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Through powder x-ray diffraction we have investigated the structural behavior of SmVO3, in which orbital and magnetic degrees of freedom are believed to be closely coupled to the crystal lattice. We have found, contrary to previous reports, that SmVO3 exists in a single, monoclinic, phase below 200 K. The associated crystallographic distortion is then stabilized through the magnetostriction that occurs below 134 K. The crystal structure has been refined using synchrotron x-ray powder diffraction data measured throughout the structural phase diagram, showing a substantial Jahn-Teller distortion of the VO6 octahedra in the monoclinic phase, compatible with the expected G-type orbital order. Changes in the vanadium ion crystal field due to the structural and magnetic transitions have then been probed by resonant x-ray diffraction., Comment: Published in Physical Review B

Orbitally ordered states evolving coincidentally with structural distortions and magnetic ordering provide a novel route to controlling electronic and magnetic properties of materials through external fields. We report an unprecedented magneto-orbital helix in CaMn7O12, found to give rise to the largest magnetically induced ferroelectric polarisation measured to date. Characterisation of the structural modulation using x-ray diffraction, and analysis of magnetic exchange shows that orbital order is crucial in stabilising a chiral magnetic structure, thus allowing for electric polarisation. Additionally, the presence of a global structural rotation enables the coupling between this polarisation and magnetic helicity required for multiferrocitiy. These novel principles open up the possibility of discovering new high-temperature multiferroics., Comment: Submitted to Nature Communications

Resonant magnetic x-ray scattering has been used to investigate the magnetic structure of the magnetoelectric multiferroic DyMn2O5. We have studied the magnetic structure in the ferroelectric phase of this material, which displays the strongest ferroelectric polarisation and magnetodielectric effect of the RMn2O5 (where R is a rare earth ion, Y or Bi) family. The magnetic structure observed is similar to that of the other members of the series, but differs in the direction of the ordered moments. In DyMn2O5 both the Dy and Mn moments lie close to the b-axis, whereas in other RMn2O5 they lie close to the a-axis., Comment: 8 pages, 8 figures

The coupling of magnetic chiralities to the ferroelectric polarisation in multiferroic RbFe(MoO$_4$)$_2$ is investigated by neutron spherical polarimetry. Because of the axiality of the crystal structure below $T_\textrm{c}$ = 190 K, helicity and triangular chirality are symmetric-exchange coupled, explaining the onset of the ferroelectricity in this proper-screw magnetic structure - a mechanism that can be generalised to other systems with "ferroaxial" distortions in the crystal structure. With an applied electric field we demonstrate control of the chiralities in both structural domains simultaneously., Comment: 5 pages, 4 figures

We have studied the high temperature multiferroic cupric oxide using polarized neutron diffraction as a function of temperature and applied electric field. We find that the chiral domain population can be varied using an external electric field applied along the b axis. Using representation analysis we derive the incommensurate magnetic structure in the multiferroic phase. The origin of the magnetoelectric coupling is consistent with models based on the inverse Dzyaloshinskii-Moriya interaction, but is different from the simple cycloidal mechanism., Comment: 7 pages, 3 figures

In rhombohedral CaMn7O12, an improper ferroelectric polarization of magnitude 2870 {\mu}C m-2 is induced by an incommensurate helical magnetic structure that evolves below TN1 = 90 K. The electric polarization was found to be constrained to the high symmetry three-fold rotation axis of the crystal structure, perpendicular to the in-plane rotation of the magnetic moments. The multiferroicity is explained by the ferroaxial coupling mechanism, which in CaMn7O12 gives rise to the largest magnetically induced, electric polarization measured to date., Comment: 10 pages, 4 figures, and 1 table. Submitted to Physical Review Letters

In multiferroic TbMn$_2$O$_5$, the behavior of the terbium ions forms a crucial part of the magneto-electric coupling. The result is a magnetically induced reversal of the electric polarization at 2 T. In this article we present the first direct measurement of the terbium magnetic structure under applied magnetic fields. Contrary to the current interpretation of the magnetic properties of \tmo, we show that upon the electric polarization reversal the terbium sub-lattice adopts a canted antiferromagnetic structure with a large component of magnetic moment parallel to the \textit{a}-axis. Furthermore, we provide evidence for a coupling between the manganese 3d magnetic structure and the terbium $4f$ magnetism, which is of great significance in the elusive magneto-electric mechanisms at play., Comment: 4 pages, 3 figures

Two members of the iso-structural R$_2$CoGa$_8$ inter-metallic series, Er$_2$CoGa$_8$ and Tm$_2$CoGa$_8$, have been studied by powder neutron diffraction. Antiferromagnetic ordering of the rare-earth sublattices was confirmed to occur at 3.0 K and 2.0 K, respectively. Furthermore, determination of the critical exponent showed Er$_2$CoGa$_8$ to adopt a 3D universality class. In spite of a common magnetic easy axis and similar structural characteristics, the antiferromagnetic structures were found to be different for the erbium and thulium based compounds. The corresponding magnetic space groups were determined to be $P_{2a}mmm'$ and $P_Cmmm$. The difference in magnetic structures is discussed based on crystal electric field effects that are known to be prevalent in such materials., Comment: 6 pages, 4 figures, 3 tables

By combining bulk properties, neutron diffraction and non-resonant X-ray diffraction measurements, we demonstrate that the new multiferroic Cu$_3$Nb$_2$O$_8$ becomes polar simultaneously with the appearance of generalised helicoidal magnetic ordering. The electrical polarization is oriented perpendicularly to the common plane of rotation of the spins --- an observation that cannot be reconciled with the "conventional" theory developed for cycloidal multiferroics. Our results are consistent with coupling between a macroscopic structural rotation, which is allowed in the paramagnetic group, and magnetically-induced structural chirality., Comment: This article is in print with Physical Review Letters

We report the direct measurement of antiferromagnetic spin polarization at the oxygen sites in the multiferroic TbMn2O5, through resonant soft x-ray magnetic scattering. This supports recent theoretical models suggesting that the oxygen spin polarization is key to the magnetoelectric coupling mechanism. The spin polarization is observed through a resonantly enhanced diffraction signal at the oxygen K edge at the commensurate antiferromagnetic wavevector. Using the fdmnes code we have accurately reproduced the experimental data. We have established that the resonance arises through the spin polarization on the oxygen sites hybridized with the square based pyramid Mn3+ ions. Furthermore we have discovered that the position of the Mn3+ ion directly influences the oxygen spin polarization., Comment: 5 pages, 4 figures

We have employed resonant x-ray magnetic scattering to specifically probe the magnetic order of the rare-earth ions in multiferroic $\mathrm{TbMn_2O_5}$. Two energy resonances were observed, one originated from the E1-E1 dipolar transition and the other from the E2-E2 quadrupolar transition. These resonances directly probe the valence 5d band and the partially occupied 4f band, respectively. First, full polarization analysis, which is a measurement of the scattered polarization as a function of incident polarization, confirmed a spin polarization of the terbium valence states (probed by the E1-E1 transition) by the $\mathrm{Mn^{4+}}$ spin density in the commensurate phase. Second, full polarization analysis data were collected in the low-temperature incommensurate and commensurate phases when tuned to the E2-E2 resonance. By employing a least-squares fitting procedure, the spin orientations of the terbium ion sublattice were refined., Comment: 10 pages, 11 figures, accepted in Physical Review B

A fully integrated, miniaturized analysis system for ions based on a centrifugal microfluidics platform and ion-selective optode membranes is described. The microfluidic architecture is composed of channels, five solution reservoirs, a measuring chamber, and a waste reservoir manufactured onto a disk-shaped substrate of poly(methyl methacrylate). Ion-selective optode membranes, composed of plasticized poly(vinyl chloride) impregnated with an ionophore, a proton chromoionophore, and a lipophilic anionic additive, were cast, with a spin-on device, onto a support layer and then immobilized on the disk. Fluid propulsion is achieved by the centrifugal force that results from spinning the disk, while a system of valves is built onto the disk to control flow. These valves operate based on fluid properties and fluid/substrate interactions and are controlled by the angular frequency of rotation. With this system, we have been able to deliver calibrant solutions, washing buffers, or "test" solutions to the measuring chamber where the optode membrane is located. An analysis system based on a potassium-selective optode has been characterized. Results indicate that optodes immobilized on the platform demonstrate theoretical responses in an absorbance mode of measurement. Samples of unknown concentration can be quantified to within 3% error by fitting the response function for a given optode membrane using an acid (for measuring the signal for a fully protonated chromoionophore), a base (for fully deprotonated chromoionophore), and two standard solutions. Further, the ability to measure ion concentrations by employing one standard solution in conjunction with acid and base and with two standards alone were studied to delineate whether the current architecture could be simplified. Finally, the efficacy of incorporating washing steps into the calibration protocol was investigated.