$PO$_4$ single crystals with $0\leq x \leq 1$. Our results confirm quasi-one-dimensional transport in LiFePO$_4$ with fast Li-diffusion along the $b$-axis. The conductivities along the crystallographic $b$-, $c$- and $a$-axis differ by a factor of about 10, respectively. Whereas, the activation energy $E_{\rm A}$ of the effective diffusion process is particularly large for the $b$-axis and smallest for the $a$-axis. Remarkably, the $b$-axis ionic bulk conductivity of LiMn$_{0.5}$Fe$_{0.5}$PO$_4$ is of the same order of magnitude as in undoped LiFePO$_4$, which implies similarly fast Li-transport even upon 50~\% Mn-doping which, owing to the higher redox potential of the Mn$^{3+}$/Mn$^{2+}$-couple, yields enhanced energy density in lithium-ion batteries. The overall results of our impedance studies draw a far more complex picture than it would be expected from a simple one-dimensional ionic conductor. Our results suggest a strong contribution of crystal defects in real materials.

cond-mat.mtrl-sci↗

arXiv2019

High-pressure optical floating-zone growth of Li2FeSiO4 single crystals

We report the growth of mm-sized Pmnb-Li2FeSiO4 single crystals by means of the optical floating-zone method at high argon pressure and describe the conditions required for a stable growth process. The crystal structure is determined and refined by single-crystal X-ray diffraction. The lattice constants amount to a = 6.27837(3) A, b = 10.62901(6) A and c = 5.03099(3) A at 100 K. In addition, we present high-resolution neutron powder diffraction data that suggest that the slight Li-Fe site exchange seems to be intrinsic to this material. High quality of the crystal is confirmed by very sharp anomalies in the static magnetic susceptibility and in the specific heat associated with the onset of long-range antiferromagnetic order at TN = 17.0(5) K and pronounced magnetic anisotropy for the three crystallographic axes. Furthermore, magnetic susceptibility excludes the presence of sizable amounts of magnetic impurity phases.

cond-mat.str-el↗

arXiv2019

Synthesis and Magnetism of a Li$_2$FeSiO$_4$ Single Crystal

A macroscopic single crystal of $γ_{\rm II}$-Li$_2$FeSiO$_4$ has been grown by means of the high-pressure optical floating-zone technique. Static magnetic susceptibility $χ$ implies that the tetrahedrally-coordinated Fe$^{2+}$ ions are in the high-spin, $S=2$, state. While a sharp decrease in $χ$ implies long-range antiferromagnetic order below \tn\ = 17.0(5)~K, the presence of a broad maximum at $T_{\rm m} = 28$~K suggests quasi-low-dimensional magnetism. Applying magnetic fields along the easy magnetic $a$-axis yields additional contributions to the susceptibility $\partial M/\partial B$ and magnetostriction for $B > 7$~T, and an anomaly at $B\approx 14.8$~T.

cond-mat.str-el↗

arXiv2017

Anisotropy governed competition of magnetic phases in the honeycomb quantum magnet Na$_3$Ni$_2$SbO$_6$ studied by dilatometry and high-frequency ESR

Thermodynamic properties as well as low-energy magnon excitations of $S=1$ honeycomb-layered Na$_3$Ni$_2$SbO$_6$ have been investigated by high-resolution dilatometry, static magnetisation, and high-frequency electron spin resonance studies in magnetic fields up to 16 T. At $T_{\rm N}$ = 16.5 K, there is a tricritical point separating two distinct antiferromagnetic phases AF1 and AF2 from the paramagnetic regime. In addition, our data imply short-range antiferromagnetic correlations at least up to $\sim 5\cdot T_{\rm N}$. Well below $T_{\rm N}$, the magnetic field $B_{\rm C1}\approx$ 9.5 T is needed to stabilize AF2 against AF1. The thermal expansion and magnetostriction anomalies at $T_{\rm N}$ and $B_{\rm C1}$ imply significant magnetoelastic coupling, both of which associated with a sign change of $\partial L/\partial B$. The transition at $B_{\rm C1}$ is associated with softening of the antiferromagnetic resonance modes observed in the electron spin resonance spectra. The anisotropy gap $Δ= 360$ GHz implies considerable uniaxial anisotropy. We conclude the crucial role of axial anisotropy favoring the AF1 spin structure over the AF2 one. While the magnetostriction data disprove a simple spin-flop scenario at $B_{\rm C1}$, the nature of a second transition at $B_{\rm C2}\approx$ 13 T remains unclear. Both the sign of the magnetostriction and Grüneisen analysis suggest the short-range correlations at high temperatures to be of AF2-type.

cond-mat.str-el↗

arXiv2017

High-pressure optical floating-zone growth of Li(Mn,Fe)PO$_4$ single crystals

Mm-sized LiMn$_{1-x}$Fe$_x$PO$_4$ single crystals with $0\leq x \leq 1$ were grown by means of the traveling floating-zone technique at elevated Argon pressure of 30~bar. For the various doping levels, the growth process was optimized with respect to the composition-dependant effective light absorption and transparency of the materials. A convex crystal/melt interface, determined by the angle of incident light, was identified to be particularly crucial for a successful growth. The resulting large single crystalline grains are stoichiometric. Structure refinement shows that lattice parameters as well as the atomic positions and bond lengths linearly depend on the Mn:Fe-ratio. Oriented cuboidal samples with several mm$^3$ of volume were used for magnetic studies which imply an antiferromagnetic ground state for all compositions. The Néel-temperature changes from $T_N$ = 32.5(5) K in LiMnPO$_4$ to 49.5(5) K in LiFePO$_4$ while the easy magnetic axis in the ordered phase flips from the crystallographic $a$- to the $b$-axis upon Fe-doping of $x<0.2$.

cond-mat.str-el↗

arXiv2017

Magnetic phase diagram of Eu$_2$CuSi$_3$ derived from thermal expansion and magnetostriction studies

Precise thermal expansion and magnetostriction studies of the intermetallic compound Eu$_2$CuSi$_3$ in the temperature range between 5 and 300 K are presented. A clear sign of magnetic second order phase transition at the ferromagnetic Curie temperature $T_{\rm C}$ = 34 K indicates strong magneto-structural coupling. Uniaxial thermal expansion data show a large anisotropy between the magnetic easy $c$-axis and the hexagonal $ab$-plane, which is associated with a strongly anisotropic magnetic coupling. A spin-reorientation regime as well as a non-uniform energy scale are indicated by Grüneisen analysis of the data at low temperatures. Anomalous contributions to the thermal expansion imply ferromagnetic correlations far above in zero magnetic field. The magnetic phase diagram is constructed, showing the evolution of short- and long-range magnetic order in magnetic fields up to 15 T. The anisotropic magnetic field effect yields anomalous magnetostrictive effects up to about 200 K.

cond-mat.str-el↗

arXiv2017

Preparation of hierarchical C@MoS2@C sandwiched hollow spheres for Lithium ion batteries

Hierarchical C@MoS2@C hollow spheres with the active MoS2 nanosheets being sandwiched by carbon layers have been produced by means of a modified template method. The process applies polydopamine (PDA) layers which inhibit morphology change of the template thereby enforcing the hollow microsphere structure. In addition, PDA forms complexes with the Mo precursor, leading to an in-situ growth of MoS2 on its surface and preventing the nanosheets from agglomeration. It also supplies the carbon that finally sandwiches the 100-150 nm thin MoS2 spheres. The resulting hierarchically structured material provides a stable microstructure where carbon layers strongly linked to MoS2 offer efficient pathways for electron and ion transfer, and concomitantly buffer the volume changes inevitably appearing during the charge-discharge process. Carbon-sandwiched MoS2-based electrodes exhibit high specific capacity of approximately 900 mA h g-1 after 50 cycles at 0.1 C, excellent cycling stability up to 200 cycles, and superior rate performance. The versatile synthesis method reported here offers a general route to design hollow sandwich structures with a variety of different active materials.

cond-mat.mtrl-sci↗

arXiv2017

A facile synthesis method and electrochemical studies of hierarchical structured MoS2/C-nanocomposite

A uniformly coated MoS2/Carbon-nanocomposite with three-dimensional hierarchical architecture based on carbonized bacterial cellulose (CBC) nanofibers is synthesized by a facile one-step hydrothermal method followed by thermal annealing at 700 °C in Ar atmosphere. Strong hydrogen bonds between the Mo precursor and the BC nanofibers are found to be crucial for the in-situ growth of MoS2 nanosheets on the nanofibers during hydrothermal process. The unique structure was maintained and the connection between MoS2 and nanofibers were strengthened in the sintering process, leading to an improved stability of the resulting nanocomposite upon electrochemical cycling. The low-cost and environmentally friendly 3D web-like structure enables binder-free and carbon-free electrodes for lithium-ion batteries, which exhibit high specific discharge capacities up to 1140 mAh/g at the C-rate of 1 C without significant capacity fading for over 50 cycles. The porous conductive hierarchical structure of the composite endows excellent rate performance by avoiding the aggregation of the MoS2 nanosheets and by accommodating mechanical stress which appears upon electrochemical cycling.

cond-mat.mtrl-sci↗

arXiv2016

Tunable Magnetic Properties of Carbon-shielded NiPt Nanoalloys

Spherical NiPt@C nanoalloys encapsulated in carbon shells are synthesized by means of high-pressure chemical vapour deposition. Upon variation of the synthesis parameters, both the alloy core composition and the particle size of the resulting spherical NixPt1-x@C nanocapsules can be controlled. The sublimation temperatures of the Ni- and Pt-precursors are found key to control the alloy composition and diameter. Depending on the synthesis parameters, the diameters of the cores are tuneable in the range of 3 - 15 nm while the carbon coatings for all conditions are 1 - 2 nm. The core particle size decreases linearly upon increasing either of the sublimation temperatures while the Ni and Pt content, respectively, are linearly increasing with the related precursor temperature. Accordingly, the magnetic properties of the nanoalloys, i.e. magnetization, remanent magnetization and critical field, are well controlled by the two sublimation temperatures. As compared to bulk NiPt, our data show an increase of Stoner enhancement by nanoscaling as ferromagnetism appears in the Pt rich NiPt nanoalloy which is not observed for the related bulk alloys. The magneto-crystalline anisotropy constants K are in the range of 0.3 - 4 x 105 J/m3 underlining that NiPt@C is a stable, highly magnetic functional nanomaterial.

cond-mat.mtrl-sci↗

arXiv2016

Static and Dynamic Magnetic Response of Fragmented Haldane-like Spin Chains in Layered Li3Cu2SbO6

The structure and the magnetic properties of layered Li3Cu2SbO6 are investigated by powder X-ray diffraction, static susceptibility, and electron spin resonance studies up to 330 GHz. The XRD data experimentally verify the space group C2/m with halved unit cell volume in contrast to previously reported C2/c. In addition, the data show significant Li/Cu-intersite exchange. Static magnetic susceptibility and ESR measurements show two magnetic contributions, i.e. quasi-free spins at low-temperature and a spin-gapped magnetic subsystem, with about half of the spins being associated to each subsystem. The data suggest ferromagnetic-antiferromagnetic alternating chains with JFM = -285 K and JAFM = 160 K with a significant amount of Li-defects in the chains. The results are discussed in the scenario of fragmented 1D S = 1 AFM chains with a rather high defect concentration of about 17% and associated S = 1/2 edge states of the resulting finite Haldane chains.

cond-mat.str-el↗

arXiv2014

Morphology and agglomeration control of LiMnPO$_4$ micro- and nanocrystals

Microwave-assisted hydrothermal synthesis was used to grow LiMnPO$_4$ micro- and nanocrystals from acetate precursors. By appropriate adjustment of the precursor concentration and the pH-value of the reactant, the product composition and purity along with the crystal size can be manipulated, resulting in particle-dimensions from around 10 mm down to a few 100 nm. Prisms and plates with hexagonal basal face as well as cuboid and rod-like particles were produced. The effects on the crystal morphology as well as on the materials texture and agglomeration tendency are discussed and a comprehensive agglomeration phase diagram is constructed.

cond-mat.mtrl-sci↗

arXiv2013

Experimental evidence for the coupling of Li-motion and structural distortions in LiMnPO$_4$

We present a detailed $^7$Li- and $^{31}$P-NMR study on single crystalline LiMnPO$_4$ in the paramagnetic and antiferromagnetic phase (AFM, $T_N \sim$ 34 K). This allows us to determine the spin directions in the field-induced spin-flop phase. In addition, the anisotropic dipolar hyperfine coupling tensor of the $^7$Li- and $^{31}$P-nuclei is also fully determined by orientation and temperature dependent NMR experiments and compared to the calculated values from crystal structure data. Deviations of the experimental values from the theoretical ones are discussed in terms of Mn disorder which is induced by Li-disorder. In fact, the disorder in the Mn-sublattice is directly revealed by our diffuse x-ray scattering data. The present results provide experimental evidence for the Li-diffusion strongly coupling to structural distortions within the MnPO$_4$ host, which is expected to significantly affect the Li-mobility as well as the performance of batteries based on this material.

cond-mat.mtrl-sci↗

arXiv2013

Growth, characterization, and magnetic properties of a Li(Mn,Ni)PO4 single crystal

Ni-doped LiMn0.95Ni0.05PO4 single crystals have been grown for the first time by the travelling-solvent floating-zone method at low Argon pressure. The grown sample exhibits large single crystalline grains as revealed by means of polarization microscopy and X-ray Laue back scattering. The composition of the crystal was determined by Energy-dispersive X-ray spectroscopy. LiMn0.95Ni0.05PO4 orders in an orthorhombic olivine-like structure as expected and phase purity was confirmed by powder X-ray diffraction. An oriented cuboid with size of 2.4 x 2.5 x 2.7 mm3 along a, b, and c crystalline directions, respectively, was used for anisotropic magnetic measurements.

cond-mat.mtrl-sci↗

arXiv2012

Structural and electronic phase diagrams of CeFeAsO1-xFx and SmFeAsO1-xFx

We have studied the structural and electronic phase diagrams of CeFeAsO1-xFx and SmFeAsO1-xFx by a detailed analysis of muon spin relaxation experiments, synchrotron X-ray diffraction, Mössbauer spectroscopy, electrical resistivity, specific heat, and magnetic susceptibility measurements (Full abstract in the main document).

cond-mat.supr-con↗

arXiv2012

Interplay of Magnetic Exchange Interactions and Ni-S-Ni Bond Angles in Polynuclear Nickel(II) Complexes

The ability of bridging thiophenolate groups to transmit magnetic exchange interactions between paramagnetic Ni(II) ions has been examined. For this purpose, dinuclear and trinuclear Ni(II)-complexes were prepared and fully characterized by IR- and UV-vis spectroscopy, X-ray crystallography, static magnetization measurements and high-field electron spin resonance (HF-ESR). We compare structural and magnetic properties of the two Ni(II)-complexes and discuss the relationships between magnetic interactions and chemical bonding.

cond-mat.str-el↗

arXiv2010

Magnetodielectric and magnetoelastic coupling in TbFe3(BO3)4

We have studied the magnetodielectric and magnetoelastic coupling in TbFe3(BO3)4 single crystals by means of capacitance, magnetostriction and Raman spectroscopy measurements. The data reveal strong magnetic field effects on the dielectric constant and on the macroscopic sample length which are associated to long range magnetic ordering and a field-driven metamagnetic transition. We discuss the coupling of the dielectric, structural, and magnetic order parameters and attribute the origin of the magnetodielectric coupling to phonon mode shifts according to the Lyddane-Sachs-Teller (LST) relation.

cond-mat.mtrl-sci↗

arXiv2009

Synthesis and physical properties of $\rm\bf LaO_{1-x}F_xFeAs$

We have prepared the newly discovered Fe-based superconducting material $\rm LaO_{1-x}F_xFeAs$ ($0\leq x\leq 0.2$) in polycrystalline form and have investigated the samples by means of structural, thermodynamic and transport measurements. Our investigations reveal a non superconducting phase at $0\leq x\lesssim0.04$ which for $x=0$ is characterized by a structural transition towards an orthorhombic distortion at $T_s\approx 160$ K and antiferromagnetic spin order at $T_N\approx138$ K. Both transitions lead to strong anomalies in various transport properties as well as in magnetization and in specific heat. Remarkably, the transition temperatures are only weakly doping dependent up $x\lesssim 0.04$. However, the transitions are abruptly suppressed at $x\geq0.05$ in favour of a superconducting phase with a critical temperature $T_c\gtrsim 20$ K. Upon further increasing the F-doping $T_c$ increases up to a maximum of $T_c=26.8$ K at $x=0.1$ which is followed by a decrease down to $T_c\approx10$ K at $x\geq0.15$.

cond-mat.supr-con↗