The layered chalcogenide Ta$_{2}$NiSe$_{5}$ has been proposed to host an excitonic condensate in its ground state, a phase that could offer a unique platform to study and manipulate many-body states at room temperature. However, identifying the dominant microscopic contribution to the observed spontaneous symmetry breaking remains challenging, perpetuating the debate over the ground state properties. Here, using broadband ultrafast spectroscopy we investigate the out-of-equilibrium dynamics of Ta$_{2}$NiSe$_{5}$ and demonstrate that the transient reflectivity in the near-infrared range is connected to the system's low-energy physics. We track the status of the ordered phase using this optical signature, establishing that high-fluence photoexcitations can suppress this order. From the sub-50 fs quenching timescale and the behaviour of the photoinduced coherent phonon modes, we conclude that electronic correlations provide a decisive contribution to the excitonic order formation. Our results pave the way towards the ultrafast control of an exciton condensate at room temperature.
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 insulators host a condensate of electron-hole pairs at equilibrium, giving rise to collective many-body effects. Although several materials have emerged as excitonic insulator candidates, evidence of long-range coherence is lacking and the origin of the ordered phase in these systems remains controversial. Here, using ultrafast pump-probe microscopy, we investigate the possible excitonic insulator Ta$_2$NiSe$_5$. Below 328 K, we observe the anomalous micrometer-scale propagation of coherent modes at velocities of the order of $\sim10^5$ m/s, which we attribute to the hybridization be…
The microscopic quantum interference associated with excitonic condensation in Ta$_2$NiSe$_5$ is studied in the BCS-type mean-field approximation. We show that in ultrasonic attenuation the coherence peak appears just below the transition temperature $T_{\rm c}$ whereas in NMR spin-lattice relaxation the rate rapidly decreases below $T_{\rm c}$; these observations can offer a crucial experimental test for the validity of the excitonic condensation scenario in Ta$_2$NiSe$_5$. We also show that the excitonic condensation manifests itself in a jump of the heat capacity at $T_{\rm c}$ as well as i…
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 origin of the second order phase transition at 328K in Ta$_2$NiSe$_5$, a prominent candidate for direct gap excitonic insulator, remains under fervent debate. The driving force for the transition can be revealed by identification of the soft mode's origin that may be deducted from polarization resolved Raman scattering experiments. Such studies were recently reported in [arXiv:2007.07344 (2020)], [arXiv:2102.07912 (2021)], [arXiv:2007.01723 (2020)] and [arXiv:2007.08212 (2020)]. In this Comment, it is shown that the parameters derived in a recent arXiv by Kwangrae Kim et. al. [arXiv:2007.0…
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…
The three-chain Hubbard model for Ta$_2$NiSe$_5$ known as a candidate material for the excitonic insulator is investigated over the wide range of energy gap $D$ between the two-fold degenerate conduction bands and the nondegenerate valence band including both semiconducting ($D>0$) and semimetallic ($D<0$) cases. In the semimetallic case, the difference of the band degeneracy inevitably causes the imbalance of each Fermi wavenumber, resulting in a remarkable excitonic state characterized by the condensation of excitons with finite center-of-mass momentum $q$, the so-called Fulde-Ferrell-Larkin…
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$^{-1}…
Femtosecond time-resolved mid-infrared reflectivity is used to investigate the electron and phonon dynamics occurring at the direct band gap of the excitonic insulator Ta$_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 …
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 …
In the presence of electron-phonon coupling, an excitonic insulator harbors two degenerate ground states described by an Ising-type order parameter. Starting from a microscopic Hamiltonian, we derive the equations of motion for the Ising order parameter in the phonon coupled excitonic insulator Ta$_2$NiSe$_5$ and show that it can be controllably reversed on ultrashort timescales using appropriate laser pulse sequences. Using a combination of theory and time-resolved optical reflectivity measurements, we report evidence of such order parameter reversal in Ta$_2$NiSe$_5$ based on the anomalous b…
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 analyze the measured optical conductivity spectra using the density-functional-theory-based electronic structure calculation and density-matrix renormalization group calculation of an effective model. We show that, in contrast to a conventional description, the Bose-Einstein condensation of preformed excitons occurs in Ta$_2$NiSe$_5$, despite the fact that a noninteracting band structure is a band-overlap semimetal rather than a small band-gap semiconductor. The system above the transition temperature is therefore not a semimetal, but rather a state of preformed excitons with a finite 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 …
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）
The layered compound $\mathrm{Ta_2NiSe_5}$ is a quasi-one-dimensional and narrow-gap semiconductor, which is proposed to undergo a transition to an excitonic insulator at $T_\mathrm{c}=326$ K. We found a clear anomaly at $T_\mathrm{c}$ in the in-plane thermal conductivities both parallel ($\parallel$ $a$) and perpendicular ($\parallel$ $c$) to the one-dimensional chains, $κ_\mathrm{a}$ and $κ_\mathrm{c}$. While $κ_\mathrm{a}$ shows a rapid decrease below $T_\mathrm{c}$, $κ_\mathrm{c}$ shows a pronounced V-shaped suppression centered at $T_\mathrm{c}$. We argue that the decrease of $κ_\mathrm{a…
We report on the nonequilibrium dynamics of the electronic structure of the layered semiconductor Ta$_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…
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…
Utilizing the unbiased time-dependent density-matrix renormalization group technique, we examine the photoemission spectra in the extended Falicov-Kimball model at zero and finite temperatures, particularly with regard to the excitonic insulator state most likely observed in the quasi-one-dimensional material Ta$_2$NiSe$_5$. Working with infinite boundary conditions, we are able to simulate all dynamical correlation functions directly in the thermodynamic limit. For model parameters best suited for Ta$_2$NiSe$_5$ the photoemission spectra show a weak but clearly visible two-peak structure, aro…
The excitonic insulator is an electronically-driven phase of matter that emerges upon the spontaneous formation and Bose condensation of excitons. Detecting this exotic order in candidate materials is a subject of paramount importance, as the size of the excitonic gap in the band structure establishes the potential of this collective state for superfluid energy transport. However, the identification of this phase in real solids is hindered by the coexistence of a structural order parameter with the same symmetry as the excitonic order. Only a few materials are currently believed to host a domi…
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…
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…
We present a combined study from angle-resolved photoemission and density-functional theory calculations of the temperature-dependent electronic structure in the excitonic insulator candidate Ta$_2$NiSe$_5$. Our experimental measurements unambiguously establish the normal state as a semimetal with a significant band overlap of $>$100~meV. Our temperature-dependent measurements indicate how these low-energy states hybridise when cooling through the well-known 327~K phase transition in this system. From our calculations and polarisation-dependent photoemission measurements, we demonstrate the im…
Using a combination of infrared ellipsometry, time-domain terahertz spectroscopy, and far-infrared reflectometry we have obtained the $ac$-plane complex dielectric function of monoclinic ($C2/c$) Ta$_2$NiSe$_5$ and orthorhombic ($Cmcm$) Ta$_2$NiS$_5$ single crystals. The identified dipole-active phonon modes polarized along $a$ and $c$ axes are in good agreement with density functional theory calculations. With increasing temperature the $a$-axis phonon modes of Ta$_2$NiSe$_5$ become poorly discernible, as they are superimposed on the electronic background which gradually fills the energy gap …
We study the temperature dependence of the orbital susceptibility of an excitonic insulator on the basis of a two-band model. It is shown that a drastic change (an anomalous enhancement) in susceptibility as a function of temperature occurs owing to the occurrence of additional orbital susceptibility due to the excitonic gap. We calculate explicitly the temperature dependence of orbital susceptibility for a model of Ta$_2$NiSe$_5$, and show that the result is consistent with experimental results.
We study the electron-hole pair (or excitonic) condensation in the extended Falicov-Kimball model at finite temperatures based on the cluster mean-field-theory approach, where we make the grand canonical exact-diagonalization analysis of small clusters using the sine-square deformation function. We thus calculate the ground-state and finite-temperature phase diagrams of the model, as well as its optical conductivity and single-particle spectra, thereby clarifying how the preformed pair states appear in the strong-coupling regime of excitonic insulators. We compare our results with experiment o…
Excitonic insulator is a coherent electronic phase that results from the formation of a macroscopic population of bound particle-hole pairs - excitons. With only a few candidate materials known, the collective excitonic behavior is challenging to observe, being obscured by crystalline lattice effects. Here we use polarization-resolved Raman spectroscopy to reveal the quadrupolar excitonic mode in the candidate zero-gap semiconductor Ta$_2$NiSe$_5$ disentangling it from the lattice phonons. The excitonic mode pronouncedly softens close to the phase transition, showing its electronic character, …
We show that in electron-hole bilayers with excitonic order arising from conduction and valence bands formed by atomic orbitals that have different parities, nonzero interlayer tunneling leads to a second order Josephson effect. This means the interlayer electrical current is related to the phase of the excitonic order parameter as $J = J_c \sin2θ$ instead of $J = J_c \sin θ$, and that the system has two degenerate ground states at $θ=0, π$ that can be switched by an interlayer voltage pulse. When generalized to a three dimensional stack of alternating electron-hole planes or a two dimensional…
The simultaneous condensation of electronic and structural degrees of freedom gives rise to new states of matter, including superconductivity and charge-density-wave formation. When exciting such a condensed system, it is commonly assumed that the ultrafast laser pulse disturbs primarily the electronic order, which in turn destabilizes the atomic structure. Contrary to this conception, we show here that structural destabilization of few atoms causes melting of the macroscopic ordered charge-density wave in 1T-TiSe2. Using ultrafast pump-probe non-resonant and resonant X-ray diffraction, we obs…
Using the band structure calculation and mean-field analysis of the derived three-chain Hubbard model with phonon degrees of freedom, we discuss the origin of the orthorhombic-to-monoclinic phase transition of the layered chalcogenide Ta$_2$NiSe$_5$. We show that the Bose-Einstein condensation of excitonic electron-hole pairs cooperatively induces the instability of the phonon mode at momentum $q\rightarrow 0$ in the quasi-one-dimensional Ta-NiSe-Ta chain, resulting in the structural phase transition of the system. The calculated single-particle spectra reproduce the deformation of the band st…
We consider a two-band spinless model describing an excitonic insulator (EI) on the two-dimensional square lattice with anisotropic hopping parameters and electron-phonon (el-ph) coupling, inspired by the EI candidate Ta$_2$NiSe$_5$. We systematically study the nature of the collective excitations in the ordered phase which originates from the interband Coulomb interaction and the el-ph coupling. When the ordered phase is stabilized only by the Coulomb interaction (pure EI phase), its collective response exhibits a massless phase mode in addition to the amplitude mode. We show that in the BEC …
An excitonic insulator phase is expected to arise from the spontaneous formation of electron-hole pairs (excitons) in semiconductors where the exciton binding energy exceeds the size of the electronic band gap. At low temperature, these ground state excitons stabilize a new phase by condensing at lower energy than the electrons at the valence band top, thereby widening the electronic band gap. The envisioned opportunity to explore many-boson phenomena in an excitonic insulator system is triggering a very active debate on how ground state excitons can be experimentally evidenced. Here, we emplo…
Using exact numerical techniques we investigate the nature of excitonic (electron-hole) bound states and the development of exciton coherence in the one-dimensional half-filled extended Falicov-Kimball model. The ground-state phase diagram of the model exhibits, besides band insulator and staggered orbital ordered phases, an excitonic insulator (EI) with power-law correlations. The criticality of the EI state shows up in the von Neumann entropy. The anomalous spectral function and condensation amplitude provide the binding energy and coherence length of the electron-hole pairs which, on their …
A three-orbital model derived from the two-dimensional projection of the $ab$ $initio$ Hamiltonian for alkaline doped fullerene A$_3$C$_{60}$ with A=Cs,Rb,K is studied by a variational Monte Carlo method. We correctly reproduce the experimental isotropic s-wave superconductivity around the $ab$ $initio$ parameters. With narrowing the bandwidth, the transition to an insulator is also reproduced, where orbital symmetry is found to be spontaneously broken with emergence of an excitonic Mott insulator for two orbitals and an antiferromagnetic insulator nearly degenerate with a spin liquid for the …
We study the dynamical phase transition out of an excitonic insulator phase after photo-excitation using a time-dependent extension of the selfconsistent GW method. We connect the evolution of the photoemission spectra to the dynamics of the excitonic order parameter and identify two dynamical phase transition points marked by a slowdown in the relaxation: one critical point is connected with the trapping in a nonthermal state with reduced exciton density and the second corresponds to the thermal phase transition. The transfer of kinetic energy from the photoexcited carriers to the exciton con…
We investigate out-of-equilibrium dynamics in an excitonic insulator (EI) with a finite momentum pairing perturbed by a laser-pulse excitation and a sudden coupling to fermionic baths. The transient dynamics of the excitonic order parameter is resolved using the full nonequilibrium Green's function approach and the generalized Kadanoff-Baym ansatz (GKBA) within the second-Born approximation. The comparison between the two approaches after a laser pulse excitation shows a good agreement in the weak and the intermediate photo-doping regime. In contrast, the laser-pulse dynamics resolved by the G…
