The two-dimensional molecular conductor kappa-(BETS)2Mn[N(CN)2]3 undergoes a sharp metal-to-insulator phase transition at TMI approximate to 21 K, which has been under scrutiny for many years. We performed comprehensive infrared investigations along the three crystallographic directions as a function of temperature down to 10 K, complemented by electron spin resonance and dc-transport studies. The in-plane anisotropy of the optical conductivity is more pronounced than in any other kappa-type BEDT-TTF or related compound. The metal-insulator transitions affect the molecular vibrations due to the coupling to the electronic system; in addition we observe a clear splitting of the charge-sensitive vibrational modes below TMI that evidences the presence of two distinct BETS dimers in this compound. The Mn[N(CN)2]-3 layers are determined by the chain structure of the anions resulting in a rather anisotropic behavior and remarkable temperature dependence of the vibronic features. At low temperatures the electron spin resonance properties are affected by the Mn2+ ions via pi-d coupling and antiferromagnetic ordering within the pi spins: The g factor shifts enormously with a pronounced in-plane anisotropy that flips as the temperature decreases; the lines broaden significantly, and the spin susceptibility increases upon cooling, with a kink at the phase transition.

The two-dimensional molecular conductor κ-(BETS)_2Mn[N(CN)_2]_3 undergoes a sharp metal-to-insulator phase transition at T_ MI≈ 21 K, which has been under scrutiny for many years. We have performed comprehensive infrared investigations along the three crystallographic directions as a function of temperature down to 10 K, complemented by electron spin resonance and dc-transport studies. The in-plane anisotropy of the optical conductivity is more pronounced than in any other κ-type BEDT-TTF or related compounds. The metal-insulator transitions affects the molecular vibrations due to the coupling to the electronic system; in addition we observe a clear splitting of the charge-sensitive vibrational modes below T_ MI that evidences the presence of two distinct BETS dimers in this compound. The Mn[N(CN)_2]_3^- layers are determined by the chain structure of the anions resulting in a rather anisotropic behavior and remarkable temperature dependence of the vibronic features. At low temperatures the ESR properties are affected by the Mn^2+ ions via π-d-coupling and antiferromagnetic ordering within the π-spins: The g-factor shifts enormously with a pronounced in-plane anisotropy that flips as the temperature decreases; the lines broaden significantly; and the spin susceptibility increases upon cooling with a kink at the phase transition.

The layered molecular conductors kappa-(BEDT-TTF)(2)X are a perfect experimental platform for studying the physics of the Mott transition and related exotic electronic states. In these materials, the subtle balance between various instabilities of the normal metallic state can be efficiently changed by applying a very moderate external pressure or by subtle chemical modifications, e.g., by a replacement of the insulating anion X-, frequently referred to as "chemical pressure." A crucially important but still unsettled issue is an exact understanding of the influence of physical and chemical pressure on the electronic structure. To elucidate this issue, we study, in a broad pressure range, magnetic quantum oscillations in two. salts, the ambient-pressure antiferromagnetic insulator with X = Cu[N(CN)(2)]Cl and the ambient-pressure superconductor with X = Cu(NCS)(2). The data obtained provide quantitative information on important parameters governing the Mott physics, including the electronic correlation strength ratio U/t and the spin frustration ratio t'/t. This allows us to directly evaluate the effects of physical and chemical pressure in the present materials. Our analysis reveals significant weakening of both the electronic correlation strength and the magnetic ordering instability under pressure. On the other hand, the anion replacement is found to considerably change the frustration parameter t'/t while leaving the correlation strength virtually unaffected.

Ferroelectricity, where electronic degrees of freedom determine the polar order—thereby enabling fast switching and phase control—is an important research field in current condensed-matter physics. Using a combination of resistance noise and dielectric spectroscopy we investigate the nature of relaxor-type electronic ferroelectricity in the organic conductor κ-(BETS)2Mn[N(CN)2]3, a system that represents a wider class of materials of correlated electron systems for which functionalities for organic spintronics recently have been discussed. The two complementary spectroscopies reveal a distinct low-frequency dynamics on different length scales, namely (i) an intrinsic relaxation that is typical for relaxor ferroelectrics which classifies the system as a possible new multiferroic, and (ii) two-level processes which we identify as fluctuating polar nanoregions (PNR), i.e., clusters of quantum electric dipoles that fluctuate collectively. The PNR preform above the metal insulator (MI) transition. Upon cooling through TMI, a drastic increase of the low-frequency 1/f-type fluctuations and slowing down of the charge carrier dynamics is accompanied by the onset of strong non-equilibrium dynamics indicating a glassy transition of interacting dipolar clusters. The freezing of PNR and non-equilibrium dynamics is suggested to be a common feature of organic relaxor-type electronic ferroelectrics.

Using a combination of resistance fluctuation (noise) and dielectric spectroscopy we investigate the nature of relaxor-type electronic ferroelectricity in the organic conductor $\kappa$-(BETS)$_2$Mn[N(CN)$_2$]$_3$, a system representative for a wider class of materials, where strong correlations of electrons on a lattice of dimerized molecules results in an insulating ground state. The two complementary spectroscopies reveal a distinct low-frequency dynamics. By dielectric spectroscopy we detect an intrinsic relaxation that is typical for relaxor ferroelectrics below the metal-to-insulator transition at $T_{\rm{MI}}\sim 25\,$K. Resistance noise spectroscopy reveals fluctuating two-level processes above $T_{\rm MI}$ which strongly couple to the applied electric field, a signature of fluctuating polar nanoregions (PNR), i.e. clusters of quantum electric dipoles fluctuating collectively. The PNR preform above the metal insulator transition. Upon cooling through $T_{\rm MI}$, a drastic increase of the low-frequency $1/f$-type fluctuations and slowing down of the charge carrier dynamics is accompanied by the onset of strong non-equilibrium dynamics indicating a glassy transition of interacting dipolar clusters, the scaling properties of which are consistent with a droplet model. The freezing of nano-scale polar clusters and non-equilibrium dynamics is suggested to be a common feature of organic relaxor-type electronic ferroelectrics and needs to be considered in theoretical models describing these materials.

The physics of the Mott metal-insulator transition (MIT) has attracted huge interest in the last decades. However, despite broad efforts, some key theoretical predictions are still lacking experimental confirmation. In particular, it is not clear whether the large coherent Fermi surface survives in immediate proximity to the bandwidth-controlled first-order MIT. A quantitative experimental verification of the predicted behavior of the quasiparticle effective mass, renormalized by many-body interactions, is also missing. Here we address these issues by employing organic κ-type salts as exemplary quasi-two-dimensional bandwidth-controlled Mott insulators and gaining direct access to their charge carrier properties via magnetic quantum oscillations. We trace the evolution of the effective cyclotron mass as the conduction bandwidth is tuned very close to the MIT by means of precisely controlled external pressure. We find that the sensitivity of the mass renormalization to tiny changes of the bandwidth is significantly stronger than theoretically predicted and is even further enhanced upon entering the transition region where the metallic and insulating phases coexist. On the other hand, even at its very edge of stability the metallic ground state preserves a large coherent Fermi surface with no significant enhancement of scattering.

Organic salts represent an ideal experimental playground for studying the interplay between magnetic and charge degrees of freedom, which has culminated in the discovery of several spin-liquid candidates such as κ-(ET)_{2}Cu_{2}(CN)_{3} (κ-Cu). Recent theoretical studies indicate the possibility of chiral spin liquids stabilized by ring exchange, but the parent states with chiral magnetic order have not been observed in this material family. In this Letter, we discuss the properties of the recently synthesized κ-(BETS)_{2}Mn[N(CN)_{2}]_{3} (κ-Mn). Based on analysis of specific heat, magnetic torque, and NMR measurements combined with ab initio calculations, we identify a spin-vortex crystal order. These observations definitively confirm the importance of ring exchange in these materials and support the proposed chiral spin-liquid scenario for triangular lattice organics.

Most of solid-state spin physics arising from spin–orbit coupling, from fundamental phenomena to industrial applications, relies on symmetry-protected degeneracies. So does the Zeeman spin–orbit coupling, expected to manifest itself in a wide range of antiferromagnetic conductors. Yet, experimental proof of this phenomenon has been lacking. Here we demonstrate that the Néel state of the layered organic superconductor κ-(BETS)2FeBr4 shows no spin modulation of the Shubnikov–de Haas oscillations, contrary to its paramagnetic state. This is unambiguous evidence for the spin degeneracy of Landau levels, a direct manifestation of the Zeeman spin–orbit coupling. Likewise, we show that spin modulation is absent in electron-doped Nd1.85Ce0.15CuO4, which evidences the presence of Néel order in this cuprate superconductor even at optimal doping. Obtained on two very different materials, our results demonstrate the generic character of the Zeeman spin–orbit coupling.

We present detailed studies of the high-field magnetoresistance of the layered organic metal kappa-(BETS)(2)Mn[N(CN)(2)](3) under a pressure slightly above the insulator-metal transition. The experimental data are analyzed in terms of the Fermi surface properties and compared with the results of first-principles band structure calculations. The calculated size and shape of the in-plane Fermi surface are in very good agreement with those derived from Shubnikov-de Haas oscillations as well as the classical angle-dependent magnetoresistance oscillations. A comparison of the experimentally obtained effective cyclotron masses with the calculated band masses reveals electron correlations significantly dependent on the electron momentum. The momentum- or band-dependent mobility is also reflected in the behavior of the classical magnetoresistance anisotropy in a magnetic field parallel to layers. Other characteristics of the conducting system related to interlayer charge transfer and scattering mechanisms are discussed based on the experimental data. Besides the known high-field effects associated with the Fermi surface geometry, new pronounced features have been found in the angle-dependent magnetoresistance, which might be caused by coupling of the metallic charge transport to a magnetic instability in proximity to the metal-insulator phase boundary.

The dependence of the resistance of a layered conductor with a quasi-two-dimensional charge carrier energy spectrum on the strength and orientation of a quantizing magnetic field is studied. The case of an organic conductor with a multisheet Fermi surface consisting of a weakly warped cylinder and two adjoining planar sheets is considered. By applying an external pressure to the conductor or doping it with impurity atoms, the gap between the cylinder and the planar sheets of the Fermi surface (FS) may be reduced so that electrons start wandering on the FS, tunneling between its different parts due to magnetic breakdown. If an electron can pass through all the different sheets of the FS several times during the mean free time, its motion in the plane orthogonal to the magnetic field becomes finite. This leads to Shubnikov–de Haas oscillations with a period determined by the area enclosed by the closed breakdown orbit of an electron in momentum space. However, even at a slight tilting of the field from the normal to the layers by an angle ϑ, the equidistance is broken and at certain angles ϑk the probability of the magnetic breakdown to one of the planar FS sheets may become so low that the electron cannot complete the magnetic-breakdown orbit and its motion over the other planar sheet and the cylindrical part of the FS becomes infinite. As a result, magnetic-breakdown quantum oscillations of magnetization and all kinetic properties vanish. This vanishing repeats periodically as a function of tan ϑ with changing the tilt angle. Possibilities for experimental observation and investigation of the influence of magnetic breakdown on quantum oscillation phenomena are discussed.

We make use of the strong spin-charge coupling in the electron-doped cuprate $\mathrm{Nd}_{2-x}\mathrm{Ce}_x\mathrm{CuO}_4$ to probe changes in its spin system via magnetotransport measurements. We present a detailed study of the out-of-plane magnetoresistance in underdoped single crystals of this compound, including the nonsuperconducting, $0.05\,\leq x\,\leq 0.115$, and superconducting, $0.12\,\leq x\,\leq 0.13$, compositions. Special focus is put on the dependence of the magnetoresistance on the field orientation in the plane of the CuO$_2$ layers. In addition to the kink at the field-induced transition between the noncollinear and collinear antiferromagnetic configurations, a sharp irreversible feature is found in the angle-dependent magnetoresistance of all samples in the high-field regime, at field orientations around the Cu--O--Cu direction. The obtained behavior can be explained in terms of field-induced reorientation of Cu$^{2+}$ spins within the collinear antiferromagnetic state. It is, therefore, considered as an unambiguous indication of the long-range magnetic order.

A new metallic radical cation salt kappa-(BETS)(2)Co0.13Mn0.87IN(CN)(2)](3), where BETS is bis(ethylenedithio) tetraselenafulvalene, C10S4Se4H8, has been synthesized. In this salt, a part of Mn2+ ions are replaced by Co2+ which acts as a magnetic dopant with a different effective magnetic moment. Crystal structure, band structure, conducting and magnetic properties of the salt have been studied. Below 30 K the material undergoes a metal-insulator transition, which is suppressed by applying a pressure of similar to 0.5 kbar, leading to a superconducting ground state. While the structural and conducting properties are very similar to those of the parent salt kappa-(BETS)(2)Mn[N(CN)(2)](3), magnetic properties associated with localized moments in the anion layer are found to be surprisingly different. (C) 2017 Elsevier B.V. All rights reserved.

We present magnetoresistance studies of the quasi-two-dimensional organic conductor kappa-(BETS)(2)Mn[N(CN)(2)](3), where BETS stands for bis(ethylenedithio) tetraselenafulvalene. Under a moderate pressure of 1.4 kbar, required for stabilizing the metallic ground state, Shubnikov-de Haas oscillations, associated with a classical and a magnetic-breakdown cyclotron orbits on the cylindrical Fermi surface, have been found at fields above 10 T. The effective cyclotron masses evaluated from the temperature dependence of the oscillation amplitudes reveal strong renormalization due to many-body interactions. The analysis of the relative strength of the oscillations corresponding to the different orbits and of its dependence on magnetic field suggests an enhanced role of electron-electron interactions on flat parts of the Fermi surface. Published by AIP Publishing.

In the organic charge transfer salt k-(BETS)2Mn[N(CN)2]3 the metallic conductivity is provided by itinerant pi-electrons in the layers of BETS molecules, whereas magnetization is largely dominated by the localized d-electrons of the Mn2+ ions in the insulating anionic layers. We study magnetic properties of the compound in its low-temperature, Mott-insulating state by means of magnetic torque technique. The complex behavior of the torque can be qualitatively explained by the coexistence of two weakly interacting magnetic subsystems associated with paramagnetic d-electron spins and antiferromagnetically ordered pi-electron spins, respectively. Based on the experimental data, we determine the principal axes of magnetization of the Mn2+ sublattice and propose a qualitative model for the pi-electron spin arrangement, implying an important role of the Dzyaloshinskii-Moriya interaction.

The mutual influence of the conduction electron system provided by organic donor layers and magnetic system localized in insulating layers of the molecular charge transfer salt κ -(BETS) 2 FeBr 4 has been studied. It is demonstrated that besides the high-field re-entrant superconducting state, the interaction between the two systems plays important role for the low-field superconductivity. The coupling of normal-state charge carriers to the magnetic system is reflected in magnetic quantum oscillations and can be evaluated based on the angle-dependent beating behavior of the oscillations. On the other hand, the conduction electrons have their impact on the magnetic system, which is revealed through the pressure-induced changes of the magnetic phase diagram of the material.

The low-temperature electronic state of the layered organic charge-transfer salt $\kappa$-(BETS)$_2$FeCl$_4$ was probed by interlayer electrical resistance measurements under magnetic field. Both above and below $T_{\mathrm{N}}=0.47\,$K, the temperature of antiferromagnetic ordering of $3d$-electron spins of Fe$^{3+}$ localized in the insulating anion layers, a non-saturating linear $R(T)$ dependence has been observed. A weak superconducting signal has been detected in the antiferromagnetic state, at temperatures $\leq 0.2\,$K. Despite the very high crystal quality, only a tiny fraction of the sample appears to be superconducting. Besides a small kink feature in the resistivity, the impact of the antiferromagnetic ordering of localized Fe$^{3+}$ spins on the conduction $\pi$-electron system is clearly manifested in the Fermi surface reconstruction, as evidenced by Shubnikov-de Haas oscillations. The "magnetic field -- temperature" phase diagrams for the field directions parallel to each of the three principal crystal axes have been determined. For magnetic field along the easy axis a spin-flop transition has been found. Similarities and differences between the present material and the sister compound $\kappa$-(BETS)$_2$FeBr$_4$ are discussed.

The mutual influence of the conduction electron system provided by organic donor layers and magnetic system localized in insulating layers of the molecular charge transfer salt $\kappa$-(BETS)$_2$FeBr$_4$ has been studied. It is demonstrated that besides the high-field re-entrant superconducting state, the interaction between the two systems plays important role for the low-field superconductivity. The coupling of normal-state charge carriers to the magnetic system is reflected in magnetic quantum oscillations and can be evaluated based on the angle-dependent beating behaviour of the oscillations. On the other hand, the conduction electrons have their impact on the magnetic system, which is revealed through the pressure-induced changes of the magnetic phase diagram of the material.

The low-temperature electronic state of the layered organic charge-transfer salt $\kappa$-(BETS)$_2$FeCl$_4$ was probed by interlayer electrical resistance measurements under magnetic field. Both above and below $T_{\mathrm{N}}=0.47\,$K, the temperature of antiferromagnetic ordering of $3d$-electron spins of Fe$^{3+}$ localized in the insulating anion layers, a non-saturating linear $R(T)$ dependence has been observed. A weak superconducting signal has been detected in the antiferromagnetic state, at temperatures $\leq 0.2\,$K. Despite the very high crystal quality, only a tiny fraction of the sample appears to be superconducting. Besides a small kink feature in the resistivity, the impact of the antiferromagnetic ordering of localized Fe$^{3+}$ spins on the conduction $\pi$-electron system is clearly manifested in the Fermi surface reconstruction, as evidenced by Shubnikov-de Haas oscillations. The "magnetic field -- temperature" phase diagrams for the field directions parallel to each of the three principal crystal axes have been determined. For magnetic field along the easy axis a spin-flop transition has been found. Similarities and differences between the present material and the sister compound $\kappa$-(BETS)$_2$FeBr$_4$ are discussed.