The origin of the gap in NiS2 as well as the pressure- and doping-induced metal-insulator transition in the NiS2-xSex solid solutions are investigated both theoretically using the first-principles band structures combined with the dynamical mean-field approximation for the electronic correlations and experimentally by means of infrared and x-ray absorption spectroscopies. The bonding-antibonding splitting in the S-S (Se-Se) dimer is identified as the main parameter controlling the size of the charge gap. The implications for the metal-insulator transition driven by pressure and Se doping are discussed.
The metal to insulator transition in the charge transfer NiS{2-x}Se{x} compound has been investigated through infrared reflectivity. Measurements performed by applying pressure to pure NiS2 (lattice contraction) and by Se-alloying (lattice expansion) reveal that in both cases an anomalous metallic state is obtained. We find that optical results are not compatible with the linear Se-alloying vs Pressure scaling relation previously established through transport, thus pointing out the substantially different microscopic origin of the two transitions.
Femtosecond time-resolved mid-infrared reflectivity is used to investigate the electron and phonon dynamics occurring at the direct band gap of the excitonic insulator Ta$_2$NiSe$_5$ below the critical temperature of its structural phase transition. We find that the phonon dynamics show a strong coupling to the excitation of free carriers at the Γ point of the Brillouin zone. The optical response saturates at a critical excitation fluence $F_C = 0.30~\pm~0.08$~mJ/cm$^2$ due to optical absorption saturation. This limits the optical excitation density in Ta$_2$NiSe$_5$ so that the system cannot …
We report on a combined measurement of high-resolution x-ray diffraction on powder and Raman scattering on single crystalline NiS2-xSex samples that exhibit the insulator-metal transition with Se doping. Via x-rays, an abrupt change in the bond length between Ni and S (Se) ions was observed at the transition temperature, in sharp contrast to the almost constant bond length between chalcogen ions. Raman scattering, a complementary technique with the unique sensitivity to the vibrations of chalcogen bonds, revealed no anomalies in the phonon spectrum, consistent with the x-ray diffraction result…
We performed ultrasonic measurements on (Ta$_{0.952}$V$_{0.048}$)$_2$NiSe$_5$ to investigate the contribution of acoustic phonons at the zone center to structural and possible excitonic transitions. The transverse elastic constant $C_{55}$ with irreducible representation $B_\mathrm{2g}$ exhibits softening over 90\% above a transition temperature of $T_\mathrm{s} = 280$ K, indicating the soft mode of corresponding TA phonons. Our analysis based on the quadrupole response indicates that the electron-phonon interaction contributes to the excitonic transition in addition to the hybridization betwe…
We investigate an interesting anisotropic van der Waals material, Ta$_{2}$NiSe$_{5}$, using optical spectroscopy. Ta$_{2}$NiSe$_{5}$ has been known as one of the few excitonic insulators proposed over 50 years ago. Ta$_{2}$NiSe$_{5}$ has quasi-one dimensional chains along the $a$-axis. We have obtained anisotropic optical properties of a single crystal Ta$_{2}$NiSe$_{5}$ along the $a$- and $c$-axes. The measured $a$- and $c$-axis optical conductivities exhibit large anisotropic electronic and phononic properties. With regard to the $a$-axis optical conductivity, a sharp peak near 3050 cm$^{-1}…
We present resistivity measurements of Mott insulator NiS2 single crystals after heat treatment. We find a strong increase of the low temperature resistivity that relaxes back towards the pristine behaviour over several days with a time constant of 45 h at room temperature. The low temperature resistivity has previously been shown to be dominated by surface conduction (T. Thio and J. Bennett, PRB 50 10574 1994). Consequently, the changes induced by heat treatment are attributed to changes to surface states. Our results suggest the creation of vacancies in the surface that re refilled from the …
Tuning many-body electronic phases by an external handle is of both fundamental and practical importance in condensed matter science. The tunability mirrors the underlying interactions, and gigantic electric, optical and magnetic responses to minute external stimuli can be anticipated in the critical region of phase change. The excitonic insulator is one of the exotic phases of interacting electrons, produced by the Coulomb attraction between a small and equal number of electrons and holes, leading to the spontaneous formation of exciton pairs in narrow-gap semiconductors/semimetals. The layer…
Excitonic insulator (EI) was proposed in 60's as a distinct insulating state originating from pure electronic interaction, but its material realization has been elusive with extremely few material candidates and with only limited evidence such as anomalies in transport properties, band dispersions, or optical transitions. We investigate the real-space electronic states of the low temperature phase in Ta$_2$NiSe$_5$ with an atomic resolution to clearly identify the quasiparticle energy gap together with the strong electron-hole band renormalization using scanning tunneling microscopy (STM) and …
The metal-insulator transition and the problem of d-electron delocalization are investigated in the pyrite system NiS_{2-x}Se_x under pressure using density functional theory (DFT). We test several approximations, including the generalized gradient approximation (GGA), the GGA+U approach, and hybrid functionals. In addition we apply the GW approximation and perform Hartree-Fock calculations. The important role of the chalcogen dimers in the electronic structure is discussed within GGA, which sufficiently describes the role of the lattice in the metal-insulator transition. In addition, the magn…
We report on the nonequilibrium dynamics of the electronic structure of the layered semiconductor Ta$_2$NiSe$_5$ investigated by time- and angle-resolved photoelectron spectroscopy. We show that below the critical excitation density of $F_{C} = 0.2$ mJ cm$^{-2}$, the band gap $narrows$ transiently, while it is $enhanced$ above $F_{C}$. Hartree-Fock calculations reveal that this effect can be explained by the presence of the low-temperature excitonic insulator phase of Ta$_2$NiSe$_5$, whose order parameter is connected to the gap size. This work demonstrates the ability to manipulate the band g…
The excitonic insulator Ta$_2$NiSe$_5$ experiences a first-order structural transition under pressure from rippled to flat layer-structure at Ps = 3 GPa, which drives the system from an almost zero-gap semiconductor to a semimetal. The pressure-induced semimetal, with lowering temperature, experiences a transition to another semimetal with a partial-gap of 0.1-0.2 eV, accompanied with a monoclinic distortion analogous to that occurs at the excitonic transition below Ps. We argue that the partial-gap originates primarily from a symmetry-allowed hybridization of Ta-conduction and Ni-valence band…
We investigate the non-equilibrium electronic structure and characteristic time scales in a candidate excitonic insulator, Ta$_2$NiSe$_5$, using time- and angle-resolved photoemission spectroscopy with a temporal resolution of 50 fs. Following a strong photoexcitation, the band gap closes transiently within 100 fs, i.e., on a time scale faster than the typical lattice vibrational period. Furthermore, we find that the characteristic time associated with the rise of the photoemission intensity above the Fermi energy decreases with increasing excitation strength, while the relaxation time of the …
The electronic structure change of NiS$_{2-x}$Se$_x$ as a function of Se concentration $x$ has been studied by Ni $L$-edge X-ray absorption spectroscopy (XAS). The XAS spectra show distinct features in Ni $L_3$ edge, indicating whether the system is insulating or metallic. These features can be semi-quantitatively explained within the framework of the configurational interaction cluster model (CICM). In the S-rich region, relatively large charge-transfer energy ($Δ\sim 5$ eV) from ligand $p$ to Ni 3$d$ states and a little small $p$-$d$ hybridization strength ($V_{pdσ} \sim 1.1$ eV) can reprodu…
Transition metal chalcogenide Ta$_2$NiSe$_5$, a promising material for the excitonic insulator, is investigated on the basis of the quasi-one-dimensional three-chain Hubbard model with two conduction ($c$) bands and one valence ($f$) band. In the semimetallic case where only one of two $c$ bands and the $f$ band cross the Fermi level, the transition from the $c$-$f$ compensated semimetal to the uniform excitonic insulator takes place at low temperature as the same as in the semiconducting case. On the other hand, when another $c$ band also crosses the Fermi level, the system shows three types …
Motivated by the existence of superconductivity in pyrite-structure CuS$_2$, we explore the possibility of ionic-liquid-gating-induced superconductivity in the proximal antiferromagnetic Mott insulator NiS$_2$. A clear gating-induced transition from a two-dimensional insulating state to a three-dimensional metallic state is observed at positive gate bias on single crystal surfaces. No evidence for superconductivity is observed down to the lowest measured temperature of 0.45 K, however. Based on transport, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, atomic force micr…
Substrate tuning of the structural and electronic transition in thin flakes of the excitonic insulator candidate Ta$_2$NiSe$_5$
Max Planck Institute for Solid State Research（马克斯·普朗克固体研究所）；Institute for Functional Matter and Quantum Technologies, University of Stuttgart（斯图加特大学功能物质与量子技术研究所）；Department of Physics, University of Tokyo（东京大学物理系）
Ta$_2$NiSe$_5$ became one of the most investigated candidate materials for hosting an excitonic insulator ground state. Many studies describe the corresponding phase transition as a condensation of excitons breaking a continuous symmetry. This view got challenged recently pointing out the importance of the loss of two mirror symmetries at a structural phase transition that occurs together with the semiconductor-excitonic insulator transition. For such a scenario an unstable optical zone-center phonon at low energy is proposed to drive the transition. Here we report on the experimental observat…
Excitonic insulator (EI) is an intriguing insulating phase of matter, where electrons and holes are bonded into pairs, so called excitons, and form a phase-coherent state via Bose-Einstein Condensation (BEC). Its theoretical concept has been proposed several decades ago, but the followed research is very limited, due to the rare occurrence of EI in natural materials and the lack of manipulating method of excitonic condensation. In this paper, we report the realization of a doping-controlled EI-to-semi-metal transition in Ta$_2$NiSe$_5$ using $in$-$situ$ potassium deposition. Combining with ang…
NiS, exhibiting a text-book example of a first-order transition with many unusual properties at low temperatures, has been variously described in terms of conflicting descriptions of its ground state during the past several decades. We calculate these physical properties within first-principle approaches based on the density functional theory and conclusively establish that all experimental data can be understood in terms of a rather unusual ground state of NiS that is best described as a self-doped, nearly compensated, antiferromagnetic metal, resolving the age-old controversy. We trace the o…
Utilizing the time-dependent density-matrix renormalization group technique, we numerically prove photoinduced pairing states in the extended Falicov-Kimball model (EFKM) at half filling, both with and without internal SU(2) symmetry. In the time-dependent photoemission spectra an extra band appears above the Fermi energy after pulse irradiation, indicating an insulator-to-metal transition. Even in the absence of the SU(2) structure, the pair correlations are enhanced during the pump, and afterwards decrease over time. This implies the possible metallization of Ta$_2$NiSe$_5$, a strong candida…
Non-collinear Altermagnetic Phases in the Mott Insulator NiS$_2$
Leibniz Institute for Solid State and Materials Research（莱布尼茨固体与材料研究所）；Technische Universitat Dresden（德累斯顿工业大学）；Laboratoire Léon Brillouin, CEA, CNRS, Université Paris-Saclay（塞奈-萨克雷大学、法国原子能与替代能源委员会、法国国家科学研究中心勒昂布里渊实验室）；Université de Sherbrooke（舍布鲁克大学）；Donostia International Physics Center（圣塞巴斯蒂安国际物理中心）；Regroupement Québécois sur les Matériaux de Pointe (RQMP)（魁北克尖端材料研究联合体）
The metal--insulator phase transition is considered on the basis of Ginzburg-Landau type equations with two different order parameters. An inclusion of magnetic field in this picture is an important step for understanding of behavior of the metal--insulator phase transition kinetics. The magnetic field leads to various singularities of the surface tension and results in drastic variations of the phase transition kinetics. The strongest singularity is due to Landau diamagnetism and determines anomalous features of MI transition kinetics. This singularity supports the well known experimental fac…
Metal-insulator transition features as a transformation, from a highly charge conductive state to another state where charge conductivity is greatly suppressed when decreasing the temperature. Here we demonstrate two consecutive transitions in NdNiO3 films with CoFe2O4 capping, in which the metal-insulator transition occurs at 85 K, followed by an unprecedented insulator-metal transition below 40 K. The emerging insulator-metal transition associated with a weak antiferromagnetic behavior is observed in 20 unit cell-thick NdNiO3 with more than 5 unit cell CoFe2O4 capping. Differently, the NdNiO…
The periodic Anderson lattice model for the crystalline electric field (CEF)split 4f quartet states is used to describe the Yb-based Kondo insulators/semiconductors. In the slave-boson mean-field approximation, we derive the hybridized quasiparticle bands, and find that decreasing the hybridization difference of the two CEF quartets may induce an insulator-to-metal phase transition. The resulting metallic phase has a hole and an electron Fermi pockets. Such a phase transition may be realized experimentally by applying pressure, reducing the difference in hybridization of the two CEF quartets.
We derived a simple metal-insulator criterion in analytical form for the doped Mott-Hubbard materials. Its readings closely related to the orbital and spin nature of the ground states of the unit cell. The available criterion readings (metal or insulator) in the paramagnetic phase points to the possibility of the insulator state of doped materials with the forbidden first removal electron states. According to its physical meaning the result is similar to Wilsons criterion in the itinerant electron systems. An application of the criterion to the high-Tc cuprates discussed.
It is well established that for non-interacting electrons, increasing disorder drives a metal into a gapless localized Anderson insulator. While in three dimensions a threshold in disorder must be crossed for the transition, in two dimensions and lower, the smallest amount of disorder destabilizes the metal. The nature of the metal-insulator transition in an interacting system remains unresolved. Here we explore the effect of disorder on a strongly correlated Mott insulator without changing the carrier concentration. Angle resolved photoemission spectroscopy (ARPES) measurements on copper inte…
The metal-insulator transition of the quarter-filled Hubbard model on triangular lattice is studied at the mean field level. We find a quasi-one dimensional metallic state with a collinear magnetic order competes closely with an insulating state with a non-coplanar magnetic order for both signs of the hopping integral $t$. In the strong correlation regime($U/|t|\gg1$), it is found that the metal-insulator transition of the system occurs in a two-step manner. The quasi-one dimensional metallic state with collinear magnetic order is found to be stable in an intermediate temperature region betwee…
We consider a heterostructure of a metal and a barrier with onsite correlation at half filling using unrestricted Hartree Fock. We find that above a certain value of correlation strength in the barrier planes, the system is a Mott insulator, while below this value the system still behaves like a gapless insulator. The energy spectrum is found to be very novel with the presence of multiple gaps. Thus the system remains non metallic for any finite value of correlation.
By means of first principles schemes based on magnetically constrained density functional theory and on the band unfolding technique we study the effect of doping on the conducting behaviour of the Lifshitz magnetic insulator NaOsO3. Electron doping is treated realistically within a supercell approach by replacing sodium with magnesium at different concentrations. Our data indicate that by increasing carrier concentration the system is subjected to two types of transition: (i) insulator to bad metal at low doping and low temperature and (ii) bad metal to metal at high doping and/or high-temper…
In contrast to the Hubbard model, the extended Hubbard model, which additionally accounts for non-local interactions, lacks systemic studies of thermodynamic properties especially across the metal-insulator transition. Using a variational principle, we perform such a systematic study and describe how non-local interactions screen local correlations differently in the Fermi-liquid and in the insulator. The thermodynamics reveal that non-local interactions are at least in parts responsible for first-order metal-insulator transitions in real materials.
The organic salt $α$-(BEDT-TTF)$_2$I$_3$ is considered a model system for metal-insulator transition due to electronic charge ordering at $T_{\rm CO}=135$~K. The optical properties obtained from polarized reflection measurements above and below $T_{\rm CO}$ can be well described by calculations based on first-principle density-functional theory (DFT). We discuss the effect of electronic correlations on the metal-insulator transition.
