There are two methods of preparation of ferrimagnetic spinel. If, during the preparation, an external magnetic field as high as 300 Oë is applied upon cooling the material is named field-cooled (FC). If the applied field is about 1Oë the material is zero-field cooled (ZFC). To explore the magnetic and thermodynamic properties of these materials we consider two-sublattice spin system, defined on the bcc lattice, with spin-$s^A$ operators $\bf{S_{i}^A}$ at the sublattice $A$ site and spin-$s^B$ operators $\bf{S_{i}^B}$ at the sublattice $B$ site, where $s^A>s^B$. The subtle point is the exchange between sublattice A and B spins, which is antiferromanetic. Applying magnetic field along the sublattice A magnetization, during preparation of the material, one compensates the Zeeman splitting, due to the exchange, of sublattice B electrons. This effectively leads to a decrease of the $s^B$ spin. We consider a model with $s^B$ varying parameter which accounts for the applied, during the preparation, magnetic field.
It is shown that the model agrees well with the observed magnetization-temperature curves of zero field cooled (ZFC) and non-zero field cooled (FC) spinel ferrimagnetic spinel and explains the anomalous temperature dependence of the specific heat.
In antiferromagnets, the interplay of spin frustration and spin-lattice coupling has been extensively studied as the source of complex spin patterns and exotic magnetism. Here, we demonstrate that, although neglected in the past, the spin-lattice coupling is essential to ferrimagnetic spinels as well. We performed ultrahigh-field magnetization measurements up to 110 T on a Yafet-Kittel ferrimagnetic spinel, MnCr$_2$S$_4$, which was complemented by measurements of magnetostriction and sound velocities up to 60 T. Classical Monte Carlo calculations were performed to identify the complex high-fie…
A two-sublattice spin-fermion model of ferrimagnetic spinel, with spin-$1/2$ itinerant electrons at the sublattice $A$ site and spin-$s$ localized electrons at the sublattice $B$ site is considered. The exchange between itinerant and localized electrons is antiferromanetic. As a result the external magnetic field, applied along the magnetization of the localized electrons, compensates the Zeeman splitting due to the spin-fermion exchange and magnon-fermion interaction induces spin anti-parallel p-wave superconductivity which coexists with magnetism. We have obtained five characteristic values …
We assess the potential of the ferrimagnetic spinel ferrites CoFe2O4 and NiFe2O4 to act as spin filtering barriers in magnetic tunnel junctions. Our study is based on the electronic structure calculated by means of first-principles density functional theory within different approximations for the exchange correlation energy. We show that, in agreement with previous calculations, the densities of states suggest a lower tunneling barrier for minority spin electrons, and thus a negative spin-filter effect. However, a more detailed analysis based on the complex band-structure reveals that both sig…
We demonstrate that the onset of complex spin orders in ACr$_2$O$_4$ spinels with magnetic A$=$Co, Fe and Cu ions lowers the lattice symmetry. This is clearly indicated by the emergence of anisotropic lattice dynamics -- as evidenced by the pronounced phonon splittings -- even when experiments probing static distortions fail. We show that the crystal symmetry in the magnetic phase is reduced from tetragonal to orthorhombic for FeCr$_2$O$_4$ and CuCr$_2$O$_4$ with Jahn-Teller active A-site ions. The conical spin structure in FeCr$_2$O$_4$ is also manifested in the phonon frequencies. In contras…
We investigate the magnetic properties of the isostructural spinel-spinel interface of NiMn2O4(NMO)-Fe3O4. Although the magnetic transition temperature of the NMO film is preserved, both bulk and interface sensitive measurements demonstrate that the interface exhibits strong interfacial magnetic coupling up to room temperature. While NMO thin films have a ferrimagnetic transition temperature of 60K, both NiFe2O4 and MnFe2O4 are ferrimagnetic at room temperature. Our experimental results suggest that these magnetic properties arise from a thin interdiffused region of (Fe,Mn,Ni)3O4 at the interf…
Neutron inelastic scattering and diffraction techniques have been used to study the MnV2O4 spinel system. Our measurements show the existence of two transitions to long-range ordered ferrimagnetic states; the first collinear and the second noncollinear. The lower temperature transition, characterized by development of antiferromagnetic components in the basal plane, is accompanied by a tetragonal distortion and the appearance of a gap in the magnetic excitation spectrum. The low-temperature noncollinear magnetic structure has been definitively resolved. Taken together, the crystal and magnetic…
We determined the magnetic structure of CuCr$_2$O$_4$ using neutron diffraction and irreducible representation analysis. The measurements identified a new phase between 155 K and 125 K as nearly collinear magnetic ordering in the Cr pyrochlore lattice. Below 125 K, a Cu-Cr ferrimagnetic component develops the noncollinear order. Along with the simultaneously obtained O positions and the quantum effect of spin-orbit coupling, the magnetic structure is understood to involve spin-orbit ordering, accompanied by an appreciably deformed orbital of presumably spin-only Cu and Cr.
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…
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…
Mn1-xZnxCr2O4 (0<x<1) single crystals have been grown by the chemical vapor transport (CVT) method. The crystallographic, magnetic, and thermal transport properties of the single crystals were investigated by the room-temperature X-ray diffraction, magnetization M(T) and specific heat CP(T) measurements. Mn1-xZnxCr2O4 crystals show a cubic structure, the lattice constant a decreases with the increasing content x of the doped Zn2+ ions and follows the Vegard law. Based on the magnetization and heat capacity measurements, the magnetic evolution of Mn1-xZnxCr2O4 crystals has been discussed. For 0…
Using density-functional theory calculations and experimental investigations on structural, magnetic and dielectric properties, we have elucidated a unique tetragonal ground state for MnTi2O4, a Ti^{3+} (3d^1)-ion containing spinel-oxide. With lowering of temperature around 164 K, cubic MnTi2O4 undergoes a structural transition into a polar P4_1 tetragonal structure and at further lower temperatures, around 45 K, the system undergoes a paramagnetic to ferrimagnetic transition. Magnetic superexchange interactions involving Mn and Ti spins and minimization of strain energy associated with co-ope…
We perform ultrasound velocity measurements on a single crystal of nearly-metallic spinel Co$_{1.21}$V$_{1.79}$O$_4$ which exhibits a ferrimagnetic phase transition at $T_C \sim$ 165 K. The experiments reveal a variety of elastic anomalies in not only the paramagnetic phase above $T_C$ but also the ferrimagnetic phase below $T_C$, which should be driven by the nearly-itinerant character of the orbitally-degenerate V 3$d$ electrons. In the paramagnetic phase above $T_C$, the elastic moduli exhibit elastic-mode-dependent unusual temperature variations, suggesting the existence of a dynamic spin-…
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…
Spinel oxides are an ideal setting to explore the interplay between configurational entropy, site selectivity, and magnetism in high entropy oxides. In this work we characterize the magnetic properties of the spinel (Cr,Mn,Fe,Co,Ni)$_3$O$_4$ and study the evolution of its magnetism as a function of non-magnetic gallium substitution. Across the range of compositions studied here, from 0% to 40% Ga, magnetic susceptibility and powder neutron diffraction measurements show that ferrimagnetic order is robust in the spinel HEO. However, we also find that the ferrimagnetic order is highly tunable, wi…
Multiferroicity in the Presence of Exchange Bias: The Case of Spinel CoMn2O4
School of Physical Science, Jawaharlal Nehru University（贾瓦哈拉尔·尼赫鲁大学物理科学学院）；Special Centre for Nanoscience, Jawaharlal Nehru University（贾瓦哈拉尔·尼赫鲁大学纳米科学特别中心）
We report on the epitaxial film growth and characterization of CoV$_2$O$_4$, a near-itinerant spinel vanadate, grown on (001) SrTiO$_3$. The symmetry lowering of the unit cell from cubic in the bulk to orthorhombic in the films results in dramatic differences in the magnetic anisotropy compared to bulk, as determined from structural and magnetic characterization. Bulk cubic CoV$_2$O$_4$ has been found to defy predictions by showing orbital degeneracy seemingly lasting to very low temperatures, with only small anomalies in magnetization and neutron experiments signaling a possible spin/orbital …
From Chemical Complexity to Tunable Magnetic Ordering in Highly Disordered High-Entropy Spinel Oxides
Thapar Institute of Engineering and Technology（塔帕尔工程技术学院）；UGC-DAE Consortium for Scientific Research（UGC-DAE科学研究联盟）；Freie Universität Berlin（柏林自由大学）；Helmholtz Zentrum Berlin für Materialien und Energie（柏林亥姆霍兹材料与能源中心）；Normandie University（诺曼底大学）
A systematic study using neutron diffraction and magnetic susceptibility are reported on Mn substituted ferrimagnetic inverse spinel Ti$_{1-x}$Mn$_{x}$Co$_2$O$_4$ in the temperature interval 1.6 K $\leq$ $T$ $\leq$ 300 K. Our neutron diffraction study reveals cooperative distortions of the $T$O$_6$ octahedral for all the Jahn-Teller active ions $T$ = Mn$^{3+}$, Ti$^{3+}$ and Co$^{3+}$, which are confirmed by the X-ray photoelectron spectroscopy. Two specific compositions ($x$ = 0.2 and 0.4) have been chosen because of their unique features: noncollinear Yafet-Kittel type ordering, and weak tet…
The canting angles and fluctuation of the magnetic ion spins of spinel oxide MnCr${}_2$O${}_4$ were studied by nuclear magnetic resonance (NMR) at low temperatures, which has a collinear ferrimagnetic order below $T_C$ and a ferrimagnetic spiral order below $T_s < T_C$. Contrary to previous reports, only one spin canting angle of Cr ions was observed. The spin canting angles of Mn and Cr ions in the ferrimagnetic spiral obtained at a liquid-He temperature were $43\,^{\circ}$ and $110\,^{\circ}$, respectively. The nuclear spin-spin relaxation was determined by the Suhl-Nakamura interaction at l…
The low temperature lattice structure and magnetic properties of Co$_{2.75}$Fe$_{0.25}$O$_4$ ferrite have been investigated using experimental results from synchrotron x-ray diffraction (SXRD), dc magnetization, ac susceptibility, neutron diffraction and neutron depolarization techniques. The samples have been prepared by chemical co-precipitation of the Fe and Co nitrates solution in high alkaline medium and subsequent thermal annealing of the precipitates in the temperature range of 200- 900 $^\circ$C. Rietveld refinement of the SXRD patterns at room temperature indicated two-phased cubic sp…
Motivated by recent experiments, we present a comprehensive theoretical study of the geometrically frustrated strongly correlated magnetic insulator Mn$_3$O$_4$ spinel oxide based on a microscopic Hamiltonian involving lattice, spin and orbital degrees of freedom. Possessing the physics of degenerate e$_g$ orbitals, this system shows a strong Jahn-Teller effect at high temperatures. Further, careful attention is paid to the special nature of the superexchange physics arising from the 90$^o$ Mn-O-Mn bonding angle. The Jahn-Teller and superexchange-based orbital-spin Hamiltonians are then analys…
Effect of Ge substitution on first order ferrimagnetic (FRI) - antiferromagnetic (AFM) transition in Mn$_2$Sb has been studied. It shows that transition temperature (T$_t$) can be tuned between 119~K - 271~K by substituting 2.5-10\% Ge at Sb site in Mn$_2$Sb. The variation of density of state at Fermi level N(E$_f$) with Ge substitution shows that dN(E)/dE is positive at E$_f$ in the AFM state. With the application of magnetic field T$_t$ shifts to low temperature, which results in a giant negative magnetoresistance (MR) reaching a value of 70\% for 2.5\% substitution. Our results show that FR…
The spinel-structured lithium manganese oxide (LiMn$_2$O$_4$) is a material currently used as cathode for secondary lithium-ion batteries, but whose properties are not yet fully understood. Here, we report a computational investigation of the inversion thermodynamics and electronic behaviour of LiMn$_2$O$_4$ derived from spin-polarised density functional theory calculations with a Hubbard Hamiltonian and long-range dispersion corrections (DFT+$U-$D3). Based on the analysis of the configurational free energy, we have elucidated a partially inverse equilibrium cation distribution for the LiMn$_2…
We have investigated the structural, magnetic, thermodynamic, and dielectric properties of polycrystalline CoCr$_2$O$_4$, an insulating spinel exhibiting both ferrimagnetic and spiral magnetic structures. Below $T_c$ = 94 K the sample develops long-range ferrimagnetic order, and we attribute a sharp phase transition at $T_N$ $\approx$ 25 K with the onset of long-range spiral magnetic order. Neutron measurements confirm that while the structure remains cubic at 80 K and at 11 K; there is complex magnetic ordering by 11 K. Density functional theory supports the view of a ferrimagnetic semiconduc…
We report the bulk magnetic properties of a yet unexplored vanadium-based multivalued spinel system, Zn3V3O8. A Curie-Weiss fit of our dc magnetic susceptibility data in the temperature region from 140 to 300 K yields a Curie constant C = 0.75cm3K/mole V, theta CW = -370 K. We have observed a splitting between the zero field cooled ZFC and field cooled FC susceptibility curves below a temperature Tirr of about 6.3 K. The value of the 'frustration parameter' nearly equals to 100 suggests that the system is strongly frustrated. From the ac susceptibility measurements we find a logarithmic variat…
The ferrimagnetic spinel MnCr2S4 shows a variety of magnetic-field-induced phase transitions owing to bond frustration and strong spin-lattice coupling. However, the site-resolved magnetic properties at the respective field-induced phases in high magnetic fields remain elusive. Our soft x-ray magnetic circular dichroism studies up to 40 T directly evidence element-selective magnetic-moment reorientations in the field-induced phases. The complex magnetic structures are further supported by entropy changes extracted from magnetocaloric-effect measurements. Moreover, thermodynamic experiments rev…
In this report, the magnetic behaviour of $NiCr_{2}O_{4}$ bulk and nanoparticle samples under different applied magnetic field has been investigated extensively. Nanoparticles of $NiCr_{2}O_{4}$ were obtained by mechanical milling of polycrystalline powder prepared by polyol method. FC-ZFC measurement of bulk at different applied magnetic field has revealed the existence of a ferrimagnetic transition around 66K followed by an antiferromagnetic transition close to 30K. However, its nano counterpart has shown remarkable change in magnetic properties - a suppression of ferrimagnetic transition ac…
We report $^{51}$V zero-field NMR of manganese vanadate spinel of MnV$_2$O$_4$, together with both ac and dc magnetization measurements. The field and temperature dependence of ac susceptibilities show a reentrant-spin-glass-like behavior below the ferrimagnetic(FEM) ordering temperature. The zero-field NMR spectrum consists of multiple lines ranging from 240 MHz to 320 MHz. Its temperature dependence reveals that the ground state is given by the simultaneous formation of a long-range FEM order and a short-range order component. We attribute the spin-glass-like anomalies to freezing and fluctu…
Neutron diffraction, magnetization and muon spin relaxation measurements, supplemented by density functional theory (DFT) calculations are employed to unravel temperature-driven magnetization reversal (MR) in inverse spinel Co$_2$VO$_4$. All measurements show a second-order magnetic phase transition at $T_{\rm C} = 168$\,K to a collinear ferrimagnetic phase. The DFT results suggest the moments in the ferrimagnetic phase are delocalized and undergo gradual localization as the temperature is lowered below $T_{\rm C}$. The delocalized-localized crossover gives rise to a maximum magnetization at $…
The spinel vanadates have become a model family for exploring orbital order on the frustrated pyrochlore lattice, and recent debate has focused on the symmetry of local crystal fields at the cation sites. Here, we present neutron scattering measurements of the magnetic excitation spectrum in $\mathrm{FeV_2O_4}$, a recent example of a ferrimagnetic spinel vanadate which is available in single crystal form. We report the existence of two emergent magnon modes at low temperatures, which draw strong parallels with the closely related material, $\mathrm{MnV_2O_4}$. We were able to reproduce the ess…
We present temperature-, magnetic-field-, and pressure-dependent Raman scattering studies of single crystal Mn3O4, combined with temperature- and field-dependent x-ray diffraction studies, revealing the novel magnetostructural phases in Mn3O4. Our temperature-dependent studies showed that the commensurate magnetic transition at T2=33K in the binary spinel Mn3O4 is associated with a structural transition from tetragonal to orthorhombic structures. Field-dependent studies showed that the onset and nature of this structural transition can be controlled with an applied magnetic field, and revealed…
The ferrimagnetic spinel Mn3O4 exhibits large and anisotropic changes in electronic and structural properties in response to an applied magnetic field. These changes are thought to result from the field-dependent tuning---via strong spin-lattice coupling---between two nearly degenerate magnetostructural phases. Recent variable-magnetic-field studies of Mn3O4 have been performed on melt-grown crystals, which can exhibit twin domains due to a Jahn-Teller structural transition below the melting temperature. Because of the near degeneracy of the magnetostructural phases, however, strain associated…
The ferrimagnetic spinels MnB2O4 (B = Mn,V) exhibit a similar series of closely spaced magnetic and structural phase transitions at low temperatures, reflecting both magnetic frustration and a strong coupling between the spin and lattice degrees of freedom. Careful studies of excitations in MnB2O4 (B = Mn,V), and the evolution of these excitations with temperature, are important for obtaining a microscopic description of the role that magnetic excitations and spin-lattice coupling play in the low temperature phase transitions of these materials. We report an inelastic light (Raman) scattering …
