Electronic Instability Research Articles

Three-dimensional higher-order saddle-point-induced flatbands in Co-based kagome metals

The saddle point (Van Hove singularity) exhibits a divergent density of states in two-dimensional systems, leading to fascinating phenomena such as strong correlations and unconventional superconductivity, yet it is seldom observed in three-dimensional (3D) systems. In this work we find two types of 3D higher-order saddle points (HOSPs) in emerging 3D kagome metals YbCo6Ge6 and MgCo6Ge6. Both HOSPs exhibit a singularity in their density of states, which is significantly enhanced compared to the ordinary saddle point. The HOSP near the Fermi energy generates a flatband extending a large area in the Brillouin zone, potentially amplifying the correlation effect and fostering electronic instabilities. Two types of HOSPs exhibit distinct robustness upon element substitution and lattice distortions in these kagome compounds. Our work paves the way for engineering exotic band structures, such as saddle points and flatbands, and exploring interesting phenomena in Co-based kagome materials. Published by the American Physical Society 2024

Topological electronic structure and electronic nematicity in candidate kagome superconductors, ATi3Bi5 (A = Rb, Cs)

Abstract The newly discovered family of titanium-based kagome metals, ATi₃Bi₅ (where A can be Rb or Cs), has been found to exhibit non-trivial band topology and fascinating electronic instabilities, including electronic nematicity and potential bulk superconductivity. Distinct from their vanadium-based counterparts (AV₃Sb₅), which display a charge density wave (CDW) phase that already breaks rotational symmetry, ATi₃Bi₅ shows no evidence of CDW, providing a unique platform to study nematicity in its pure form and its interplay with other correlated quantum phenomena, such as superconductivity. In this review, we highlight recent progress in both experimental and theoretical research on ATi₃Bi₅ and discuss the unresolved questions and challenges in this burgeoning field.

Collapse of metallicity and high-Tc superconductivity in the high-pressure phase of FeSe0.89S0.11

We investigate the high-pressure phase of the iron-based superconductor FeSe0.89S0.11 using transport and tunnel diode oscillator studies using diamond anvil cells. We construct detailed pressure-temperature phase diagrams that indicate that the superconducting critical temperature is strongly enhanced by more than a factor of four towards 40 K above 4 GPa. The resistivity data reveal signatures of a fan-like structure of non-Fermi liquid behaviour which could indicate the existence of a putative quantum critical point buried underneath the superconducting dome around 4.3 GPa. With further increasing the pressure, the zero-field electrical resistivity develops a non-metallic temperature dependence and the superconducting transition broadens significantly. Eventually, the system fails to reach a fully zero-resistance state, and the finite resistance at low temperatures becomes strongly current-dependent. Our results suggest that the high-pressure, high-Tc phase of iron chalcogenides is very fragile and sensitive to uniaxial effects of the pressure medium, cell design and sample thickness. This high-pressure region could be understood assuming a real-space phase separation caused by nearly concomitant electronic and structural instabilities.

Identifying the β-to-α phase transition during the long cycling process in Na2FePO4F cathode

Na2FePO4F has emerged as a promising cathode for large-scale electrochemical energy storage, primarily due to its abundance of raw materials and distinctive two-dimensional ion channels. Counterintuitively, pristine Na2FePO4F lacks the long-term stability typically seen in polyanionic cathodes, which severely impedes its practical application. Traditionally, the origin of this problem has been only phenomenologically attributed to the poor intrinsic electronic conductivity and structural instability of Na2FePO4F. Here, we identify that rapid capacity fading of Na2FePO4F is closely related to the β-to-α phase transition during the long cycling process. Furthermore, we develop a practical high-entropy doping strategy and the corresponding microstructure engineering to mitigate the impact of the phase transition on the crystal structure, thereby increasing the capacity retention from 56 % to 94 % over 400 cycles at 0.5C in coin cell, and attain almost 100 % capacity retention after 300 cycles at 0.1C in pouch cell. Overall, this work unveils the mechanism of rapid capacity decay in Na2FePO4F and lays the groundwork for the rational design of durable polyanionic electrodes.

Numerical investigations of spatiotemporal dynamics of space-charge limited collisional sheaths

Electrostatic particle-in-cell (PIC) and direct simulation Monte Carlo (DSMC) methods are used to compare the plasma dynamics of collisionless with collisional emissive sheaths in partially ionized environments. Space-charge limited emissive sheaths submersed in a plasma with a density of ∼1017 m−3 are examined using a PIC-DSMC solver, CHAOS. Collisionless emissive sheaths with plasma domains sufficiently long (30 and 60 Debye lengths, λD) are subject to strong oscillations due to two-stream electron instability, whereas emissive sheaths in weakly collisional conditions with a short domain (15 λD) exhibit self-spike (sawtooth) oscillations in the plasma field due to the trapped charge-exchange (CEX) ion population within the virtual cathode (VC) region. The two-stream electron instability leads to strong temporal fluctuations in the total emission current, with maximum deviations of 60% and 100% from the time-averaged current for the long plasma domains, whereas CEX collisions cause strong spikes in the emission current if the domain size is short. Our PIC-DSMC simulations show for the first time that the interaction of the two types of instabilities causes the strength of the self-spike to be weakened due to the strong fluctuations caused by the two-stream instability when a sufficiently long computational domain with ion-neutral collisions is employed. By conducting a two-dimensional Fast Fourier Transform (FFT) on the collisional and collisionless sheaths with long domains, we show that the transient evolution of CEX entrapment in the VC increases frequency of sheath oscillations up to two times the ion-acoustic frequencies observed in the collisionless sheath. CEX collisions weaken the VC region and result in a total emission current more than that obtained from the collisionless case for the same domain length. With a more rarefied neutral environment of 1019 m−3 in the plasma sheath, the total emission current increases only 4% in comparison with 14% for one order of magnitude denser environment, within 20 μs. In addition, the spike period is tested with different neutral temperatures and densities. While we do not observe any self-spike in the more rarefied environment, the spike period increased from 5 to 7.5 μs when the neutral temperature is increased from 300 to 2000 K in the denser environment with the simulation time of 20 μs.

Dynamical decoding of the competition between charge density waves in a kagome superconductor

The kagome superconductor CsV3Sb5 hosts a variety of charge density wave (CDW) phases, which play a fundamental role in the formation of other exotic electronic instabilities. However, identifying the precise structure of these CDW phases and their intricate relationships remain the subject of intense debate, due to the lack of static probes that can distinguish the CDW phases with identical spatial periodicity. Here, we unveil the out-of-equilibrium competition between two coexisting 2 × 2 × 2 CDWs in CsV3Sb5 harnessing time-resolved X-ray diffraction. By analyzing the light-induced changes in the intensity of CDW superlattice peaks, we demonstrate the presence of both phases, each displaying a significantly different amount of melting upon excitation. The anomalous light-induced sharpening of peak width further shows that the phase that is more resistant to photo-excitation exhibits an increase in domain size at the expense of the other, thereby showcasing a hallmark of phase competition. Our results not only shed light on the interplay between the multiple CDW phases in CsV3Sb5, but also establish a non-equilibrium framework for comprehending complex phase relationships that are challenging to disentangle using static techniques.

Breakdown Time Phenomena: Analyzing the Conductive Channel of Positive Impulse Voltage Discharges under Standard Temperature and Pressure Air Conditions

Even though the streamer process can be identified in nanoseconds and microseconds through experimental measurements, the breakdown time of air discharge is still unknown. The instability of electrons is suspected to be an attachment-instability phenomenon of the channel conductivity. We investigated breakdown time across milliseconds to better understand how the oxygen excitations of the 200–400 nm range influence a high-conductivity channel even with a weaker applied voltage. Experiments were performed with positive impulse voltages ranging from +42 to +75 kV in the step of +6 kV at a 3 cm gap between needle-to-plane electrodes in a horizontal configuration. A spectrometer with an integration time of 70 ms was used to capture the spectra during voltage discharge. The shortest breakdown time was found at +60 kV with 77 ns compared to +66, +72, and +75 kV. We conclude that the shorter breakdown time at +60 kV is primarily due to the oxygen-excited state in O IV at 262.999 nm. This state helps maintain electron flow by preventing electron loss, with a decay time of 2.5 µs, while releasing Joule heat at a temperature of 26,003 K, which optimizes conductivity. This process occurs before the recombination of the O I line at 777.417 nm, which has a significantly shorter decay time of 27 ns.

Formation of hollow stepped FePBA@rGO anode for high-performance lithium-ion batteries

Prussian blue and its analogues (PBAs) have been considered promising anode materials for lithium-ion batteries (LIBs) owing to their high theoretical capacity and cost-effectiveness. However, they often encounter challenges such as poor electronic conductivity and structural instability. Herein, we introduce a hollow stepped FePBA framework structure coated with reduced graphene oxide (FePBA@rGO). This sophisticated design significantly improves electronic conductivity and optimizes the diffusion pathways for lithium ions, leading to exceptional cycling stability and rate performance. The FePBA@rGO-15 anode developed in this study shows a notable rate capability of 294 mAh g−1 at a current density of 2 A g−1. More significantly, it demonstrates exceptional lithium storage performance, maintaining a capacity of 1245 mAh g−1 after 600 cycles at a current density of 1 A g−1. Density functional theory simulations further support our findings by illustrating that the robust interface between FePBA and rGO significantly accelerates the reactions kinetics of Li+ within the FePBA framework. This study represents a significant advancement towards improving the capacity and cycling stability of PBA-based anode materials, offering promising prospects for future battery applications.

Understanding Atomic-Scale Dynamics of Defects in Complex Oxides for Memristive Devices

The exceptional resistive switching characteristics of complex oxides make them promising for use in memristors to mimic biological synapses in neuromorphic computing architectures in an energy-efficient manner. Specifically, the electrical conductance of complex oxides can be controllable switched across multiple orders of magnitude by either (a) electroforming a conduction channel (e.g., in tungsten oxide), or (b) inducing Mott-Hubbard transition (e.g., in rare-earth nickelates)– both via controlled migration of defects (such as oxygen vacancies) under applied bias. However, development of accurate neuromorphic computers (i.e., low variability) remains extremely challenging due to a lack of fundamental understanding of the atomic-scale processes that underlie migration and spatiotemporal evolution of oxygen vacancies (and other extended defects) over nano-to-mesoscopic length/timescales under applied electric field. Here, we demonstrate that a synergistic integration of density functional theory (DFT) calculation, ab initio/classical molecular dynamics (AIMD/CMD) simulations, precision synthesis, and multi-modal X-ray imaging experiments provides an effective route to address this knowledge gap. First, we use a combination of multi-modal X-ray imaging (with chemical/structural sensitivity) and CMD simulations to show that the intrinsic randomness of electroforming process in tungsten-oxide memristors can be minimized by careful introduction of sharp protrusions in the electrode gap. We find that sharp protrusions confine the electric field, which yields a reproducible distribution of oxygen vacancies over several switching cycles; and reliably form conduction channel in a specific location in the memristor. Next, we employed a large dataset of data from DFT calculations and short AIMD trajectories to develop deep neural network (DNN) models to accurately capture energetics, atomic forces, atomic charges, and maximally localized Wannier centers in rare-earth nickelates (RNO). CMD simulations based on these newly developed DNNs show that metal-insulator transition (MIT) in RNO occurs via a local structural distortion in the extended nickel structure, which facilitates the electronic instability and causes a sharp concomitant Ni-O bond and Ni-charge disproportion with decreasing temperature; this MIT is also strongly influenced by applied pressure and rare-earth ion. Furthermore, DFT calculations reveal the correlations the oxygen stoichiometry, OV distribution (including different NiOx motifs), OV transport, and electron-lattice coupling in perovskite nickelates. These results will be discussed in the context of controlling defect-induced transitions to design accurate and reliable memristive devices for neuromorphic computing platforms that are vital for artificial intelligence technologies.

Ion–Electron Instabilities in the Precursors of Weakly Magnetized, Transrelativistic Shocks

Collisionless shocks are known to induce turbulence via upstream ion reflection within the precursor region. This study elucidates the properties of electrostatic and electromagnetic instabilities, exploring their role over the transrelativistic range. Notably, the growth of oblique Buneman waves and previously overlooked, secondary, small-scale ion–electron instabilities is observed to be particularly promoted in the relativistic regime. Furthermore, the growth of large-scale electromagnetic modes encounters severe limitations in any cold, baryon-loaded precursor. It is argued that electron preheating in electrostatic modes may alleviate these constraints, facilitating the subsequent growth of large-scale filamentation modes in the precursors of transrelativistic shocks.

Absence of E2g Nematic Instability and Dominant A1g Response in the Kagome Metal CsV3Sb5

Ever since the discovery of the charge density wave (CDW) transition in the kagome metal CsV3Sb5, the nature of its symmetry breaking has been under intense debate. While evidence suggests that the rotational symmetry is already broken at the CDW transition temperature (TCDW), an additional electronic nematic instability well below TCDW has been reported based on the diverging elastoresistivity coefficient in the anisotropic channel (mE2g). Verifying the existence of a nematic transition below TCDW is not only critical for establishing the correct description of the CDW order parameter, but also important for understanding low-temperature superconductivity. Here, we report elastoresistivity measurements of CsV3Sb5 using three different techniques probing both isotropic and anisotropic symmetry channels. Contrary to previous reports, we find the anisotropic elastoresistivity coefficient mE2g is temperature independent, except for a step jump at TCDW. The absence of nematic fluctuations is further substantiated by measurements of the elastocaloric effect, which show no enhancement associated with nematic susceptibility. On the other hand, the symmetric elastoresistivity coefficient mA1g increases below TCDW, reaching a peak value of 90 at T*=20 K. Our results strongly indicate that the phase transition at T* is not nematic in nature and the previously reported diverging elastoresistivity is due to the contamination from the A1g channel. Published by the American Physical Society 2024

Electronic instability in pressured black phosphorus under strong magnetic field

In this paper, we have systematically studied the electronic instability of pressured black phosphorous (BP) under strong magnetic field. We first present an effective model Hamiltonian for pressured BP near the Lifshitz point. Then we show that when the magnetic field exceeds a critical value, the nodal-line semimetal (NLSM) state of BP with a small band overlap re-enters the semiconductive phase by re-opening a small gap. This results in a narrow-bandgap semiconductor with a partially flat valence band edge. Moreover, we demonstrate that above this critical magnetic field, two possible instabilities, i.e. charge density wave phase and excitonic insulator (EI) phase, are predicted as the ground state for high and low doping concentrations, respectively. By comparing our results with the experiment (Sun et al 2018 Sci. Bull. 63 1539), we suggest that the field-induced instability observed experimentally corresponds to an EI. Furthermore, we propose that the semimetallic BP under pressure with small band overlaps may provide a good platform to study the magneto-exciton insulators. Our findings bring the first insight into the electronic instability of topological NLSM in the quantum limit.

In-situ electrochemical conversion of V2O3@C into Zn3(OH)2V2O7·2H2O@C for high-performance aqueous Zn-ion batteries

Open-framework crystal structured vanadates have been extensively investigated as cathode materials for aqueous zinc-ion batteries (ZIBs). However, the inherent challenges of poor electronic conductivity and structural instability compromise the rate capability and overall cycle life. Herein, we first successfully synthesized octahedral MIL-101(V) and prepared the Zn3(OH)2V2O7·2H2O@C (ZVOH@C) composite by in-situ electrochemical conversion of MIL-101(V)-derived crystalline V2O3 and carbon composite (V2O3@C). The ZVOH@C composite of open-framework crystal structured Zn3(OH)2V2O7·2H2O and conductive carbon skeleton not only possesses more active sites, more stable crystal structure and higher electrical conductivity, but also provides faster Zn2+ diffusion kinetics. As expected, the ZVOH@C composite electrode exhibits excellent capacity of 506.3 mAh/g at a current density of 1.0 A/g, exceptional rate performance (375.7 mAh/g at 20.0 A/g), and impressive long-term cycling stability, maintaining 314.5 mAh/g over 5000 cycles at 20.0 A/g. This study demonstrates a promising method for designing new cathode materials through in-situ electrochemical synthesis for ZIBs.

Hidden Charge Order and Multiple Electronic Instabilities in EuTe4.

The rare-earth telluride compound EuTe4 exhibits a charge density wave (CDW) and an unconventional thermal hysteresis transition. Herein, we report a comprehensive study of the CDW states in EuTe4 by using low-temperature scanning tunneling microscopy. Two types of charge orders are observed at 4 K, including a newly discovered spindle-shaped pattern and a typical stripe-like pattern. As an exotic charge order, the spindle-shaped CDW is off-axis and barely visible at 77 K, indicating that it is a hidden order developed at low temperature. Based on our first-principles calculations, we reveal the origins of the observed electronic instabilities. The spindle-shaped charge order stems from a subsequent transition based on the stripe-like CDW phase. Our work demonstrates that the competition and cooperation between multiple charge orders can generate exotic quantum phases.

Defect-mediated structural phase transition in Ta2NiSe5 visualized via in situ TEM

Extensive experimental and theoretical efforts have been devoted to elucidating the origin of either structural or electronic instability in the formation of excitonic state in Ta2NiSe5, whereas the effects of lattice defects on actual structural phase transition in Ta2NiSe5 remain elusive. Here, we perform in situ transmission electron microscopy (TEM) experiments to investigate the structural phase transition of Ta2NiSe5 thin films, with a particular focus on the influence of microstructural features and lattice defects on the phase transition. In the cyclic in situ heating-cooling TEM experiments, we track the reversible orthorhombic to monoclinic (vice versa) phase transitions via twinning variant contrast in TEM images and via changes in reflection splitting in diffraction patterns. We further investigate the effects of dislocations and grain boundaries on the phase transition of Ta2NiSe5 thin films. Our findings reveal that individual dislocations can inhibit the transition from monoclinic to orthorhombic phases while simultaneously promoting the reverse transition from orthorhombic to monoclinic phases. Furthermore, we observe a phenomenon of metastable to stable phase transition within grain-boundary-confined regions of Ta2NiSe5 thin films. These in situ TEM observations offer a comprehensive microscopic perspective on defect-mediated phase transitions in Ta2NiSe5. This insight may extend to other varieties of transition-metal chalcogenides, thus implying a broader applicability.

Toward 1D Transport in 3D Materials: SOC-Induced Charge-Transport Anisotropy in Sm3ZrBi5.

1D charge transport offers great insight into strongly correlated physics, such as Luttinger liquids, electronic instabilities, and superconductivity. Although 1D charge transport is observed in nanomaterials and quantum wires, examples in bulk crystalline solids remain elusive. In this work, it is demonstrated that spin-orbit coupling (SOC) can act as a mechanism to induce quasi-1D charge transport in the Ln3MPn5 (Ln = lanthanide; M = transition metal; Pn = Pnictide) family. From three example compounds, La3ZrSb5, La3ZrBi5, and Sm3ZrBi5, density functional theory calculations with SOC included show a quasi-1D Fermi surface in the bismuthide compounds, but an anisotropic 3D Fermi surface in the antimonide structure. By performing anisotropic charge transport measurements on La3ZrSb5, La3ZrBi5, and Sm3ZrBi5, it is demonstrated that SOC starkly affects their anisotropic resistivity ratios (ARR) at low temperatures, with an ARR of ≈4 in the antimonide compared to ≈9.5 and ≈22 (≈32 after magnetic ordering) in La3ZrBi5 and Sm3ZrBi5, respectively. This report demonstrates the utility of spin-orbit coupling to induce quasi-low-dimensional Fermi surfaces in anisotropic crystal structures, and provides a template for examining othersystems.

Evidences for local non-centrosymmetricity and strong phonon anomaly in EuCu2As2: a Raman spectroscopy and lattice dynamics study

Phonon modes and their association with the electronic states have been investigated for the metallic EuCu2As2 system. In this work, we present the Raman spectra of this pnictide system which clearly shows the presence of seven well defined peaks above 100 cm−1 that is consistent with the locally non-centrosymmetric P4/nmm crystal structure, contrary to that what is expected from the accepted symmorphic I4/mmm structure. Lattice dynamics calculations using the P4/nmm symmetry attest that there is a commendable agreement between the calculated phonon spectra at the Γ point and the observed Raman mode frequencies, with the most intense peak at ∼232 cm−1 being ascribed to the A 1g mode. Temperature dependent Raman measurements show that there is a significant deviation from the expected anharmonic behaviour around 165 K for the A 1g mode, with anomalies being observed for several other modes as well, although to a lesser extent. Attempts are made to rationalize the observed anomalous behavior related to the hardening of the phonon modes, with parallels being drawn from metal dichalcogenide and allied systems. Similarities in the evolution of the Raman peak frequencies with temperature seem to suggest a strong signature of a subtle electronic density wave instability below 165 K in this compound.

Study of Electron Energy Distribution Function, Transport Parameters and Instability Analysis of Argon Plasma confined by a Dipole Magnet

This theoretical study is to investigate production and properties of plasma confined by a dipole magnet. A cylindrical permanent magnet (N40 grade) having a surface magnetic field of nearly 1Tesla is simulated to create a dipole magnetic field. Plasma is created by electron cyclotron resonance heating. Heating is accomplished using microwaves operating in continuous mode at 2.45 GHz and electron cyclotron resonance. The investigation is performed in systems of cylindrical geometries at varying pressures (0.5 mTorr – 1.5 mTorr). The electron temperature lies in the range of 1 - 5 eV, is hotter near the magnets and follows a downstream fashion throughout the region.Electron Energy Distribution Function (EEDF) growth investigation throughout the region was done to understand the role of magnetic field confinement. The EEDF was calculated numerically from steady state Boltzmann equation, considering plasma follows druyvesteyn distribution. Followed by analysing transport parameters such as diffusion coefficient, drift velocity, mobility, and recombination rates in plasma. A comparative study for all plots gave been done with respect to pressure. The instability analysis of elastic collisional frequency with inelastic collisions, real frequency and growth factor with wave vector has been also listed in the study.

Study of magnetic field evolution by Weibel instability in counter-streaming electron–positron plasma flows

Study of magnetic field evolution by Weibel instability in counter-streaming electron–positron plasma flows

Dual quantum spin Hall insulator by density-tuned correlations in TaIrTe4.

The convergence of topology and correlations represents a highly coveted realm in the pursuit of new quantum states of matter1. Introducing electron correlations to a quantum spin Hall (QSH) insulator can lead to the emergence of a fractional topological insulator and other exotic time-reversal-symmetric topological order2-8, not possible in quantum Hall and Chern insulator systems. Here we report a new dual QSH insulator within the intrinsic monolayer crystal of TaIrTe4, arising from the interplay of its single-particle topology and density-tuned electron correlations. At charge neutrality, monolayer TaIrTe4 demonstrates the QSH insulator, manifesting enhanced nonlocal transport and quantized helical edge conductance. After introducing electrons from charge neutrality, TaIrTe4 shows metallic behaviour in onlya small range of charge densities but quickly goes into a new insulating state, entirely unexpected on the basis of the single-particle band structure of TaIrTe4. This insulating state could arise from a strong electronic instability near the van Hove singularities, probably leading to a charge density wave (CDW). Remarkably, within this correlated insulating gap, we observe a resurgence of the QSH state. The observation of helical edge conduction in a CDW gap could bridge spin physics and charge orders. The discovery of a dual QSH insulator introduces a new method for creating topological flat minibands through CDW superlattices, which offer a promising platform for exploring time-reversal-symmetric fractional phases and electromagnetism2-4,9,10.