MAGNETIC AND ORBITAL ORDERS COUPLED TO NEGATIVE THERMAL EXPANSION IN MOTT INSULATORS, CA2RU1-XMXO4 (M = 3D TRANSITION METAL ION)

Ca2RuO4 is a structurally-driven Mott insulator with a metal-insulator (MI) transition at TMI = 357K, followed by a well-separated antiferromagnetic order at TN = 110 K. Slightly substituting Ru with a 3d transition metal ion M effectively shifts TMI and induces exotic magnetic behavior below TN. Moreover, M doping for Ru produces negative thermal expansion in Ca2Ru1-xMxO4 (M = Cr, Mn, Fe or Cu); the lattice volume expands on cooling with a total volume expansion ratio reaching as high as 1%. The onset of the negative thermal expansion closely tracks TMI and TN, sharply contrasting classic negative thermal expansion that shows no relevance to electronic properties. In addition, the observed negative thermal expansion occurs near room temperature and extends over a wide temperature interval. These findings underscores new physics driven by a complex interplay between orbital, spin and lattice degrees of freedom. These materials constitute a new class of Negative Thermal Expansion (NTE) materials with novel electronic and magnetic functions

High-energy electronic excitations in Sr2_2IrO4_4 observed by Raman scattering

Spin-orbit interaction in Sr$_2$IrO$_4$ leads to the realization of the $J_{\mathrm{eff}}$ = 1/2 state and also induces an insulating behavior. Using large-shift Raman spectroscopy, we found two high-energy excitations of the d-shell multipletat at 690 meV and 680 meV with $A_{1g}$ and $B_{1g}$ symmetry respectively. As temperature decreases, the $A_{1g}$ and $B_{1g}$ peaks narrow, and the $A_{1g}$ peak shifts to higher energy while the energy of the $B_{1g}$ peak remains the same. When 25$\%$ of Ir is substituted with Rh the $A_{1g}$ peak softens by 10$\%$ but the $B_{1g}$ peak does not. We show that both pseudospin-flip and non-pseudosin-flip dd electronic transitions are Raman active, but only the latter are observed

The magnetic and crystal structures of Sr2IrO4: A neutron diffraction study

We report a single-crystal neutron diffraction study of the layered $\rm Sr_2IrO_4$. This work unambiguously determines the magnetic structure of the system and reveals that the spin orientation rigidly tracks the staggered rotation of the $\rm IrO_6$ octahedra in $\rm Sr_2IrO_4$. The long-range antiferromagnetic order has a canted spin configuration with an ordered moment of 0.208(3) $\mu_B$/Ir site within the basal plane; a detailed examination of the spin canting yields 0.202(3) and 0.049(2) $\mu_B$/site for the a axis and the b axis, respectively. It is intriguing that forbidden nuclear reflections of space group $I4_1/acd$ are also observed in a wide temperature range from 4 K to 600 K, which suggests a reduced crystal structure symmetry. This neutron-scattering work provides a direct, well-refined experimental characterization of the magnetic and crystal structures that are crucial to the understanding of the unconventional magnetism exhibited in this unusual magnetic insulator.Comment: the version appeared in PR

Direct evidence of a zigzag spin chain structure in the honeycomb lattice: A neutron and x-ray diffraction investigation on single crystal Na2IrO3\rm Na_2IrO_3

We have combined single crystal neutron and x-ray diffractions to investigate the magnetic and crystal structures of the honeycomb lattice $\rm Na_2IrO_3$. The system orders magnetically below $18.1(2)$ K with Ir$^{4+}$ ions forming zigzag spin chains within the layered honeycomb network with ordered moment of $\rm 0.22(1) \mu_B$/Ir site. Such a configuration sharply contrasts the N{\'{e}}el or stripe states proposed in the Kitaev-Heisenberg model. The structure refinement reveals that the Ir atoms form nearly ideal 2D honeycomb lattice while the $\rm IrO_6$ octahedra experience a trigonal distortion that is critical to the ground state. The results of this study provide much-needed experimental insights into the magnetic and crystal structure crucial to the understanding of the exotic magnetic order and possible topological characteristics in the 5$d$-electron based honeycomb lattice.Comment: Revised version as that to appear in PR

High-Energy Electronic Excitations in Sr\u3csub\u3e2\u3c/sub\u3eIrO\u3csub\u3e4\u3c/sub\u3e Observed by Raman Scattering

Spin-orbit interaction in Sr2IrO4 leads to the realization of the Jeff=1/2 state and also induces an insulating behavior. Using large-shift Raman spectroscopy, we found two high-energy excitations of the d-shell multiplet at 690 and 680 meV with A1g and B1g symmetry, respectively. As temperature decreases, the A1g and B1g peaks narrow, and the A1g peak shifts to higher energy while the energy of the B1g peak remains the same. When 25% of Ir is substituted with Rh the A1g peak softens by 10% but the B1g peak does not. We show that both pseudospin-flip and non-pseudo-spin-flip d-d electronic transitions are Raman active, but only the latter are observed. Our experiments and analysis place significant new constraints on the possible electronic structure of Sr2IrO4

Magnetic and Crystal Structures of Sr\u3csub\u3e2\u3c/sub\u3eIrO\u3csub\u3e4\u3c/sub\u3e: A Neutron Diffraction Study

We report a single-crystal neutron diffraction study of the layered Sr2IrO4. This work unambiguously determines the magnetic structure of the system and reveals that the spin orientation rigidly tracks the staggered rotation of the IrO6 octahedra in Sr2IrO4. The long-range antiferromagnetic order has a canted spin configuration with an ordered moment of 0.208(3) μB/Ir site within the basal plane; a detailed examination of the spin canting yields 0.202(3) and 0.049(2) μB/site for the a axis and the b axis, respectively. It is intriguing that forbidden nuclear reflections of space group I41/acd are also observed in a wide temperature range from 4 K to 600 K, which suggests a reduced crystal structure symmetry. This neutron-scattering work provides a direct, well-refined experimental characterization of the magnetic and crystal structures that are crucial to the understanding of the unconventional magnetism exhibited in this unusual magnetic insulator

A Low Temperature Nonlinear Optical Rotational Anisotropy Spectrometer for the Determination of Crystallographic and Electronic Symmetries

Nonlinear optical generation from a crystalline material can reveal the symmetries of both its lattice structure and underlying ordered electronic phases and can therefore be exploited as a complementary technique to diffraction based scattering probes. Although this technique has been successfully used to study the lattice and magnetic structures of systems such as semiconductor surfaces, multiferroic crystals, magnetic thin films and multilayers, challenging technical requirements have prevented its application to the plethora of complex electronic phases found in strongly correlated electron systems. These requirements include an ability to probe small bulk single crystals at the micron length scale, a need for sensitivity to the entire nonlinear optical susceptibility tensor, oblique light incidence reflection geometry and incident light frequency tunability among others. These measurements are further complicated by the need for extreme sample environments such as ultra low temperatures, high magnetic fields or high pressures. In this review we present a novel experimental construction using a rotating light scattering plane that meets all the aforementioned requirements. We demonstrate the efficacy of our scheme by making symmetry measurements on a micron scale facet of a small bulk single crystal of Sr$_2$IrO$_4$ using optical second and third harmonic generation.Comment: 8 pages, 5 figure

X-ray Absorption Spectroscopy Study of the Effect of Rh Doping in Sr\u3csub\u3e2\u3c/sub\u3eIrO\u3csub\u3e4\u3c/sub\u3e

We investigate the effect of Rh doping in Sr2IrO4 using X-ray absorption spectroscopy (XAS). We observed appearance of new electron-addition states with increasing Rh concentration (x in Sr2Ir1−xRhxO4) in accordance with the concept of hole doping. The intensity of the hole-induced state is however weak, suggesting weakness of charge transfer (CT) effect and Mott insulating ground states. Also, Ir Jeff = 1/2 upper Hubbard band shifts to lower energy as x increases up to x = 0.23. Combined with optical spectroscopy, these results suggest a hybridisation-related mechanism, in which Rh doping can weaken the (Ir Jeff = 1/2)–(O 2p) orbital hybridisation in the in-planar Rh-O-Ir bond networks