Cu [ N Research Articles

Monomer Mott Insulator (BEDT-TTF)Cu[N(CN)2]2 as a Potential Nodal Line System

We report the band structure calculations and the experimental results of resistivity and magnetic susceptibility in a spin-1/2 (BEDT-TTF)$^{\bullet +}$ monomer Mott insulator (BEDT-TTF)Cu[N(CN)$_2$]$_2$. The band calculations indicate a Dirac semimetal state with nodal lines at the Fermi level. The resistivity and the magnetic susceptibility as functions of temperature are well interpreted in terms of the monomer Mott insulating state instead of the expected semimetal state probably owing to strong electron correlation. In addition, we find that an Arrhenius-type steep reduction of the paramagnetic susceptibility appears below approximately 25 K, which indicates a spin-singlet ground state.

Low-power anisotropic molecular electronic memristors

A molecular electronic memristor, programmable resistive memory device, promises to revolutionize next-generation flexible data storage units, offering fast, dense and ultralow power solutions. Here we report anisotropic resistive switching in molecular κ-(BEDT-TTF)2Cu[N(CN)2]Cl memristors, consisting of alternatively segregated bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) and Cu[N(CN)2]Cl layers. Electron resistance switching behavior controlled by charge tunneling in molecular memristors show a low set voltage of 0.5 V (10 V/cm) with the ON/OFF ratio of 2.3×103 along a-axis and a high-level endurance of 1.25×104 cycles along all axes. The findings of such molecular electronic crystals promise for low-power data storage memristors.

Persistence of fermionic spin excitations through a genuine Mott transition in κ -type organics

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 $\kappa$-[(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 excitations persist. We propose that the transition can be classified into a genuine Mott transition.

Emerged Metallicity in Molecular Ferromagnetic Wires.

Supramolecular engineering bridges molecular assembly with macromolecular charge-transfer salts, promising the design to construct supramolecular architectures that integrate cooperative properties difficult or impossible to find in conventional lattices. Here, we report the crystal engineering design and kinetic growth of one-dimensional supramolecular wires composed of bis(ethylenedithio)tetrathiafulvalene (ET+) cation and polymeric Cu[N(CN)2]2- anion. A bulk ferromagnetic order is discovered for filling up the gap where strong ferromagnetism is missing in such ET molecule-based charge-transfer salts. Metallicity is induced by electric current from the semiconducting wire, which is attributed to strain effect by tuning its close molecular contact. This structural feature is evidenced through the combination of various mechanistic spectroscopic studies. Electric dipole is established from the close molecular contacts and is suggestive to stabilize ferromagnetic spin interaction through anions bridging spin sites. The breakthrough shown here provides a pathway to explore low-dimensional supramolecular materials exhibiting strong electron correlation, metallicity, and ferromagnetism.

Phase Diagram for Light-Induced Superconductivity in κ-(ET)_{2}-X.

Resonant optical excitation of certain molecular vibrations in κ-(BEDT-TTF)_{2}Cu[N(CN)_{2}]Br has been shown to induce transient superconductinglike optical properties at temperatures far above equilibrium T_{c}. Here, we report experiments across the bandwidth-tuned phase diagram of this class of materials, and study the Mott insulator κ-(BEDT-TTF)_{2}Cu[N(CN)_{2}]Cl and the metallic compound κ-(BEDT-TTF)_{2}Cu(NCS)_{2}. We find nonequilibrium photoinduced superconductivity only in κ-(BEDT-TTF)_{2}Cu[N(CN)_{2}]Br, indicating that the proximity to the Mott insulating phase and possibly the presence of preexisting superconducting fluctuations are prerequisites for this effect.

Emergence of unconventional spin glass-like state in κ - (ET)2Cu[N(CN)2]Cl by introducing weak randomness

Recently, Urai et al. [Phys. Rev. Lett. 124, 117204 (2020)] reported that an antiferromagnetic long-range-ordered state in $\ensuremath{\kappa}$-${(\mathrm{ET})}_{2}\mathrm{Cu}\mathrm{[N}{(\mathrm{CN})}_{2}\mathrm{]Cl}$ changes into a quantum spin liquid via an unconventional spin glass-like state as randomness is introduced by x-ray irradiation. Here, we focused on the spin glass-like state and conducted a detailed investigation into it using $^{13}\mathrm{C}$-NMR measurements on 150-h x-ray-irradiated $\ensuremath{\kappa}$-$({\mathrm{ET})}_{2}\mathrm{Cu}\mathrm{[N(}{\mathrm{CN})}_{2}\mathrm{]Cl}$. We found that the spin glass-like state is composed of two components: the major component inherits the spin structure of nonirradiated $\ensuremath{\kappa}$-$({\mathrm{ET})}_{2}\mathrm{Cu}\mathrm{[N(}{\mathrm{CN})}_{2}\mathrm{]Cl}$, whereas the minor component differs from that of nonirradiated $\ensuremath{\kappa}$-${(\mathrm{ET})}_{2}\mathrm{Cu}\mathrm{[N(}{\mathrm{CN})}_{2}\mathrm{]Cl}$. We also found that in the spin glass-like state, spin moments fluctuate very slowly around stable directions even at low temperatures, which is very likely related to the Griffiths physics.

Symmetry change of d -wave superconductivity in κ -type organic superconductors

Magnetic-field-angle-resolved heat capacity of dimer-Mott organic superconductors $\kappa$-(BEDT-TTF)$_2$$X$ is reported. Temperature and field dependence of heat capacity indicates that the superconductivity has line nodes on the Fermi surface, which is a typical feature of $d$-wave superconductivity. In-plane field-angle dependence exhibits fourfold oscillations as well as twofold oscillations due to anisotropy of superconducting gap functions. From analyses of the fourfold term, the gap symmetry is determined as $d_{x^{2}-y^{2}}$+$s_{\pm}$ for $X$=Cu[N(CN)$_2$]Br and $d_{xy}$ for $X$=Ag(CN)$_2$H$_2$O. We suggest that the symmetry difference comes from the competition of $d_{xy}$ and $d_{x^{2}-y^{2}}$ antiferromagnetic fluctuations depending on lattice geometry.

Interacting electron spins in κ−(BEDT-TTF)2Cu[N(CN)2]I investigated by ESR spectroscopy

We performed angular and temperature-dependent electron-spin-resonance measurements in the quasi-two-dimensional organic conductor $\kappa$-(BEDT-TTF)$_2$Cu[N(CN)$_2$]I. The interlayer spin-diffusion is much weaker compared to the Cl- and Br-analogues, which are antiferromagnetic insulator and paramagnetic metal, respectively; $\kappa$-(BEDT-TTF)$_2$Cu[N(CN)$_2$]I behaves insulating when cooled below $T$ = 200 K. A spin gap ($\Delta\approx$ 18 K) opens at low temperatures leading to a spin-singlet state. Due to intrinsic disorder a substantial number of spins ($\sim$ 1 $\%$) remains unpaired. We observe additional signals below $T$ = 4 K with a pronounced anisotropy indicating the presence of local magnetic moments coupled to some fraction of those unpaired spins.

Dynamical Order and Superconductivity in a Frustrated Many-Body System.

In triangular lattice structures, spatial anisotropy and frustration can lead to rich equilibrium phase diagrams with regions containing complex, highly entangled states of matter. In this work, we study the driven two-rung triangular Hubbard model and evolve these states out of equilibrium, observing how the interplay between the driving and the initial state unexpectedly shuts down the particle-hole excitation pathway. This restriction, which symmetry arguments fail to predict, dictates the transient dynamics of the system, causing the available particle-hole degrees of freedom to manifest uniform long-range order. We discuss implications of our results for a recent experiment on photoinduced superconductivity in κ-(BEDT-TTF)_{2}Cu[N(CN)_{2}]Br molecules.

Competition between Interactions and Randomness in Photoinduced Synchronization of Charge Oscillations on a Dimer Lattice

The synchronization of charge oscillations after photoexcitation that has been realized through the emergence of an electronic breathing mode on dimer lattices is studied here from the viewpoint of the competition between interactions and randomness. We employ an extended Hubbard model at three-quarter filling on a simple dimer lattice and add random numbers to all transfer integrals between nearest-neighbor sites. Photoinduced dynamics are calculated using the time-dependent Schr\"odinger equation by the exact diagonalization method. Although the randomness tends to unsynchronize charge oscillations on different bonds during and after photoexcitation, sufficiently strong on-site repulsion $U$ overcomes this effect and synchronizes these charge oscillations some time after strong photoexcitation. The degree of synchronization is evaluated using an order parameter that is derived from the time profiles of the current densities on all bonds. As to the nearest-neighbor interaction $V$, if $V$ is weakly attractive, it increases the order parameter by facilitating the charge oscillations. The relevance of these findings to previously reported experimental and theoretical results for the organic conductor $\kappa$-(bis[ethylenedithio]tetrathiafulvalene)$_2$Cu[N(CN)$_2$]Br is discussed.

Polarized Time-Resolved Spectroscopy of Electronic Phase Separation in a Dimer-Mott Organic Insulator

The electronic state of the organic single crystal $\kappa -\left [ \left (\text {d-BEDT-TTF} \right )_{0.5} \left (\text {h-BEDT-TTF}\right )_{0.5}\right ]_{2}$ Cu[N(CN)2]Br, in which $\sim $ 50 percent of the BEDT-TTF molecules are substituted by fully deuterated molecules (d-BEDT-TTF), has been characterized by resistance and polarized time-resolved spectroscopy measurements. We found that while the resistance shows no sign of a superconducting transition, the polarized time-resolved spectroscopy reveals a slow decay dynamics associated with the superconducting phase at a low temperature. The result suggests phase separation between the insulating and superconducting phases in the vicinity of the first-order Mott transition. In addition, we found that this slow component shows a steep increase below $\sim $ 18 K, suggesting a fluctuating superconductivity in the conducting domains. Furthermore, the component persists up to at least $\sim $ 50 K, which is almost consistent with the onset temperature of the anomalous magnetic-field-dependent signals observed by the previous Nernst effect measurements (Nam et al. Sci. Rep.3:3390, 2013) of the alloy κ-(BEDT-TTF)2Cu[N(CN)2]Cl0.27Br0.73. While interpretation of these anomalies is still debatable, there exists a possibility of the onset of superconducting paring at a very high temperature.

Lattice Dynamics Coupled to Charge and Spin Degrees of Freedom in the Molecular Dimer-Mott Insulator κ-(BEDT-TTF)_{2}Cu[N(CN)_{2}]Cl.

Inelastic neutron scattering measurements on the molecular dimer-Mott insulator κ-(BEDT-TTF)_{2}Cu[N(CN)_{2}]Cl reveal a phonon anomaly in a wide temperature range. Starting from T_{ins}∼50-60 K where the charge gap opens, the low-lying optical phonon modes become overdamped upon cooling towards the antiferromagnetic ordering temperature T_{N}=27 K, where also a ferroelectric ordering at T_{FE}≈T_{N} occurs. Conversely, the phonon damping becomes small again when spins and charges are ordered below T_{N}, while no change of the lattice symmetry is observed across T_{N} in neutron diffraction measurements. We assign the phonon anomalies to structural fluctuations coupled to charge and spin degrees of freedom in the BEDT-TTF molecules.

Unified Assessment of the Effects of Van der Waals Interactions on the Structural and Electronic Properties of Some Layered Organic Solids κ-(BEDT-TTF)2X

Proper inclusion of van der Waals interactions (vdW) in ab initio calculations based on the density functional theory (DFT) is crucial to describe soft, organic, layered solids such as κ -(BEDT-TTF) 2 X . Since no consensus has been reached on the reliability of available vdW DFT functionals, most of the first principles calculations have been based on experimental crystal structure data without any structural optimization. Here, we explore optimal DFT-based schemes that account for the effects of vdW interactions on the structural and electronic band properties of three paradigmatic charge transfer salts, κ -(BEDT-TTF) 2 Cu 2 (CN) 3 , κ -(BEDT-TTF) 2 Ag 2 (CN) 3 , and κ -(BEDT-TTF) 2 Cu[N(CN) 2 ]Cl, for which a unified optimization of the structure is possible. Detailed examination of the prototype test system κ -(BEDT-TTF) 2 Cu[N(CN) 2 ]Cl shows that the optB88-vdW functional performs slightly better than the PBE-vdW and that the choice of pseudopotentials is critical to obtaining realistic results.

Low‐Frequency Charge Carrier Dynamics in Ferroelectric κ‐(BEDT‐TTF)2X – A Comparative Study of X = Cu[N(CN)2]Cl and X = Hg(SCN)2Cl

This paper presents a comparative study of the low‐frequency charge carrier fluctuations of κ‐(ET)2Cu[N(CN)2]Cl (κ‐Cl) and κ‐(ET)2Hg(SCN)2Cl (κ‐Hg‐Cl), two organic charge‐transfer salts exhibiting a Mott‐insulating and charge‐ordered ground state, respectively, accompanied by ferroelectric order. For κ‐Cl, pronounced random telegraph signals are found, which are enhanced over the 1/f‐background fluctuations at characteristic temperatures where changes of either the structural or the electronic dynamics occur. From the shift of the characteristic frequencies with temperature, the corresponding activation energies are extracted. The switching of polar nanoregions related to relaxor ferroelectricity of the investigated sample is suggested as origin of the observed transport dynamics around TFE. For κ‐Hg‐Cl (showing long‐range ferroelectric order accompanied by a charge ordering metal–insulator transition), strong changes and a sharp peak in the low‐frequency fluctuations at TMI are found. For this compound also, spatially correlated and electric field‐dependent fluctuations are observed in the ferroelectric phase.

Fluctuating superconductivity in κ-type organic compounds probed by polarized time-resolved spectroscopy

In this work, polarized time-resolved spectroscopy was carried out to investigate a superconducting (SC) state of the organic compounds κ-(BEDT-TTF)2X (X = Cu(NCS)2 (κ-NCS, Tc ∼ 9K) and Cu[N(CN)2]Br (κ-Br, Tc ∼ 12 K)), which have different effective electron correlations. We found that the SC response, which was characterized by probe polarization anisotropy with slow relaxation time, decreases steeply at approximately in κ-NCS with increasing temperature, corresponding to the closing of the SC gap. On the other hand, in κ-Br the SC response persisted significantly above . The results indicate that fluctuating superconductivity (FSC) emerges in κ-Br but not in κ-NCS, suggesting that strong electron correlation can play a critical role for FSC.

Electrodynamics in Organic Dimer Insulators Close to Mott Critical Point

Organic layered charge-transfer salts κ -(BEDT-TTF) 2 X form highly frustrated lattices of molecular dimers in which strong correlations give rise to Mott insulating states situated close to the metal-to-insulator phase boundary. The salts κ -(BEDT-TTF) 2 Cu 2 (CN) 3 and κ -(BEDT-TTF) 2 Ag 2 (CN) 3 have been considered as prime candidates for a quantum spin liquid, while κ -(BEDT-TTF) 2 Cu[N(CN) 2 ]Cl has been suggested as a prototypical charge-order-driven antiferromagnet. In this paper, we summarize and discuss several key results, including some not reported previously, obtained in search to clarify the competition of these two ground states. The origin of anomalous dielectric response found at low temperatures in all three salts is also discussed. We conclude by pointing out the relevant new insights into the role of frustration and random disorder in the suppression of magnetic ordering and formation of the spin liquid state.

Orbital effect for the Fulde-Ferrell-Larkin-Ovchinnikov phase in a quasi-two-dimensional superconductor in a parallel magnetic field

We theoretically study the orbital destructive effect against superconductivity in a parallel magnetic field in the Fulde-Ferrell-Larkin-Ovchinnikov (FFLO or LOFF) phase at zero temperature in a quasi-two-dimensional (Q2D) conductor. We demonstrate that at zero temperature a special parameter, $\lambda = l_{\perp}(H)/d$, is responsible for strength of the orbital effect, where $l_{\perp}(H)$ is a typical "size" of the quasi-classical electron orbit in a magnetic field and $d$ is the inter-plane distance. We discuss applications of our results to the existing experiments on the FFLO phase in the organic Q2D conductors $\kappa$-(ET)$_2$Cu(NCS)$_2$ and $\kappa$-(ET)$_2$Cu[N(CN)$_2$]Cl.

Effects of Disorder on the Pressure-Induced Mott Transition in κ-(BEDT-TTF)2Cu[N(CN)2]Cl

We present a study of the influence of disorder on the Mott metal-insulator transition for the organic charge-transfer salt κ -(BEDT-TTF) 2 Cu[N(CN) 2 ]Cl. To this end, disorder was introduced into the system in a controlled way by exposing the single crystals to X-ray irradiation. The crystals were then fine-tuned across the Mott transition by the application of continuously controllable He-gas pressure at low temperatures. Measurements of the thermal expansion and resistance show that the first-order character of the Mott transition prevails for low irradiation doses achieved by irradiation times up to 100 h. For these crystals with a moderate degree of disorder, we find a first-order transition line which ends in a second-order critical endpoint, akin to the pristine crystals. Compared to the latter, however, we observe a significant reduction of both, the critical pressure p c and the critical temperature T c . This result is consistent with the theoretically-predicted formation of a soft Coulomb gap in the presence of strong correlations and small disorder. Furthermore, we demonstrate, similar to the observation for the pristine sample, that the Mott transition after 50 h of irradiation is accompanied by sizable lattice effects, the critical behavior of which can be well described by mean-field theory. Our results demonstrate that the character of the Mott transition remains essentially unchanged at a low disorder level. However, after an irradiation time of 150 h, no clear signatures of a discontinuous metal-insulator transition could be revealed anymore. These results suggest that, above a certain disorder level, the metal-insulator transition becomes a smeared first-order transition with some residual hysteresis.

N-Type Superconductivity in an Organic Mott Insulator Induced by Light-Driven Electron-Doping.

The presence of interface dipoles in self-assembled monolayers (SAMs) gives rise to electric-field effects at the device interfaces. SAMs of spiropyran derivatives can be used as photoactive interface dipole layer in field-effect transistors because the photochromism of spiropyrans involves a large dipole moment switching. Recently, light-induced p-type superconductivity in an organic Mott insulator, κ-(BEDT-TTF)2 Cu[N(CN)2 ]Br (κ-Br: BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene) has been realized, thanks to the hole carriers induced by significant interface dipole variation in the spiropyran-SAM. This report explores the converse situation by designing a new type of spiropyran monolayer in which light-induced electron-doping into κ-Br and accompanying n-type superconducting transition have been observed. These results open new possibilities for novel electronics utilizing a photoactive SAMs, which can design not only the magnitude but also the direction of photoinduced electric-fields at the device interfaces.

About the air- and water-stable copper(I) dicyanamide: synthesis, crystal structure, vibrational spectra and DSC/TG analysis of Cu[N(CN)2

Abstract Light-yellow microcrystalline samples of Cu[dca] ([dca]−≡[N(CN)2]−≡dicyanamide anion) were obtained by blending an in-situ generated aqueous Cu+ brine with stoichiometric amounts of Na[dca] dissolved in water. The crystal structure of Cu[dca] was solved and refined from powder X-ray diffraction (PXRD) data. Cu[dca] crystallizes in the orthorhombic space group Cmcm (no. 63) with the lattice parameters of a=356.28(3), b=611.10(9) and c=1525.87(10) pm. The crystal structure contains undulated chains of alternating Cu+ and boomerang-shaped [N≡C–N–C≡N]− ions with C 2v symmetry running along [100]. It is closely related to that of Ag[dca] crystallizing in space group Pnma (no. 62). The vibrational spectra for Cu[dca] and Cu[dca]2 were recorded exhibiting modes typical for the dicyanamide anion. Comparative DSC/TG measurements were performed for both copper dicyanamides and the cyanide Cu[CN].