Lattice Fluctuations Research Articles

Understanding the superconductivity and charge density wave interaction through quasi-static lattice fluctuations

In unconventional superconductors, coupled charge and lattice degrees of freedom can manifest in ordered phases of matter that are intertwined. In the cuprate family, fluctuating short-range charge correlations can coalesce into a longer-range charge density wave (CDW) order which is thought to intertwine with superconductivity, yet the nature of the interaction is still poorly understood. Here, by measuring subtle lattice fluctuations in underdoped YBa2Cu3O6+y on quasi-static timescales (thousands of seconds) through X-ray photon correlation spectroscopy, we report sensitivity to both superconductivity and CDW. The atomic lattice shows remarkably faster relaxational dynamics upon approaching the superconducting transition at Tc ≈ 65 K. By tracking the momentum dependence, we show that the intermediate scattering function almost monotonically scales with the relaxation distance of atoms away from their average positions above Tc and in the presence of the CDW state, while this peculiar trend is reversed for other temperatures. These observations are consistent with an incipient CDW stabilized by local strain. This work provides insights into the crucial role of relaxational atomic fluctuations for understanding the electronic physics cuprates, which are inherently disordered due to carrier doping.

Effects of lattice instability on the thermoelectric behavior of kagome metal ScV6Sn6

Kagome metal ScV6Sn6 has been a subject of interest due to the emergence of a first-order structural phase transition with intriguing charge density wave behavior below the transition temperature Tc ∼ 92 K. To explore the thermoelectric properties and provide experimental insights into the nature of the phase transition, we have carried out a combined study by means of the electrical resistivity, Seebeck coefficient, and thermal conductivity measurements on single crystalline ScV6Sn6. Pronounced features near Tc have been characterized by all measured physical quantities. In particular, the Seebeck coefficient exhibits a marked reduction as lowering temperature across Tc, attributed to an imbalance of the contribution from different type of carriers induced by the structural phase transition. From the examination of the electronic and lattice thermal conductivities, we obtained a confirmation that the observed enhancement at Tc is essentially caused by the change of the lattice thermal conductivity, demonstrating the primary importance of lattice distortions for the heat transport of ScV6Sn6. In addition, the lattice thermal conductivity above Tc was found to increase monotonically with temperature. We associated the peculiar phenomenon with lattice fluctuations, highlighting the essence of structural instability in the kagome lattice ScV6Sn6. These results add to the knowledge about the thermal transport properties in kagome materials with a hexagonal HfFe6Ge6-type structure.

Unveiling the effect of solvent for hydrogen evolution in Pt-doped MXenes and corresponding high-entropy phase

Effect of solvent at the water/solid interface plays a non-negligible role in chemical reactions. Explicit solvation has been proved for its important effect on thermodynamics and kinetics of catalytic reactions. However, systematic studies about this perspective are still absence. In this work, using the model of single platinum atom immobilized on the metal vacancies of a series of MXenes, we systematically investigate the implicit/explicit solvent effect on their catalytic performance of the hydrogen evolution reaction (HER). We find that the solvent effect plays a significant role in affecting the calculation results for some systems. For TiNbC–PtNb, the value of ΔGH* decreases from −0.121 to −0.511 (−0.583) eV when considering implicit (explicit) correction, implying the decisive role of solvent effect for calculating HER in this system. Bader charge analysis and AIMD simulations reveal that TiNbC–PtNb surface is sensitive to H2O, thus causing this abnormal case. Surprisingly high-entropy phases of MXene overall are less sensitive to solvent compared to the pure phases, which could be due to their alloyed lattice with a strong ability against electronic and lattice fluctuations induced by solvent. Several systems like V2C–PtV, TiMoC–PtMo, and VNbC–PtV are predicted to be excellent electrocatalysts for alkaline HER with the appropriate Gibbs free energy of hydrogen adsorption and kinetic barrier of water dissociation. The perspective exemplified in this work highlights that more feasible operando should be considered, e.g., influence of water, to better simulate the reaction process. Our work suggests that Pt-doped MXenes are perfect systems for hosting atomic catalyst as well.

Coupled spin-lattice dynamics from the tight-binding electronic structure

We developed a method which performs the coupled adiabatic spin and lattice dynamics based on the tight-binding electronic structure model, where the intrinsic magnetic field and ionic forces are calculated from the converged self-consistent electronic structure at every time step. By doing so, this method allows us to explore limits where the physics described by a parameterized spin-lattice Hamiltonian is no longer accurate. We demonstrate how the lattice dynamics is strongly influenced by the underlying magnetic configuration, where disorder is able to induce significant lattice distortions. The presented method requires significantly less computational resources than methods, such as time-dependent density functional theory (TD-DFT). Compared to parameterized Hamiltonian-based methods, it also describes more accurately the dynamics of the coupled spin and lattice degrees of freedom, which becomes important outside of the regime of small lattice and spin fluctuations. Published by the American Physical Society 2024

Boosting exciton mobility approaching Mott-Ioffe-Regel limit in Ruddlesden−Popper perovskites by anchoring the organic cation

Exciton transport in two-dimensional Ruddlesden−Popper perovskite plays a pivotal role for their optoelectronic performance. However, a clear photophysical picture of exciton transport is still lacking due to strong confinement effects and intricate exciton-phonon interactions in an organic-inorganic hybrid lattice. Herein, we present a systematical study on exciton transport in (BA)2(MA)n−1PbnI3n+1 Ruddlesden−Popper perovskites using time-resolved photoluminescence microscopy. We reveal that the free exciton mobilities in exfoliated thin flakes can be improved from around 8 cm2 V−1 s−1 to 280 cm2V−1s−1 by anchoring the soft butyl ammonium cation with a polymethyl methacrylate network at the surface. The mobility of the latter is close to the theoretical limit of Mott-Ioffe-Regel criterion. Combining optical measurements and theoretical studies, it is unveiled that the polymethyl methacrylate network significantly improve the lattice rigidity resulting in the decrease of deformation potential scattering and lattice fluctuation at the surface few layers. Our work elucidates the origin of high exciton mobility in Ruddlesden−Popper perovskites and opens up avenues to regulate exciton transport in two-dimensional materials.

Quenched lattice fluctuations in optically driven SrTiO3

Crystal lattice fluctuations, which are known to influence phase transitions of quantum materials in equilibrium, are also expected to determine the dynamics of light-induced phase changes. However, they have only rarely been explored in these dynamical settings. Here we study the time evolution of lattice fluctuations in the quantum paraelectric SrTiO3, in which mid-infrared drives have been shown to induce a metastable ferroelectric state. Crucial in these physics is the competition between polar instabilities and antiferrodistortive rotations, which in equilibrium frustrate the formation of long-range ferroelectricity. We make use of high-intensity mid-infrared optical pulses to resonantly drive the Ti–O-stretching mode at 17 THz, and we measure the resulting change in lattice fluctuations using time-resolved X-ray diffuse scattering at a free-electron laser. After a prompt increase, we observe a long-lived quench in R-point antiferrodistortive lattice fluctuations. Their enhancement and reduction are theoretically explained by considering the fourth-order nonlinear phononic interactions to the driven optical phonon and third-order coupling to lattice strain, respectively. These observations provide a number of testable hypotheses for the physics of light-induced ferroelectricity.

Uncovering the mechanisms of efficient upconversion in two-dimensional perovskites with anti-Stokes shift up to 220 meV.

Phonon-assisted photon upconversion holds great potential for numerous applications, e.g., optical refrigeration. However, traditional semiconductors face energy gain limitations due to thermal energy, typically achieving only ~25 milli-electron volts at room temperature. Here, we demonstrate that quasi-two-dimensional perovskites, with a soft hybrid organic-inorganic lattice, can efficiently upconvert photons with an anti-Stokes shift exceeding 200 milli-electron volts. By using microscopic transient absorption measurements and density functional theory calculations, we explicate that the giant energy gain stems from strong lattice fluctuation leading to a picosecond timescale transient band energy renormalization with a large energy variation of around ±180 milli-electron volts at room temperature. The motion of organic molecules drives the deformation of inorganic framework, providing energy and local states necessary for efficient upconversion within a time constant of around 1 ps. These results establish a deep understanding of perovskite-based photon upconversion and offer previously unknown insights into the development of various upconversion applications.

Tensile Microstrain Fluctuations in the BaPbO Units in Superconducting BaPb1−xBixO3 by Scanning Dispersive Micro-XANES

BaPb1−xBixO3 (BPBO) bismuthate, showing high TC superconductivity for 0.05 < x < 0.35, is an archetypal system for studying the complex inhomogeneity of perovskite lattice favoring the emergence of quantum coherence, called the superstripes phase. Local lattice fluctuations, detected by EXAFS; nanoscale stripes, detected by electron microscopy; and two competing crystalline structures, detected by diffraction, are known to characterize the superconducting phase. At nanoscale [BaBiO3] centered nanoscale units (BBO) coexist with BaPbO3 centered (BPO) units in the BPBO perovskite; therefore, we expect a tensile microstrain in BPO units due the misfit strain between the two different lattices. Here, we report the measurement of the spatial micro-fluctuations of the local tensile microstrain ε in the BaPO units in superconducting Ba(Pb1−xBix)O3 crystals with x1 = 0.19 an x2 = 0.28. We show here the feasibility of applying the scanning dispersive micro-X-ray absorption near edge structure (SdμXANES) technique, using focused synchrotron radiation, to probe the microscale spatial fluctuations of the microstrain in BPO units. This unconventional real-space SdμXANES microscopy at the Pb L3 edge has been collected in the dispersive mode. Our experimental method allows us to measure either the local Bi chemical concentration x and the local lattice microstrain of local BBO and BPO units. The 5 × 5 micron-size spots from the focused X-ray beam allowed us to obtain maps of 1600 points covering an area of 200 × 200 microns. The mapping shows a substantial difference between the spatial fluctuations of the microstrain ε and the chemical inhomogeneity x. Moreover, we show the different relations ε(x) in samples with lower (x1 = 0.19) and higher (x2 = 0.28) doping respect to the optimum doping (x = 0.25).

Temporal Evolution and Fluence Dependence of Band Structure in Photoexcited Ta2Ni0.9Co0.1Se5 Probed by Time- and Angle-Resolved Photoemission Spectroscopy

We have investigated the temporal evolution and fluence dependence of band structure in Ta2Ni0.9Co0.1Se5 by means of time- and angle-resolved photoemission spectroscopy (tr-ARPES). With the fluence of 3.00 mJ cm−2 and the delay time of 170 fs, the conduction band crossing the Fermi level (EF) and the valence band reaching EF are observed indicating the photoinduced semimetal phase. However, at the delay time of 70 fs, the valence band top does not reach EF creating a partial gap or a pseudogap, and the transition from the excitonic insulator state to the semimetal state is not completed. The conduction band crossing EF is observed even with the shorter delay time (down to 50–70 fs) and/or the lower fluence (down to 0.32 mJ cm−2). On the other hand, the valence band top stays well below EF up to the fluence of 1.39 mJ cm−2 even at the delay time of 160–170 fs. The different optical responses of the valence and conduction bands suggest a vital role of the lattice fluctuations pointed out by Nakano et al. [Phys. Rev. B 98, 045139 (2018)] on the residual pseudogap at 70 fs after the photoexcitation.

Local instability in GdBa2Cu3O7-x/La0.7Sr0.3MnO3 superconducting bilayer: Temperature-dependent EXAFS study

This study investigated the effect of local structural coupling between the buffer and the superconducting layers on the superconductivity of a GdBa2Cu3O7-x (GdBCO)/La0.7Sr0.3MnO3 (LSMO) bilayer. Epitaxial bilayers consisting of GdBCO with varying thicknesses (100, 300, and 500 nm), with and without LSMO (100 nm), were fabricated on a (001) SrTiO3 substrate. To investigate the local structural distortion within the GdBCO/LSMO system, the temperature-dependent extended X-ray absorption fine structure (EXAFS) spectra were measured at the Mn- and Cu–K absorption edges. The EXAFS analyses revealed local structural non-uniformity, which manifested as anomalies in the temperature dependence of both the Mn–O and Cu–O bond distributions. A strong correlation exists between the local structural distortion of the Mn–O bond and the degree of lattice instability in the CuO2 plane, which exhibits a strong thickness dependence. The inter-atomic potential of oxygen oscillations with an anharmonic approximation was adopted to interpret the structural anomalies. As a result, a double-well potential was obtained near Tc, owing to the occurrence of longer Cu–O bonds in the CuO2 plane. The difference in the degree of structural anomalies depending on the GdBCO thickness manifested as a difference in the distance between the two wells, which closely correlates with the appearance of a superconducting state. These experimental results demonstrate the role of local lattice fluctuations in the superconducting mechanism of the GdBCO/LSMO bilayer.

Spatial coherence effects of stochastic optical beams in periodic potentials

The interaction between a partially coherent field with a one-dimensional periodic photonic environment is investigated within the framework of Floquet-Bloch modes. To this end, we describe the interplay between lattice properties and field fluctuations by considering the optical beam as a linear combination of Floquet-Bloch modes, whose coefficients are described by a stationary random process. It is demonstrated that the propagation of partially coherent beams depends not only on the average of the excitation of each band but also on the correlations existent among the various bands supported by the lattice.

Q-Balls in the Pseudogap Phase of Superconducting HgBa2CuO4+y

Fast and local probes, such as X-ray spectroscopy, X-ray diffraction (XRD), and X-ray microscopy, have provided direct evidence for nanoscale phase separation in high temperature perovskite superconductors composed of (i) free particles coexisting with (ii) Jahn Teller polarons (i.e., charges associated with local lattice distortions) not detected by slow experimental methods probing only delocalized states. Moreover, these experimental probes have shown the formation of a superstripes phase in the pseudogap regime below T* in cuprates. Here, we focus on the anomalous temperature dependence of short range X-ray diffraction CDW reflection satellites with high momentum transfer, probing both charge and lattice fluctuations in superconducting HgBa2CuO4+y (Hg1201) in the pseudogap regime below T* and above Tc. We report compelling evidence of the anomalous anticorrelation of the coherence volume with the peak maximum amplitude of the CDW XRD satellite by cooling below T*. This anomalous temperature trend of the short-range striped Jahn Teller polaronic CDW puddles is in agreement with predictions of the Q-ball theory of the quark gluon plasma extended to cuprates, providing compelling evidence for non topological soliton puddles of striped condensate of pairs in the pseudogap phase.

Electron correlations rule the phonon-driven instability in single-layer TiSe2

We investigate the controversial case of charge-density-wave (CDW) order in single layer 1T-TiSe$_2$ by employing the density functional perturbation theory with on-site Hubbard interactions. The results emphasize the crucial role of electron correlations via Hubbard corrections in order to capture the accurate electronic structure, low- and high-temperature limits of the CDW phonon mode, and temperature-charge phase diagram. We show, in close agreement with the experiments, that total phase diagram consists of both commensurate and incommensurate CDW regions, where the latter coincide with the superconductive phase and might be instrumental for its formation. In addition to the established roles of quantum lattice fluctuations and excitonic interactions, our analysis emphasizes the overlooked crucial role of the momentum dependent electron-phonon coupling and electron correlations for the CDW phase transition in single layer TiSe$_2$.

Lattice shear and non-random rotation of Au nanoparticles under electron-beam irradiation

Structural evolution of Au nanoparticles on amorphous carbon under electron-beam irradiation was examined at the atomic scale through in situ high-resolution transmission electron microscopy. Under electron-beam irradiation, some nanoparticles underwent lattice shear and fluctuation. The d-spacing and interplanar angle constantly and gradually changed, revealing metastable structures deviating from face-centered cubic Au. Rather than undergoing lattice fluctuation, some nanoparticles rotated. The nanoparticles did not rotate randomly, but followed a rule. As a nanoparticle rotated, one family of lattice planes constituting an initial zone axis remained parallel to the incident electron beam. Although the structural change and motion of nanoparticles under electron-beam irradiation have been examined in the literature, the aforementioned atomistic behavior has never been unveiled. We relate the phenomena to electron-beam-induced heating caused by inelastic collision between incident electrons and atomic electrons and momentum transfer during electron irradiation.

Doping fingerprints of spin and lattice fluctuations in moiré superlattice systems

Twisted Van der Waals systems offer the unprecedented possibility to tune different states of correlated quantum matter with external noninvasive electrostatic doping. The nature of the superconducting order presents a recurring open question in this context. In this work, we assess quantitatively the case of spin-fluctuation-mediated pairing for $\mathrm{\ensuremath{\Gamma}}$-valley twisted transition metal dichalcogenide homobilayers. We calculate self-consistently and dynamically the doping-dependent superconducting transition temperature ${T}_{\mathrm{c}}$ revealing a superconducting dome with a maximal ${T}_{\mathrm{c}}\ensuremath{\approx}0.1--1\phantom{\rule{0.16em}{0ex}}\mathrm{K}$ depending on twist angle. We compare our results with conventional phonon-mediated superconductivity, and we identify clear fingerprints in the doping dependence of ${T}_{\mathrm{c}}$, which enable experiments to distinguish between different pairing mechanisms.

Coherent interaction and action–counteraction theory in small polaron systems, and ground state properties

Based on the coherent interaction and action–counteraction principles, we investigate the ground state properties for small polaron systems, the coherent-squeezed fluctuation correction, and the anomalous lattice quantum fluctuation, with the new variational generator containing correlated squeezed-coherent coupling and quantum entanglement. Noting that −2t is the T.B.A. energy, for the coherent interaction effect, we find the ground-state energy E 0 to be −2.428t, in which the coherent squeezed fluctuation correction −A 0 t is −0.463t (where t is the hopping integral, ω is the phonon frequency), with the electron–one-phonon coupling constant g = 1 and the electron–two-phonon coupling constant g 1 = −0.1. However, as a result of the action–counteraction effect, is −2.788t, but is −0.735t. As to the polaron binding energy (E P), for the coherent interaction effect, E P is −1.38ω, but for the action–counteraction effect, is −1.88ω. In particular, the electron–two-phonon interaction noticeably enlarges the coherent interaction and the coherent squeezed quantum fluctuation correction. By intervening with the quantum entanglement, the evolutions of the squeezed coherent state and the lattice quantum fluctuation begin to take control. At that time, we encounter a new quantum phase coherence phenomenon — the collapse and revival of inversion repeatedly for the coherent state in the entangled evolution.

Study of the thermodynamic properties of SrTiO3 perovskite by the statistical moment method with improved interatomic potential

We study the thermodynamic properties of cubic SrTiO3 perovskite going beyond the statistical moment method within approximation up to the fourth-order of the power moments of the atomic displacements. The analytic expressions of the thermodynamic quantities, such as the free energy, thermal expansion coefficients, and heat capacity at the constant volume and constant pressure of SrTiO3, are obtained. The potential with the partial charge model and functions of Demontis and Pedone is used to calculate the numerical thermodynamic quantities of SrTiO3 from room temperature up to high temperature. The numerical results of the thermodynamic quantities of SrTiO3 by the statistical moment method are in good agreement with the previous theoretical and experimental results for a wide temperature range. Our research also shows that the anharmonic effects of the lattice fluctuations affect the thermodynamic properties of SrTiO3 dominantly. It has a good potential to develop the statistical moment method for investigating the temperature effects on the thermodynamic quantities of the perovskite–structure materials.

Photo-induced enhancement of lattice fluctuations in metal-halide perovskites

The optoelectronic properties of metal-halide perovskites (MHPs) are affected by lattice fluctuations. Using ultrafast pump-probe spectroscopy, we demonstrate that in state-of-the-art mixed-cation MHPs ultrafast photo-induced bandgap narrowing occurs with a linear to super-linear dependence on the excited carrier density ranging from 1017 cm−3 to above 1018 cm−3. Time-domain terahertz spectroscopy reveals carrier localization increases with carrier density. Both observations, the anomalous dependence of the bandgap narrowing and the increased carrier localization can be rationalized by photo-induced lattice fluctuations. The magnitude of the photo-induced lattice fluctuations depends on the intrinsic instability of the MHP lattice. Our findings provide insight into ultrafast processes in MHPs following photoexcitation and thus help to develop a concise picture of the ultrafast photophysics of this important class of emerging semiconductors.

Origin of Ferroelectricity in Two Prototypical Hybrid Organic-Inorganic Perovskites.

Hybrid organic-inorganic perovskite (HOIP) ferroelectrics are attracting considerable interest because of their high performance, ease of synthesis, and lightweight. However, the intrinsic thermodynamic origins of their ferroelectric transitions remain insufficiently understood. Here, we identify the nature of the ferroelectric phase transitions in displacive [(CH3)2NH2][Mn(N3)3] and order-disorder type [(CH3)2NH2][Mn(HCOO)3] via spatially resolved structural analysis and ab initio lattice dynamics calculations. Our results demonstrate that the vibrational entropy change of the extended perovskite lattice drives the ferroelectric transition in the former and also contributes importantly to that of the latter along with the rotational entropy change of the A-site. This finding not only reveals the delicate atomic dynamics in ferroelectric HOIPs but also highlights that both the local and extended fluctuation of the hybrid perovskite lattice can be manipulated for creating ferroelectricity by taking advantages of their abundant atomic, electronic, and phononic degrees of freedom.

Dynamically preferred state with strong electronic fluctuations from electrochemical synthesis of sodium manganate

<h2>Summary</h2> Electrochemical (de)intercalation is a delicate method to precisely control the alkaline ion composition in alkaline transition metal oxides. Because of complicated interactions, metal charge ordering patterns can form spontaneously at special fractional alkaline compositions and orderings. Here, we show that this elegant electrochemical process can create dynamically preferred structures in an anharmonic energy landscape that conventional syntheses and computations can rarely visit. Specifically, electrochemically prepared Na_1/2MnO₂ ordering exhibits abnormal structure distortions, charge orderings, and dynamical activities. Strong magnetic fluctuations and lattice dynamics are observed in an unusually wide temperature range in Na_1/2MnO₂, which distinguishes it from all other Na_xMnO₂ at higher or lower Na compositions. The results emphasize the unique opportunity of using electrochemical processes to design and create novel quantum states with strongly coupled and mutually enhanced electronic and lattice fluctuations, likely through a special dynamic charge flux functional, as suggested by our computational investigations.