We show by means of ab-initio calculations that the organic molecular crystal TTF-CA is multiferroic: it has an instability to develop spontaneously both ferroelectric and magnetic ordering. Ferroelectricity is driven by a Peierls transition of the TTF-CA in its ionic state. Subsequent antiferromagnetic ordering strongly enhances the opposing electronic contribution to the polarization: it is so large that it switches the direction of the total ferroelectric moment. Within an extended Hubbard model we capture the essence of the electronic interactions in TTF-CA, confirm the presence of a multiferroic groundstate and clarify how this state develops microscopically.
The energy level alignment of the two organic materials forming the TTF-TCNQ interface is analyzed by means of a local orbital DFT calculation, including an appropriate correction for the transport energy gaps associated with both materials. These energy gaps are determined by a combination of some experimental data and the results of our calculations for the difference between the TTF_{HOMO} and the TCNQ_{LUMO} levels. We find that the interface is metallic, as predicted by recent experiments, due to the overlap (and charge transfer) between the Density of States corresponding to these two le…
The interface between the tetrathiafulvalene / tetracyanoquinodimethane (TTFTCNQ) organic blend and the Au(111) metal surface is analyzed by Density Functional Theory calculations, including the effect of the charging energies on the molecule transport gaps. Given the strong donor and acceptor characters of the TTF and TCNQ molecules, respectively, there is a strong intermolecular interaction, with a relatively high charge transfer between the two organic materials. We find that the TCNQ LUMO peak is very close to the Fermi level; due to the interaction with the metal surface, the organic blen…
(BEDT-TFF)$_2$I$_3$ charge transfer salts are reported to show superconductivity and pressure induced quasi two-dimensional Dirac cones at the Fermi level. By performing state of the art ab initio calculations in the framework of density functional theory, we investigate the structural and electronic properties of the three structural phases $α$, $β$ and $κ$. \edit{We furthermore report about the irreducible representations of the corresponding electronic band structures, symmetry of their crystal structure, and discuss the origin of band crossings. Additionally, we discuss the chemically indu…
We show a zero-gap semiconducting (ZGS) state in the quasi-two-dimensional organic conductor $α$-(BEDT-TTF)$_2$I$_3$ salt, which emerges under uniaxial pressure along the a-axis (the stacking axis of the BEDT-TTF molecule). The ZGS state is the state in which a Dirac cone with the band spectrum of a linear dispersion exists around the Fermi point connecting an unoccupied (electron) band with an occupied (hole) band. The spectrum exhibits a large anisotropy in velocity, which depends on the direction from the Fermi point. By varying the magnitude of several transfer energies of a tight-binding …
We report a $^{13}$C-NMR study on the ambient-pressure metallic phase of the layered organic conductor $θ$-(BEDT-TTF)$_{2}$I$_{3}$ [BEDT-TTF: bisethylenedithio-tetrathiafulvalene], which is expected to connect the physics of correlated electrons and Dirac electrons under pressure. The orientation dependence of the NMR spectra shows that all BEDT-TTF molecules in the unit cell are to be seen equivalent from a microscopic point of view. This feature is consistent with the orthorhombic symmetry of the BEDT-TTF sublattice and also indicates that the monoclinic $I_{3}$ sublattice, which should make…
Highly ordered epitaxial interfaces between organic semiconductors are considered as a promising avenue for enhancing the performance of organic electronic devices including solar cells, light emitting diodes, and transistors, thanks to their well-controlled, uniform electronic properties and high carrier mobilities. Although the phenomenon of organic epitaxy has been known for decades, computational methods for structure prediction of epitaxial organic interfaces have lagged far behind the existing methods for their inorganic counterparts. We present a method for structure prediction of epita…
We demonstrate that ethylammonium copper chloride, (C2H5NH3)2CuCl4, a member of the hybrid perovskite family is an electrically polar and magnetic compound with dielectric anomaly around the Curie point (247 K). We have found large spontaneous electric polarization below this point accompanied with a color change in the sample. The system is also ferroelectric, with large remnant polarization (37μC/cm2) that is comparable to classical ferroelectric compounds. The results are ascribed to hydrogen-bond ordering of the organic chains. The coexistence of ferroelectricity and dominant ferromagnetic…
Layered organic conductors (BEDO-TTF)_2ReO_4*H_2O (metal) and (BEDT-TTF)_xDy(NO_3)_z (paramagnetic insulator) are studied by CW-EPR and SQUID methods. A correlation in resonance and transport properties of both compounds is attributed to a similar mechanism of fine anion ordering (AO) at T_AO=200 K. Due to the hydrogen bonds motif the small configuration changes in anion sub-lattice bring a profound effect on electronic properties. It is shown that the spin system of (BEDO-TTF)_2ReO_4*H_2O consists of a fraction of delocalized pi-type holes (I_epr=n(e_F)), I_epr(300K)=1,62*10^(-4) emu/mol and …
Spin-current injection into an organic semiconductor $\rm{κ\text{-}(BEDT\text{-}TTF)_2Cu[N(CN)_2]Br}$ film induced by the spin pumping from an yttrium iron garnet (YIG) film. When magnetization dynamics in the YIG film is excited by ferromagnetic or spin-wave resonance, a voltage signal was found to appear in the $\rm{κ\text{-}(BEDT\text{-}TTF)_2Cu[N(CN)_2]Br}$ film. Magnetic-field-angle dependence measurements indicate that the voltage signal is governed by the inverse spin Hall effect in $\rm{κ\text{-}(BEDT\text{-}TTF)_2Cu[N(CN)_2]Br}$. We found that the voltage signal in the $\rm{κ\text{-}(…
The conducting state of the quasi-two-dimensional organic conductor, $α$-(BEDT-TTF)$_2$I$_3$, at ambient pressure is investigated with $^{13}$C NMR measurements, which separate the local electronic states at three nonequivalent molecular sites (A, B, and C). The spin susceptibility and electron correlation effect are revealed in a locally resolved manner. While there is no remarkable site-dependence around room temperature, the local spin susceptibility gradually disproportionates among the nonequivalent sites with decreasing temperature. The disproportionation-ratio yields 5:4:6 for A:B:C mol…
The Dirac electron in the organic conductor $α$-(BEDT-TTF)$_2$I$_3$ under pressure is analyzed using a tight-binding model with nearest-neighbor transfer energies and four molecules per unit cell. By noting that the Dirac point between the first and second energy bands emerges or merges followed by the level crossing at a time-reversal invariant momentum (TRIM), an effective Hamiltonian is derived on the basis of these two wave functions at the TRIM, which have different parities associated with an inversion symmetry around the inversion center. We demonstrate that the Dirac point is determine…
We present the results of our $^{13}$C NMR study of the quasi-two-dimensional organic conductor $θ$-(BEDT-TTF)$_2$I$_{3}$ under pressure, which is suggested to be a zero-gap conductor by transport measurements. We found that NMR spin shift is proportional to $T$ and that spin-lattice relaxation rate follows the power law $T^α$ ($α=3 \sim 4$), where $T$ is the temperature. This behavior is consistent with the cone-like band dispersion and provides microscopic evidence for the realization of the zero-gap state in the present material under pressure.
An electronic band with quasi-one dimensional dispersion is found at the interface between a monolayer of a charge-transfer complex (TTF-TCNQ) and a Au(111) surface. Combined local spectroscopy and numerical calculations show that the band results from a complex mixing of metal and molecular states. The molecular layer folds the underlying metal states and mixes with them selectively, through the TTF component, giving rise to anisotropic hybrid bands. Our results suggest that, by tuning the components of such molecular layers, the dimensionality and dispersion of organic-metal interface states…
We investigated the magnetism under a magnetic field in the quasi-two-dimensional organic Mott insulator $κ$-(BEDT-TTF)$_{2}$Cu[N(CN)$_{2}$]Cl through magnetization and $^{13}$C-NMR measurements. We found that in the nominally paramagnetic phase (i.e., above Néel temperature) the field-induced local moments have a staggered component perpendicular to the applied field. As a result, the antiferromagnetic transition well defined at a zero field becomes crossover under a finite field. This unconventional behavior is qualitatively reproduced by the molecular-field calculation for Hamiltonian inclu…
We have performed charge transfer phase formation studies on the donor/acceptor system bis(ethylendithio)tetrathiafulvalene,(BEDT-TTF)/tetracyanoquinodimethane,(TCNQ) by means of physical vapor deposition. We prepared donor/acceptor bilayer structures on glass and Si(100)/SiO_2 substrates held at room temperature and analyzed the layer structures by optical microscopy, X-ray diffraction and focused ion beam cross sectioning before and after annealing. We found clear evidence for the formation of a charge transfer phase during the annealing procedure. For the as-grown samples we could not detec…
We theoretically investigate possible photoinduced topological phase transitions in the organic salt $α$-(BEDT-TTF)$_2$I$_3$, which possesses a pair of inclined massless Dirac-cone bands between the conduction and valence bands under uniaxial pressure. The Floquet analyses of a driven tight-binding model for this material reveal rich photoinduced variations of band structures, Chern numbers, and Hall conductivities under irradiation with elliptically polarized light. The obtained phase diagrams contain a variety of nonequilibrium steady phases, e.g., the Floquet Chern insulator, Floquet semime…
We study the Seebeck effect in the $τ$-type organic conductors, $τ$-(EDO-$S$,$S$-DMEDT-TTF)$_{2}$(AuBr$_{2}$)$_{1+y}$ and $τ$-(P-$S$,$S$-DMEDT-TTF)$_{2}$(AuBr$_{2}$)$_{1+y}$, where EDO-$S$,$S$-DMEDT-TTF and P-$S$,$S$-DMEDT-TTF are abbreviated as OOSS and NNSS, respectively, both experimentally and theoretically. Theoretically in particular, we perform first-principles band calculation for the two materials and construct a two-orbital model, on the basis of which we calculate the Seebeck coefficient. We show that the calculated temperature dependence of the Seebeck coefficient $S$ is semi-quant…
We performed third-order electrical conductivity measurements on the organic conductor $α$-(BEDT-TTF)$_2$I$_3$ using an ac bridge technique sensitive to nonlinear signals. Third-order conductance $G_3$ is clearly observed even at low electric fields, and interestingly, $G_3$ is critically enhanced above the charge-order transition temperature $T_{\rm CO}=136$~K. The observed frequency dependence of $G_3$ is incompatible with a percolation model, in which a Joule heating in a random resistor network is relevant to the nonlinear conduction. We instead argue the nonlinearity of the relaxation tim…
The synthesis and design of organic biradicals with tunable singlet-triplet gaps has become the subject of significant research interest, owing to their possible photochemical applications and use in the development of molecular switches and conductors. Recently, tetrathiafulvalene tetrathiolate (TTFtt) has been demonstrated to exhibit such organic biradical character in doubly ionized bimetallic complexes. In this article we use high-level {\em ab initio} calculations to interrogate the electronic structure of a series of TTFtt-bridged metal complexes, resolving the factors governing their bi…
We investigate the continuous variation of electronic states from a Fermi liquid to a quantum spin liquid induced by chemical substitution in the organic dimer-Mott system of $κ$-[(BEDSe-TTF)$_x$(BEDT-TTF)$_{1-x}$]$_2$Cu[N(CN)$_2$]Br. Electrical transport measurements reveal that the mixing of BEDSe-TTF into the BEDT-TTF layers induces a quantum Mott transition around $x$=0.10. Although a charge gap disappears at this point, magnetic susceptibility and heat capacity measurements indicate that fermionic low-energy excitations remain in the insulating salts, suggesting that fermionic spin excita…
To determine how electron correlations open a gap in two-dimensional massless Dirac electrons in the organic compounds $α$-(BEDT-TTF)$_2$I$_3$ [$α$-(ET)$_2$I$_3$] and $α$-(BEDT-TSeF)$_2$I$_3$ [$α$-(BETS)$_2$I$_3$], we derive and analyze $ab$ $initio$ low-energy effective Hamiltonians for these two compounds. We find that the horizontal stripe charge ordering opens a gap in the massless Dirac electrons in $α$-(ET)$_2$I$_3$, while an insulating phase without explicit symmetry breaking appears in $α$-(BETS)$_2$I$_3$. We clarify that the combination of the anisotropic transfer integrals and the el…
We report the dielectric, magnetic, and ultrasonic properties of a one-dimensional organic salt TTF-QBr$_3$I. These indicate that TTF-QBr$_3$I shows a ferroelectric spin-Peierls (FSP) state in a quantum critical regime. In the FSP state, coupling of charge, spin, and lattice leads to emergent excitation of spin solitons as topological defects. Amazingly, the solitons are highly mobile even at low temperatures, although they are normally stationary because of pinning. Our results suggest that strong quantum fluctuations enhanced near a quantum critical point enable soliton motion governed by at…
Confined electrons in low dimensions host desirable material functions for downscaled electronics as well as advanced energy technologies. Thermoelectricity is a most fascinating example, since the dimensionality modifies the electron density of states dramatically, leading to enhanced thermopower as experimentally examined in artificial two-dimensional (2D) structures. However, it is still an open question whether such an enhanced thermopower in low dimensions is realized in layered materials with strong 2D characters such as cuprates. Here, we report unusual enhancement of the thermopower in…
We discuss the surface magnetotransport in the quantum Hall (QH) ferromagnetic state expected in the organic Dirac fermion system α-(BEDT-TTF)_2I_3. The QH ferromagnetic state is one of the possible ν=0 QH states in the two-dimensional Dirac fermion system resulting from the degeneracy breaking of the n=0 Landau level. It is characterized by the helical edge state. We have studied the interlayer surface transport via helical edge state in the multilayer QH ferromagnet, in which the bulk region is insulating. We have clarified that the surface conductivity is much less than e^2/h and decreases …
To elucidate a novel pressure-temperature phase diagram of the quasi-one-dimensional mixed-stack charge-transfer (CT) complex TTF-CA, we study the quasi-one-dimensional spin-1 Blume-Emery-Griffith (BEG) model. In addition to the local charge transfer energy and the inter-stack polar (dipole-dipole) interaction, we take account of the inter-stack electrostriction effect. Using the self-consistent chain-mean-field theory, where the intra-stack degrees of freedom are exactly treated by the transfer-matrix method, we reproduce the gas-liquid-solid like phase diagram corresponding to the neutral (N…
We present high-resolution measurements of the relative length change as a function of temperature of the organic charge-transfer salt $κ$-(BEDT-TTF)$_2$Hg(SCN)$_2$Cl. We identify anomalous features at $T_g \approx\,63$ K which can be assigned to a kinetic glass-like ordering transition. By determining the activation energy $E_A$, this glass-like transition can be related to conformational degrees of freedom of the ethylene endgroups of the organic building block BEDT-TTF. As opposed to other $κ$-(BEDT-TTF)$_2X$ salts, we identify a peculiar ethylene endgroup ordering in the present material i…
In this contribution to the special issue on multiferroics we focus on multiferroicity driven by different forms of charge ordering. We will present the generic mechanisms by which charge ordering can induce ferroelectricity in magnetic systems. There is a number of specific classes of materials for which this is relevant. We will discuss in some detail $(i)$ perovskite manganites of the type (PrCa)MnO$_3$, $(ii)$ the complex and interesting situation in magnetite Fe$_3$O$_4$, $(iii)$ strongly ferroelectric frustrated LuFe$_2$O$_4$, $(iv)$ an example of a quasi one-dimensional organic system. …
