Dynamic Spin Fluctuations in the Frustrated A-site Spinel CuAl2O4
Hwanbeom Cho, R. Nirmala, Jaehong Jeong, Peter J. Baker, Hikaru Takeda, Nobuyoshi Mera, Stephen J. Blundell, Masashi Takigawa, D. T. Adroja, Je-Geun Park
We performed nuclear magnetic resonance (NMR) and muon spin relaxation (μSR) experiments to identify the magnetic ground state of the frustrated quantum A-site spinel, CuAl2O4. Our results verify that the ground state does not exhibit a long-range magnetic ordering, but a glass-like transition manifests at T*=2.3 K. However, the Gaussian shape and the weak longitudinal field dependence of μSR spectra below T* show that the ground state has dynamic spin fluctuations, distinct from those of conventional spin-glasses.
We analyzed the magnetic susceptibilities of several Cr spinels using two recent models for the geometrically frustrated pyrochlore lattice, the Quantum Tetrahedral Mean Field model and a Generalized Constant Coupling model. Both models can describe the experimental data for ACr2 O4 (with A = Zn, Mg, and Cd) satisfactorily, with the former yielding a somewhat better agreement with experiment for A = Zn, Mg. The obtained exchange constants for nearest and next-nearest neighbors are discussed.
Different from other magnetically frustrated spinel systems, GeCu$_{2}$O$_{4}$ is a strongly tetragonal distorted spinel cuprate in which edge-sharing CuO$_{2}$ ribbons are running along alternating directions perpendicular to the $c$-axis. Here, GeCu$_{2}$O$_{4}$ samples of high quality were prepared via high pressure synthesis (at 4 GPa) and the corresponding magnetic and dielectric properties were investigated. For the first time, we observed a ferroelectric polarization emerging at T$_{N}$ $\sim$ 33~K. Although the ferroelectric polarization is weak in GeCu$_{2}$O$_{4}$ ($P$ $\sim$ 0.2$μ$C…
Frustrated magnets can host numerous exotic many-body quantum and topological phenomena. GeNi$_2$O$_4$ is a three dimensional $S=1$ frustrated magnet with an unusual two-stage transition to the two-dimensional antiferromagnetic ground state, while GeCu$_2$O$_4$ is a high-pressure phase with a strongly tetragonally elongated spinel structure and magnetic lattice formed by $S=1/2$ CuO$_2$ linear chains with frustrated exchange interactions and exotic magnetic behavior. Here we report on the first thin-film epitaxial stabilization of these two compounds. Developed growth mode, surface morphology,…
A hexamer-type spin excitation seen in spinel chromates $A$Cr$_2$O$_4$ ($A$ = Mg, Zn, or Cd) is the representative spin-liquid-like state caused by geometrical frustration. To clarify an origin of the state, we comparatively studied spin excitations in an isomorphic material HgCr$_2$O$_4$ by inelastic neutron scattering, and observed a different molecular-type excitation. Numerical analyses performed using model Hamiltonians suggest that these two types of spin excitations originate from a spin-3/2 molecular singlet hidden in a magnetically ordered phase. The difference between the molecular t…
We report on negative thermal expansion (NTE) in the high-field, half-magnetization plateau phase of the frustrated magnetic insulator CdCr2O4. Using dilatometry, we precisely map the phase diagram at fields of up to 30T, and identify a strong NTE associated with the collinear half-magnetization plateau for B > 27T. The resulting phase diagram is compared with a microscopic theory for spin-lattice coupling, and the origin of the NTE is identified as a large negative change in magnetization with temperature, coming from a nearly-localised band of spin excitations in the plateau phase. These res…
We describe powder and single-crystal inelastic neutron scattering experiments on a spinel-type antiferromagnet GeCo$_2$O$_4$, represented by an effective total angular momentum J_eff = 1/2. Several types of non-dispersive short-range magnetic excitations were discovered. The scattering intensity maps in $\vec{Q}$ space are well reproduced by dynamical structure factor analyses using molecular model Hamiltonians. The results of analyses strongly suggest that the molecular excitations below T_N arise from a hidden molecular-singlet ground state, in which ferromagnetic subunits are antiferromagn…
The ground state of the frustrated A-site magnetic spinel CoAl2O4 has been a controversial issue whether it is a collinear antiferromagnetic ordering or a spiral spin - liquid state, as the ratio of the two competing interactions, J2/J1 lies close to the boundary between these two ground states. Here, we address the magnetic ground state in CoAl2O4 with different amount of Co2+/Al3+ site disorder from the study of magnetoelectric effect and Monte Carlo simulations. CoAl2O4 with low site disorder exhibits linear magnetoelectric effect below the magnetic ordering temperature. With increasing dis…
The crossover from localized- to itinerant-electron behavior is associated with many intriguing phenomena in condensed-matter physics. In this paper, we investigate the crossover from localized to itinerant regimes in the spinel system Mn$_{1-x}$Co$_x$V$_2$O$_4$. At low Co doping, orbital order (OO) of the localized electrons on the V3+ ions suppresses magnetic frustration by triggering a tetragonal distortion. With Co doping, electronic itinerancy melts the OO and suppresses the structural phase transition while the reduced spin-lattice coupling produces magnetic frustration. Neutron scatteri…
We have investigated the magnetic-field induced phases of a typical three-dimensional frustrated magnet, CdCr$_2$O$_4$, in magnetic fields of up to 120 T that is generated by the single-turn coil techniques. We focused on magnetic phase transitions in proximity of a saturated magnetization moment. We utilized both the electromagnetic induction method using magnetic pick-up coils and magneto-optical spectroscopies of the $d$-$d$ transitions and the exciton-magnon-phonon transitions to study the magnetic properties subjected to ultra-high magnetic fields. Anomalies were observed in magneto-optic…
The temperature dependence of eigenfrequencies and intensities of the IR active modes has been investigated for the antiferromagnetic chromium spinel compounds CdCr2O4, ZnCr2O4, ZnCr2S4, ZnCr2Se4, and HgCr2S4 by IR spectroscopy for temperatures from 5 K to 300 K. At the transition into the magnetically ordered phases, and driven by spin-phonon coupling, most compounds reveal significant splittings of the phonon modes. This is true for geometrically frustrated CdCr2O4, and ZnCr2O4, for bond frustrated ZnCr2S4 and for ZnCr2Se4, which also is bond frustrated, but dominated by ferromagnetic exchan…
Localized spins and itinerant electrons rarely coexist in geometrically-frustrated spinel lattices. We show that the spinel CoV2O4 stands at the crossover from insulating to itinerant behavior and exhibits a complex interplay between localized spins and itinerant electrons. In contrast to the expected paramagnetism, localized spins supported by enhanced exchange couplings are frustrated by the effects of delocalized electrons. This frustration produces a non-collinear spin state and may be responsible for macroscopic spin-glass behavior. Competing phases can be uncovered by external perturbati…
Mn$_3$O$_4$ is a spin frustrated magnet that adopts a tetragonally distorted spinel structure at ambient conditions and a CaMn$_2$O$_4$-type postspinel structure at high pressure. We conducted both optical measurements and \emph{ab} \emph{initio} calculations, and systematically studied the electronic band structures of both the spinel and postspinel Mn$_3$O$_4$ phases. For both phases, theoretical electronic structures are consistent with the optical absorption spectra, and display characteristic band-splitting of the conduction band. The band gap obtained from the absorption spectra is 1.91(…
Nuclear magnetic resonance (NMR), neutron diffaction (ND), x-ray diffraction, magnetic susceptibility and specific heat measurements on the frustrated A-site spinel CoAl2O4 compound reveal a collinear antiferromagnetic ordering below Tn = 9.8(2) K. A high quality powder sample characterized by x-ray diffraction that indicates a relatively low Co-Al inversion parameter x = 0.057(20) in (Co1-xAlx)[Al2-xCox]O4, shows a broad maximum around 15 K in magnetic susceptibility and a sharp peak at Tn in heat capacity. The average ordered magnetic moment of Co^2+ (S = 3/2) ions at the A-site is estimated…
Ultrasound velocity measurements of the orbitally-frustrated GeCo$_2$O$_4$ reveal unusual elastic instabilities due to the phonon-spin coupling within the antiferromagnetic phase. Shear moduli exhibit anomalies arising from the coupling to short-range ferromagnetic excitations. Diplike anomalies in the magnetic-field dependence of elastic moduli reveal magnetic-field-induced orbital order-order transitions. These results strongly suggest the presence of geometrical orbital frustration which causes novel orbital phenomena within the antiferromagnetic phase.
Using neutron powder diffraction and Monte-Carlo simulations we show that a spin-liquid regime emerges at $all compositions in the diamond-lattice antiferromagnets Co(Al1-xCox)2O4. This spin-liquid regime induced by frustration due to the second-neighbour exchange coupling J2, is gradually superseded by antiferromagnetic collinear long-range order (k=0) at low temperatures. Upon substitution of Al3+ by Co3+ in the octahedral B-site the temperature range occupied by the spin-liquid regime narrows and TN increases. To explain the experimental observations we considered magnetic anisotropy D or t…
We have theoretically studied successive transitions in vanadium spinel oxides with (t_2g)^2 electron configuration. These compounds show a structural transition at ~ 50K and an antiferromagnetic transition at ~ 40K. Since threefold t_2g orbitals of vanadium cations are occupied partially and vanadiums constitute a geometrically-frustrated pyrochlore lattice, the system provides a particular example to investigate the interplay among spin, orbital and lattice degrees of freedom on frustrated lattice. We examine the models with the Jahn-Teller coupling and/or the spin-orbital superexchange inte…
Ultrasound velocity measurements of the orbital-degenerate frustrated spinel MgV$_2$O$_4$ are performed in the high-purity single crystal which exhibits successive structural and antiferromagnetic phase transitions, and in the disorder-introduced single crystal which exhibits spin-glass-like behavior. The measurements reveal that two-types of unusual temperature dependence of the elastic moduli coexist in the cubic paramagnetic phase, which are resolved by magnetic-field and disorder sensitivities: huge Curie-type softening with decreasing temperature, and concave temperature dependence with a…
Pyrochlore lattices, which are found in two important classes of materials -- the $A_2B_2X_7$ pyrochlore family and the $AB_2X_4$ spinel family -- are the quintessential 3-dimensional frustrated lattice architecture. While historically oxides ($X =$~O) have played the starring role in this field, the past decade has seen materials synthesis breakthroughs that have lead to the emergence of fluoride ($X =$~F) and chalcogenide ($X =$~S, Se) pyrochlore lattice materials. In this Research Update, we summarize recent progress in understanding the magnetically frustrated ground states in three famili…
The origin of negative thermal expansion (NTE) in the bond frustrated ZnCr2Se4 has been explored. ESR and FTIR document an ideal paramagnetic state above 100 K, below which ferromagnetic clusters coexist with the paramagnetic state down to TN. By fitting the inverse susceptibility above 100 K using a modified paramagnetic Curie-Weiss law, an exponentially changeable exchange integral J is deduced. In the case of the variable J, magnetic exchange and lattice elastic energy couple with each other effectively via magnetoelastic interaction in the ferromagnetic clusters, where NTE occurs at a loss…
The pronounced enhancement of the effective mass is the primary phenomenon associated with strongly correlated electrons. In the presence of local moments, the large effective mass is thought to arise from Kondo coupling, the interaction between itinerant and localised electrons. However, in d electron systems, the origin is not clear because of the competing Hund's rule coupling. Here we experimentally address the microscopic origin for the heaviest d fermion in a vanadium spinel LiV2O4 having geometrical frustration. Utilising orbital-selective 51V NMR, we elucidate the orbital-dependent loc…
We investigate analytically and numerically the classical ground states of frustrated Heisenberg models on pyrochlore and kagome lattices in zero and finite magnetic fields. Each model has a wide region in the microscopic parameter space, where the propagation vector is turned to a commensurate position equal to a half of the reciprocal lattice vector with a nontrivial star. Within these regions the zero-field ground states for both models correspond to noncoplanar triple-k spin configurations. A universal appearance of the 3-k states can be related to the spin-space dimensionality. A strong m…
muSR experiments on the geometrically frustrated spinel oxide, Li2Mn2O4, show the development of spin correlations over a range of length scales with decreasing temperature. Increased relaxation below 150 K is consistent with the onset of spin correlations. Below 50 K, spin order on a length scale, which is long range for the muSR probe, appears abruptly in temperature, consistent with prior neutron diffraction results. The oscillations in the zero field asymmetry are analyzed using a three frequency model. By locating the muon site this is shown to be consistent with the unexpected 2D q = roo…
The $T$-dependence (2- 400 K) of the electron paramagnetic resonance (EPR), magnetic susceptibility, $χ(T)$, and specific heat, $C_{v}(T)$, of the $normal$ antiferromagnetic (AFM) spinel ZnCr$_{2}$O$_{4}$ and the spin-glass (SG) Zn$_{1-x}$Cd$_{x}$Cr$_{2}$O$_{4}$ ($x=0.05,0.10$) is reported. These systems behave as a strongly frustrated AFM and SG with $% T_{N}$ $ \approx T_{G}\approx 12$ K and -400 K $\gtrsim Θ_{CW}\gtrsim -500$ K. At high-$T$ the EPR intensity follows the $χ(T)$ and the $g$-value is $T$-independent. The linewidth broadens as the temperature is lowered, suggesting the existenc…
Ultrasound and magnetization studies of bond-frustrated ZnCr2S4 spinel are performed in static magnetic fields up to 18 T and in pulsed fields up to 62 T. At temperatures below the antiferromagnetic transition at T_N1 14 K the sound velocity as function of magnetic field reveals a sequence of steps followed by plateaus indicating a succession of crystallographic structures with constant stiffness. At the same time, the magnetization evolves continuously with field up to full magnetic polarization without any plateaus in contrast to geometrically frustrated chromium oxide spinels. The observed …
We re-investigate the magnetically frustrated, {\it diamond-lattice-antiferromagnet} spinels FeAl$_2$O$_4$ and MnAl$_2$O$_4$ using magnetization measurements and diffuse scattering of polarized neutrons. In FeAl$_2$O$_4$, macroscopic measurements evidence a "cusp" in zero field-cooled susceptibility around 13~K. Dynamic magnetic susceptibility and {\it memory effect} experiments provide results that do not conform with a canonical spin-glass scenario in this material. Through polarized neutron scattering studies, absence of long-range magnetic order down to 4~K is confirmed in FeAl$_2$O$_4$. B…
We review the mechanism of spin-lattice coupling in relieving the geometrical frustration of pyrochlore antiferromagnets, in particular spinel oxides. The tetrahedral unit, which is the building block of the pyrochlore lattice, undergoes a spin-driven Jahn-Teller instability when lattice degrees of freedom are coupled to the antiferromagnetism. By restricting our considerations to distortions which preserve the translational symmetries of the lattice, we present a general theory of the collective spin-Jahn-Teller effect in the pyrochlore lattice. One of the predicted lattice distortions breaks…
We report the synthesis and characterization of Li2ZnV3O8, which is a new Zn-doped LiV2O4 system containing only tetravalent vanadium. A Curie-Weiss susceptibility with a Curie-Weiss temperature of <theta>CW ~214 K suggests the presence of strong antiferromagnetic correlations in this system. We have observed a splitting between the zero-field cooled ZFC and field cooled FC susceptibility curves below 6 K. A peak is present in the ZFC curve around 3.5 K suggestive of spin-freezing . Similarly, a broad hump is also seen in the inferred magnetic heat capacity around 9 K. The consequent entropy c…
Using first-principles density functional calculations, we perform a comparative study of two Fe based spinel compounds, FeCr2S4 and FeSc2S4. Though both systems contain an orbitally active A site with an Fe2+ ion, their properties are rather dissimilar. Our study unravels the microscopic origin of their behavior driven by the differences in hybridization of Fe d states with Cr/Sc d states and S p states in the two cases. This leads to important differences in the nature of the magnetic exchanges as well as the nearest versus next nearest neighbor exchange parameter ratios, resulting into sign…
Massachusetts Institute of Technology（麻省理工学院）；Flatiron Institute（平顿研究所）；University of British Columbia（不列颠哥伦比亚大学）；Canadian Light Source, Inc.（加拿大光源公司）；Lund University（隆德大学）；Brookhaven National Laboratory（布鲁克海文国家实验室）；Lawrence Berkeley National Laboratory（劳伦斯伯克利国家实验室）；Max Planck Institute for Solid State Research（马克斯·普朗克固态研究所）；Universität Würzburg（维尔茨堡大学）；Ludwig- Maximilians-Universität München（慕尼黑路德维希-马克西米利安大学）；Munich Center for Quantum Science and Technology (MCQST)（慕尼黑量子科学与技术中心）；Université Paris-Saclay（巴黎萨克雷大学）；CNRS（法国国家科学研究中心）；CEA（法国原子能和替代能源委员会）；Institut de Physique Théorique（理论物理研究所）；University of Tokyo（东京大学）；University of Stuttgart（斯图加特大学）；Collège de France（法兰西公学院）；Université PSL（巴黎文理研究大学）；Ecole Polytechnique（巴黎综合理工学院）；IP Paris（巴黎理工学院）；Université de Genève（日内瓦大学）
Frustration refers to competition between different interactions that cannot be simultaneously satisfied, a familiar feature in many magnetic solids. Strong frustration results in highly degenerate ground states, and a large suppression of ordering by fluctuations. Key challenges in frustrated magnetism are characterizing the fluctuating spin-liquid regime and determining the mechanism of eventual order at lower temperature. Here, we study a model of a diamond lattice antiferromagnet appropriate for numerous spinel materials. With sufficiently strong frustration a massive ground state degenera…
By studying the dielectric properties of the geometrically frustrated spinel CdV2O4, we observe ferroelectricity developing at the transition into the collinear antiferromagnetic ground state. In this multiferroic spinel, ferroelectricity is driven by local magnetostriction and not by the more common scenario of spiral magnetism. The experimental findings are corroborated by ab-initio calculations of the electric polarization and the underlying spin and orbital order. The results point towards a charge rearrangement due to dimerization, where electronic correlations and the proximity to the in…
The inversion and volume effects on magnetism in a spinel-type magnetically frustrated compound, CoAl2O4, and its gallium-substituted system, CoAl2-xGaxO4, were investigated. Magnetically frustrated Co2+ with spin S = 3/2 on the tetrahedral site formed a diamond lattice in CoAl2O4 located in the vicinity of the magnetic phase boundary between Neel and spin-spiral states. In the Ga-substituted system, the number of Co ions, the so-called inversion h dominating the octahedral site, increased with increasing x. From comprehensive crystallographic, magnetic, and thermal measurements, increments of…
Insulating spinel materials, with the chemical formula $AB_2X_4$, behave as diamond lattice antiferromagnets when only the A-site atom is magnetic. Many exhibit classic signatures of frustration, induced not geometrically but by competing first and second neighbor exchange interactions. In this paper, we further develop a theory of the magnetism of these materials, focusing on the physics observable within the ordered state. We derive a phenomenological Landau theory that predicts the orientation of the spins within incommensurate spiral ordered states. It also describes how the spins reorient…
In frustrated spinel antiferromagnets, dilution with non-magnetic ions can be a powerful strategy for probing unconventional spin states or uncovering interesting phenomena. Here, we present X-ray, neutron scattering and thermodynamic studies of the effects of magnetic dilution of the tetragonally-distorted A-site spinel antiferromagnet, CuRh$_2$O$_4$, with non-magnetic Zn$^{2+}$ ions. Our data confirm the helical spin order recently identified at low-temperatures in this material, and further demonstrate a systematic suppression of the associated Néel temperature with increasing site dilution…
Using elastic and inelastic neutron scattering we show that a cubic spinel, CdCr$_2$O$_4$, undergoes an elongation along the c-axis ($c > a = b$) at its spin-Peierls-like phase transition at $T_N$ = 7.8 K. The Néel phase ($T < T_N$) has an incommesurate spin structure with a characteristic wave vector \textbf{Q}$_M$ = (0,$δ$,1) with $δ\sim$ 0.09 and with spins lying on the $ac$-plane. This is in stark contrast to another well-known Cr-based spinel, ZnCr$_2$O$_4$, that undergoes a c-axis contraction and a commensurate spin order. The magnetic excitations of the incommensurate Néel state has a w…
We report the magnetic properties of $A$-site spinel compound MnSc$_2$Se$_4$. The macroscopic magnetic measurements uncovers successive magnetic transitions at $T_{\rm{N1}}$= 2.04 K, followed by two further transitions at $T_{\rm{N2}}$=1.8 K and $T_{\rm{N3}}$=1.6 K. Neutron powder diffraction reveals that both, $T_{\rm{N2}} < T < T_{\rm{N1}}$ and $T <T_{\rm{N3}}$, orders are associated with the propagation vector $k$=(3/4 3/4 0), while the magnetic structures are collinear amplitude modulated and helical, respectively. Using neutron powder spectroscopy we demonstrated the effect of substitutio…
This review summarizes more than 100 years of research on spinel compounds, mainly focusing on the progress in understanding their magnetic, electronic, and polar properties during the last two decades. Many spinel compounds are magnetic insulators or semiconductors; however, a number of spinel-type metals exists including superconductors and some rare examples of d-derived heavy-fermion compounds. In the early days, they gained importance as ferrimagnetic or even ferromagnetic insulators with relatively high saturation magnetization and high ordering temperatures, with magnetite being the fir…
In this study, we have performed the magnetocaloric effect and the specific heat measurements of chromium spinel oxide HgCr$_2$O$_4$, wherein the magnetic Cr$^{3+}$ ions form a highly frustrated pyrochlore lattice with significant spin-lattice coupling. In addition to the known magnetic-field-induced phases, our thermodynamic measurements detect a novel quantum phase just before the saturation of the magnetization, which has not been expected from the classical theories of the pyrochlore lattice antiferromagnet with spin-lattice coupling. Based on recent theoretical model calculation, we discu…
The inconsistency about the degree of geometrical frustration has been a long issue in AV$_{2}$O$_{4}$ (A $\equiv$ Zn, Cd and Mg) compounds, which arises from the two experimental results: (i) frustration indices and (ii) magnetic moments. In the present study, we try to understand such inconsistency by using {\it ab initio} electronic structure calculations. The orbital degrees of freedom are found to play an important role in understanding the geometrically frustrated magnetic behaviour of these compounds. The inclusion of the orbital and spin angular momenta for calculating the frustration …
We have characterized the magnetic and structural properties of the CdLn2Se4 (Ln = Dy, Ho), and CdLn2S4 (Ln = Ho, Er, Tm, Yb) spinels. We observe all compounds to be normal spinels, possessing a geometrically frustrated sublattice of lanthanide atoms with no observable structural disorder. Fits to the high temperature magnetic susceptibilities indicate these materials to have effective antiferromagnetic interactions, with Curie-Weiss temperatures theta ~ -10 K, except CdYb2S4 for which theta ~ -40 K. The absence of magnetic long range order or glassiness above T = 1.8 K strongly suggests that …
In an attempt to explain inelastic neutron scattering data for LiV2O4 the dynamical spin susceptibility χ(Q,w) at zero temperature is calculated. Starting point is a weak coupling approach based on the LDA bandstructure for that material. It is supplemented by a RPA treatment of local on-site interactions and contains an adjustable parameter. Due to the geometrically frustrated lattice structure the magnetic response is strongly enhanced in the vicinity of a nearly spherical surface in Q-space. We compare these results with recent low-temperature neutron scattering data. The measured spin rela…
We report detailed dc and ac magnetic susceptibilities, specific heat, and thermal conductivity measurements on the frustrated magnet ZnCr$_2$Se$_4$. At low temperatures, with increasing magnetic field, this spinel material goes through a series of spin state transitions from the helix spin state to the spiral spin state and then to the fully polarized state. Our results indicate a direct quantum phase transition from the spiral spin state to the fully polarized state. As the system approaches the quantum criticality, we find strong quantum fluctuations of the spins with the behaviors such as …
We present a neutron diffraction study of FeV2O4, which is rare in exhibiting spin and orbital degrees of freedom on both cation sublattices of the spinel structure. Our data confirm the existence of three structural phase transitions previously identified with x-ray powder diffraction, and reveal that the lower two transitions are associated with sequential collinear and canted ferrimagnetic transitions involving both cation sites. Through consideration of local crystal and spin symmetry, we further conclude that Fe2+ cations are ferro-orbitally ordered below 135K and V3+ orbitals order at 60…
We present our theoretical and numerical results on thermodynamic properties and the microscopic mechanism of two successive transitions in vanadium spinel oxides $A$V$_2$O$_4$ ($A$=Zn, Mg, or Cd) obtained by Monte Carlo calculations of an effective spin-orbital-lattice model in the strong correlation limit. Geometrical frustration in the pyrochlore lattice structure of V cations suppresses development of spin and orbital correlations, however, we find that the model exhibits two transitions at low temperatures. First, a discontinuous transition occurs with an orbital ordering assisted by the …
Our polycrystalline sample study on the Yb-based chalcogenide spinels $A$Yb$_2$$X_4$ ($A =$ Cd, Mg, $X =$ S, Se) has revealed frustrated magnetism due to the antiferromagnetically coupled Heisenberg spin on the pyrochlore lattice. Our crystal electric field analysis indicates the Yb ground state has nearly Heisenberg spins with a strong quantum character of the ground doublet. All the materials exhibit an antiferromagnetic order at 1.4-1.8 K, much lower temperature than the antiferromagnetic exchange coupling scale of $\sim 10$ K. The magnetic specific heat $C_{\rm M}$ shows a $T^{3}$ dependen…
We present a unique study of the frustrated spinel MgV2O4 which possesses highly coupled spin, lattice and orbital degrees of freedom. Using large single-crystal and powder samples, we find a distortion from spinel at room temperature (space group F-43m) which allows for a greater trigonal distortion of the VO6 octahedra and a low temperature space group (I-4m2) that maintains the mirror plane symmetry. The magnetic structure that develops below 42 K consists of antiferromagnetic chains with a strongly reduced moment while inelastic neutron scattering reveals one-dimensional behavior and a sin…
We propose a scenario for the two phase transitions in $A$V$_2$O$_4$ ($A$=Zn, Mg, Cd), based on an effective spin-orbital model on the pyrochlore lattice. At high temperatures, spin correlations are strongly frustrated due to the lattice structure, and the transition at $\sim$50 [K] is an orbital order, supported by Jahn-Teller lattice distortion. This orbital order introduces spatial modulation of spin exchange couplings depending on the bond direction. This partially releases the frustration, and leads to a spin order at $\sim$40 [K]. We also study the stable spin configuration by taking acc…
Magnetic systems are fertile ground for the emergence of exotic states when the magnetic interactions cannot be satisfied simultaneously due to the topology of the lattice - a situation known as geometrical frustration. Spinels, AB2O4, can realize the most highly frustrated network of corner-sharing tetrahedra. Several novel states have been discovered in spinels, such as composite spin clusters and novel charge-ordered states. Here we use neutron and synchrotron X-ray scattering to characterize the fractional magnetization state of HgCr2O4 under an external magnetic field, H. When the field i…
The crystal and magnetic structures of stoichiometric ZnCr2Se4 have been investigated using synchrotron X-ray and neutron powder diffraction, muon spin relaxation (muSR) and inelastic neutron scattering. Synchrotron X-ray diffraction shows a spin-lattice distortion from the cubic spinel to a tetragonal I41/amd lattice below TN = 21 K, where powder neutron diffraction confirms the formation of a helical magnetic structure with magnetic moment of 3.04(3) μB at 1.5 K; close to that expected for high-spin Cr3+. MuSR measurements show prominent local spin correlations that are established at temper…
Magneto-optical effects have been investigated over the infrared{visible spectral range in ACr2O4 (A = Fe, Co) spinel oxides with non-collinear spin orders in their ground states. We found large magneto-optical Kerr rotation and ellipticity at the on-site d-d transitions of the A2+ ions located within the charge gap. The magneto-optical Kerr rotation of 12 deg observed in CoCr2O4 is unprecedentedly large among magnetic semiconductors and points towards the uniqueness of tetrahedrally coordinated Co2+ ions in generating a strong magneto-optical response. Criteria of strong magneto-optical effec…
GeCu$_2$O$_4$ is a high-pressure recoverable cuprate with a strongly tetragonally elongated spinel structure and magnetic lattice formed by $S=1/2$ CuO$_2$ linear chains with frustrated exchange interactions and exotic magnetic behavior. Here we report on the first stabilization of epitaxial thin films of GeCu$_2$O$_4$ on (001)-oriented MgAl$_2$O$_4$ substrate. Developed growth mode, surface morphology, crystal structure and copper valence state were characterized by \emph{in-situ} reflection high-energy electron diffraction, atomic force microscopy, X-ray reflectivity, X-ray diffraction and X…
We present our theoretical results on the electronic state in vanadium spinel oxide AlV$_2$O$_4$. The material is a mixed-valent system with the average valence V$^{2.5+}$, and V cations constitute a frustrated pyrochlore structure. It shows a structural transition at $\sim 700$ K, leading to the formation of seven V-sites clusters -- heptamers. We study the electronic state of the heptamer by explicitly taking account of orbital degree of freedom as well as electron correlations. We show that the ground state of the heptamer for realistic parameters becomes spin-singlet because of strong $σ$-…
Single-crystalline thin film of an iridium dioxide polymorph Ir2O4 has been fabricated by the pulsed laser deposition of LixIr2O4 precursor and the subsequent Li-deintercalation using soft chemistry. Ir2O4 crystallizes in a spinel (AB2O4) without A cations in the tetrahedral site, which is isostructural to lambda-MnO2. Ir ions form a pyrochlore sublattice, which is known to give rise to a strong geometrical frustration. This Ir spinel was found to be a narrow gap insulator, in remarkable contrast to the metallic ground state of rutile-type IrO2. We argue that an interplay of strong spin-orbit …
Above 40K, the magnetic susceptibility of the heavy Fermion spinel LiV2O4 has many features in common with those of geometrically frustrated magnetic insulators, while its room temperature resistivity comfortably exceeds the Mott-Regel limit. This suggests that local magnetic moments, and the underlying geometry of the pyrochlore lattice, play an important role in determining its magnetic properties. We extend a recently introduced tetragonal mean field theory for insulating pyrochlore antiferromagnets to the case where individual tetrahedra contain spins of different lengths, and use this as …
We report single-crystal neutron diffraction studies on a spinel antiferromagnet GeCo$_2$O$_4$, which exhibits magnetic order with a trigonal propagation vector and tetragonal lattice expansion ($c/a\simeq1.001$) below $T_{\rm N}=21$ K. For this inconsistency between spin and lattice in symmetry, magnetic Bragg reflections with a tetragonal propagation vector were discovered below $T_{\rm N}$. We discuss spin and orbital states of Co$^{2+}$ ion underlying the new magnetic component.
The spinel MnV_2O_4 is a two-sublattice ferrimagnet, with site A occupied by the Mn^{2+} ion and site B by the V^{3+} ion. The magnon of the system, the transversal fluctuation of the total magnetization, is a complicated mixture of the sublattice A and B transversal magnetic fluctuations. As a result, the magnons' fluctuations suppress in a different way the manganese and vanadium magnetic orders and one obtains two phases. At low temperature (0,T^*) the magnetic orders of the Mn and V ions contribute to the magnetization of the system, while at the high temperature (T^*,T_N), the vanadium ma…
