arXiv subjects

Mark S. Senn

Publications and source records attributed to Mark S. Senn.

24 records · Page 2Linked to original sources

arXiv2021

Soft mode anisotropy in negative thermal expansion material ReO$_3$

We use a symmetry-motivated approach to analyse neutron pair distribution function data to investigate the mechanism of negative thermal expansion (NTE) in ReO$_3$. This analysis shows that the local structure of ReO$_3$ is dominated by an in-phase octahedral tilting mode and that the octahedral units are far less flexible to scissoring type deformations than the octahedra in the related compound ScF$_3$. These results support the idea that structural flexibility is an important factor in NTE materials, allowing the phonon modes that drive a volume contraction of the lattice to occupy a greater volume in reciprocal space. The lack of flexibility in ReO$_3$ restricts the NTE-driving phonons to a smaller region of reciprocal space, limiting the magnitude and temperature range of NTE. In addition, we investigate the thermal expansion properties of the material at high temperature and do not find the reported second NTE region. Finally, we show that the local fluctuations, even at elevated temperatures, respect the symmetry and order parameter direction of the observed $P4/mbm$ high pressure phase of ReO$_3$. The result indicates that the motions associated with rigid unit modes are highly anisotropic in these systems.

cond-mat.mtrl-sci↗

arXiv2020

From first- to second-order phase transitions in hybrid improper ferroelectrics through entropy stabilisation

Hybrid improper ferroelectrics (HIFs) have been intensely studied over the last few years to gain understanding of their temperature induced phase transitions and ferroelectric switching pathways. Here we report a switching from first- to second-order phase transition pathway for topical HIFs $Ca_{3-x}Sr_xTi_2O_7$, which is driven by the differing entropies of the phases that we identify as being associated with the dynamic motion of octahedral tilts and rotations. A greater understanding of the transition pathways in this class of layered perovskites, which host many physical properties that are coupled to specific symmetries and octahedral rotation and tilt distortions -- such as superconductivity, negative thermal expansion, fast ion conductivity, ferroelectricity, among others -- is a crucial step in creating novel functional materials by design.

cond-mat.mtrl-sci↗

arXiv2018

A Corkscrew Model for Highly Coupled Anisotropic Compliance in Ruddlesden-Popper Oxides with Frozen Octahedral Rotations

A "corkscrew" mechanism, that couples changes in the in-plane rotation angle to strains along the layering axis, has been proposed previously to explain increased compliance in certain Ruddlesden-Popper phases that facilitates uniaxial negative thermal expansion over a wide temperature range. Following the procedure developed to study many simple, auxetic geometries, in the present study we derive the elastic compliances predicted by this corkscrew mechanism assuming that the four shortest metal-anion bonds remain stiff and changes in bond angle are modelled by a harmonic angle potential. We subsequently analyse the limitations of this model and show that it may be extended to An+1BnO3n+1 Ruddlesden-Popper oxide phases of general layer thickness n.

cond-mat.mtrl-sci↗

arXiv2018

A Group-theoretical Approach to Enumerating Magnetoelectric and Multiferroic Couplings in Perovskites

We use a group theoretical approach to enumerate the possible couplings between magnetism and ferroelectric polarisation in the parent $Pm\bar{3}m$ perovskite structure. We show that third order magnetoelectric coupling terms must always involve magnetic ordering at the A and B-site which either transforms both as R-point or both as X-point time odd irreducible representations (irreps). For fourth order couplings we demonstrate that this criterion may be relaxed allowing couplings involving irreps at X, M and R-points which collectively conserve crystal momentum, producing a magnetoelectric effect arising from only B-site magnetic order. In this case, exactly two of the three irreps entering the order parameter must be time-odd irreps and either one or all must be even with respect to inversion symmetry. We are able to show that the time-even irreps in this triad must transform as one of: X$_{1}^{-}$, M$_{3,5}^{-}$ and R$_{5}^{+}$, corresponding to A-site cation order, A-site anti-polar displacements or anion rock-salt ordering. This greatly reduces the search-space for (type-II multiferroic) perovskites. We use similar arguments to demonstrate how weak ferromagnetism may be engineered, and we propose a variety of schemes for coupling this to ferroelectric polarisation. We illustrate our approach with DFT calculations on magnetoelectric couplings, and by considering the literature we suggest which avenues of research are likely to be most promising in the design of novel magnetoelectric materials.

cond-mat.mtrl-sci↗

arXiv2018

Improper Ferroelectric Polarisation in a Perovskite driven by Inter-site Charge Transfer and Ordering

It is of great interest to design and make materials in which ferroelectric polarisation is coupled to other order parameters such as lattice, magnetic and electronic instabilities. Such materials will be invaluable in next-generation data storage devices. Recently, remarkable progress has been made in understanding improper ferroelectric coupling mechanisms that arise from lattice and magnetic instabilities. However, although theoretically predicted, a compact lattice coupling between electronic and ferroelectric (polar) instabilities has yet to be realised. Here we report detailed crystallographic studies of a novel perovskite Hg$^{\textbf{A}}$Mn$^{\textbf{A'}}_{3}$Mn$^{\textbf{B}}_{4}$O$_{12}$ that is found to exhibit a polar ground state on account of such couplings that arise from charge and orbital ordering on both the A' and B-sites, which are themselves driven by a highly unusual Mn$^{A'}$-Mn$^B$ inter-site charge transfer. The inherent coupling of polar, charge, orbital and hence magnetic degrees of freedom, make this a system of great fundamental interest, and demonstrating ferroelectric switching in this and a host of recently reported hybrid improper ferroelectrics remains a substantial challenge.

cond-mat.str-el↗

arXiv2012

Charge order at the frontier between the molecular and solid states in Ba3NaRu2O9

We show that the valence electrons of Ba3NaRu2O9, which has a quasi-molecular structure, completely crystallize below 210 K. Using an extended Hubbard model, we show that the charge ordering instability results from long-range Coulomb interactions. However, orbital ordering, metal-metal bonding and formation of a partial spin gap enforce the magnitude of the charge separation. The striped charge order and frustrated hcp lattice of Ru2O9 dimers lead to competition with a quasi-degenerate charge-melted phase under photo-excitation at low temperature. Our results establish a broad class of simple metal oxides as models for emergent phenomena at the border between the molecular and solid states.

cond-mat.str-el↗