arXiv subjects

Long-Qing Chen

Publications and source records attributed to Long-Qing Chen.

At least 55 records · Page 3Linked to original sources

arXiv2025

Identifying Independent Components and Internal Process Order Parameters in Nonequilibrium Multicomponent Nonstoichiometric Compounds

In CALPHAD-type thermodynamic databases, nonstoichiometric compounds are typically described by sublattice models where the sublattice site fractions represent the occupation probability of different atomic, ionic or defect species on different sublattices. Here, we develop a general procedure and corresponding linear algebra tools for converting the sublattice site fractions to a combination of independent component compositions and internal process order parameters describing the extent of internal atomic exchange, electronic redox and defect generation reactions. We apply them to a number of nonstoichiometric phases in thermodynamic databases and literature. The general procedure can be applied to constructing thermodynamic databases in terms of internal process order parameters for nonstoichiometric phases in multicomponent systems such as high-entropy oxides and alloys, which can be utilized to model their kinetics of nonequilibrium processes and microstructure evolution.

cond-mat.mtrl-sci↗

arXiv2024

Thermodynamic Theory of Linear Optical and Electro-Optic Properties of Ferroelectrics

Ferroelectric materials underlie key optical technologies in optical communications, integrated optics and quantum computing. Yet, there is a lack of a consistent thermodynamic framework to predict the optical properties of ferroelectrics and the mutual connections among ferroelectric polarization, optical properties, and optical dispersion. For example, there is no existing thermodynamic model for establishing the relationship between the ferroelectric polarization and the optical properties in the visible spectrum. Here we present a thermodynamic theory of the linear optical and electro-optic properties of ferroelectrics by separating the lattice and electronic contributions to the total polarization. We introduce a biquadratic coupling between the lattice and electronic contributions validated by both first-principles calculations and experimental measurements. As an example, we derive the temperature and wavelength-dependent anisotropic optical properties of BaTiO3, including the full linear optical dielectric tensor and the linear electro-optic (Pockels) effect through multiple ferroelectric phase transitions, which are in excellent agreement with existing experimental data and first principles calculations. This general framework incorporates essentially all optical properties of materials, including coupling between the ionic and electronic order parameters, as well as their dispersion and temperature dependence, and thus offers a powerful theoretical tool for analyzing light-matter interactions in ferroelectrics-based optical devices.

cond-mat.mtrl-sci↗

arXiv2024

Integral boundary conditions in phase field models

Modeling the chemical, electric, and thermal transport as well as phase transitions and the accompanying mesoscale microstructure evolution within a material in an electronic device setting involves the solution of partial differential equations often with integral boundary conditions. Employing the familiar Poisson equation describing the electric potential evolution in a material exhibiting insulator-to-metal transitions, we exploit a special property of such an integral boundary condition, and we properly formulate the variational problem and establish its well-posedness. We then compare our method with the commonly-used Lagrange multiplier method that can also handle such boundary conditions. Numerical experiments demonstrate that our new method achieves an optimal convergence rate in contrast to the conventional Lagrange multiplier method. Furthermore, the linear system derived from our method is symmetric positive definite, and can be efficiently solved by Conjugate Gradient method with algebraic multigrid preconditioning.

math.NA↗

arXiv2024

Unprecedented Enhancement of Piezoelectricity in Wurtzite Nitride Semiconductors via Thermal Annealing

The incorporation of rare-earth elements in wurtzite nitride semiconductors, e.g., scandium alloyed aluminum nitride (ScAlN), promises dramatically enhanced piezoelectric responses, critical to a broad range of acoustic, electronic, photonic, and quantum devices and applications. Experimentally, however, the measured piezoelectric responses of nitride semiconductors are far below what theory has predicted. Here, we show that the use of a simple, scalable, post-growth thermal annealing process can dramatically boost the piezoelectric response of ScAlN thin films. We achieve a remarkable 3.5-fold increase in the piezoelectric modulus, d33 for 30% Sc content ScAlN, from 12.3 pC/N in the as-grown state to 45.5 pC/N, which is eight times larger than that of AlN. The enhancement in piezoelectricity has been unambiguously confirmed by three separate measurement techniques. Such a dramatic enhancement of d33 has been shown to impact the effective electromechanical coupling coefficient kt2 : increasing it from 13.8% to 76.2%, which matches the highest reported values in millimeter thick lithium niobate films but is achieved in a 100 nm ScAlN with a 10,000 fold reduction in thickness, thus promising extreme frequency scaling opportunities for bulk acoustic wave resonators for beyond 5G applications. By utilizing a range of material characterization techniques, we have elucidated the underlying mechanisms for the dramatically enhanced piezoelectric responses, including improved structural quality at the macroscopic scale, more homogeneous and ordered distribution of domain structures at the mesoscopic scale, and the reduction of lattice parameter ratio (c/a) for the wurtzite crystal structure at the atomic scale. Overall, the findings present a simple yet highly effective pathway that can be extended to other material families to further enhance their piezo responses.

cond-mat.mtrl-sci↗

arXiv2024

Theory of nonlinear terahertz susceptibility in ferroelectrics

An analytical theory is developed for predicting the nonlinear susceptibility of ionic polarization to continuous electromagnetic waves in both bulk and strained thin film ferroelectrics. Using a perturbation method for solving the nonlinear equation of motion for ionic polarization within the framework of Landau-Ginzburg-Devonshire theory, the full second-order nonlinear susceptibility tensor is derived as a function of frequency, temperature, and strain. The theory predicts the coexistence of a significantly enhanced second-order dielectric susceptibility and a relatively low dielectric loss in BaTiO3 films with a strain-stabilized monoclinic ferroelectric phase and in a strained SrTiO3 film near its temperature-driven second-order ferroelectric-to-paraelectric phase transition. This work establishes a theoretical framework for predicting and exploiting nonlinear interactions between THz waves and ferroelectric materials, and more generally, suggests exciting opportunities to strain-engineer nonlinear dynamical properties of ferroelectrics beyond the static and quasi-static limits.

cond-mat.mtrl-sci↗

arXiv2024

Inoculating solid-state homogeneous precipitation by impurity atoms through a spinodal decomposition like pathway

Solid-state homogeneous precipitation of nano-sized precipitates is one of the most effective processes to strengthen metal alloys, where the final density and size distribution of precipitates are largely controlled by the precipitation kinetics. Here, we report a strategy to inoculate the homogeneous precipitation of coherent precipitates to enhance the precipitation strengthening. Using the technologically important dilute Al-Zr alloys as an example, we demonstrate that an addition of a trace level of economical and readily available, non-L1$_{2}$ phase forming impurity atoms, X (X= Sn, Sb, Bi or Cd) and Si, can significantly enhance the diffusivity of Zr atoms and overturn the precipitation of L1$_{2}$-structured Al$_{3}$Zr nanoparticles from the classical homogeneous nucleation and growth pathway into a nonclassical nucleation pathway: Al$_{3}$Zr forms through the spontaneous formation of nano-scale local concentration fluctuations of Zr atoms on Zr-X(-Si)-vacancy clusters followed by a continuous increase of the concentration and chemical short-range ordering (CSRO). Such an impurity atoms induced heterogeneous nucleation based on a "spinodal decomposition like" mechanism dramatically accelerates the precipitation kinetics, leading to an order of magnitude higher number density of precipitates and a record high hardening efficiency of solute Zr atoms. By formulating the generalized selection principles for inoculating impurity elements, this inoculation strategy should be extendable to a broader range of materials to further explore the precipitation strengthening potentials.

cond-mat.mtrl-sci↗

arXiv2024

Optical Control of Adaptive Nanoscale Domain Networks

Adaptive networks can sense and adjust to dynamic environments to optimize their performance. Understanding their nanoscale responses to external stimuli is essential for applications in nanodevices and neuromorphic computing. However, it is challenging to image such responses on the nanoscale with crystallographic sensitivity. Here, the evolution of nanodomain networks in (PbTiO3)n/(SrTiO3)n superlattices was directly visualized in real space as the system adapts to ultrafast repetitive optical excitations that emulate controlled neural inputs. The adaptive response allows the system to explore a wealth of metastable states that were previously inaccessible. Their reconfiguration and competition were quantitatively measured by scanning x-ray nanodiffraction as a function of the number of applied pulses, in which crystallographic characteristics were quantitatively assessed by assorted diffraction patterns using unsupervised machine-learning methods. The corresponding domain boundaries and their connectivity were drastically altered by light, holding promise for light-programmable nanocircuits in analogy to neuroplasticity. Phase-field simulations elucidate that the reconfiguration of the domain networks is a result of the interplay between photocarriers and transient lattice temperature. The demonstrated optical control scheme and the uncovered nanoscopic insights open opportunities for remote control of adaptive nanoscale domain networks.

cond-mat.mes-hall↗

arXiv2024

Untangling individual cation roles in rock salt high-entropy oxides

We unravel the distinct roles each cation plays in phase evolution, stability, and properties within Mg1/5Co1/5Ni1/5Cu1/5Zn1/5O high-entropy oxide (HEO) by integrating experimental findings, thermodynamic analyses, and first-principles predictions. Our approach is through sequentially removing one cation at a time from the five-component high-entropy oxide to create five four-component derivatives. Bulk synthesis experiments indicate that Mg, Ni, and Co act as rock salt phase stabilizers whereas only Mg and Ni enthalpically enhance single-phase rock salt stability in thin film growth; synthesis conditions dictate whether Co is a rock salt phase stabilizer or destabilizer. By examining the competing phases and oxidation state preferences using pseudo-binary phase diagrams and first-principles calculations, we resolve the stability differences between bulk and thin film for all compositions. We systematically explore HEO macroscopic property sensitivity to cation selection employing both predicted and measured optical spectra. This study establishes a framework for understanding high-entropy oxide synthesizability and properties on a per-cation basis that is broadly applicable to tailoring functional property design in other high-entropy materials.

cond-mat.mtrl-sci↗

arXiv2024

Order evolution from a high-entropy matrix: understanding and predicting paths to low temperature equilibrium

Interest in high-entropy inorganic compounds originates from their ability to stabilize cations and anions in local environments that rarely occur at standard temperature and pressure. This leads to new crystalline phases in many-cation formulations with structures and properties that depart from conventional trends. The highest-entropy homogeneous and random solid-solution is a parent structure from which a continuum of lower-entropy offspring can originate by adopting chemical and/or structural order. This report demonstrates how synthesis conditions, thermal history, and elastic and chemical boundary conditions conspire to regulate this process in Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O, during which coherent CuO nano-tweeds and spinel nano-cuboids evolve. We do so by combining structured synthesis routes, atomic-resolution microscopy and spectroscopy, density functional theory, and a phase field modeling framework that accurately predicts the emergent structure and local chemistry. This establishes a framework to appreciate, understand, and predict the macrostate spectrum available to a high-entropy system that is critical to rationalize property engineering opportunities.

cond-mat.mtrl-sci↗

arXiv2024

Analytical model and dynamical phase-field simulation of terahertz transmission across ferroelectrics

We theoretically investigate the steady-state transmission of continuous terahertz (THz) wave across a freestanding ferroelectric slab. Based on the Landau-Ginzburg-Devonshire theory of ferroelectrics and the coupled equations of motion for polarization and electromagnetic (EM) waves, we derive the analytical expressions of the frequency- and thickness-dependent dielectric susceptibility and transmission coefficient at the thin slab limit in the harmonic excitation regime. When the slab thickness is much smaller than the THz wavelength in the ferroelectric, the analytical predictions agree well with the numerical simulations from a dynamical phase-field model that incorporates the coupled dynamics of strain, polarization, and EM wave in multiphase systems. At larger thicknesses, the transmission is mainly determined by the frequency-dependent attenuation of THz waves in the ferroelectric and the formation of a standing polarization/THz wave. Our results advance the understanding of the interaction between THz wave and ferroelectrics and suggest the potential of exploiting ferroelectrics to achieve low-heat-dissipation, nonvolatile voltage modulation of THz transmission for high-data-rate wireless communication.

cond-mat.mes-hall↗

arXiv2023

Light-Induced Transitions of Polar State and Domain Morphology of Photo-Ferroelectric Nanoparticles

Using the Landau-Ginzburg-Devonshire approach, we study light-induced phase transitions, evolution of polar state and domain morphology in photo-ferroelectric nanoparticles (NPs). Light exposure increases the free carrier density near the NP surface and may in turn induce phase transitions from the nonpolar paraelectric to the polar ferroelectric phase. Using the uniaxial photo-ferroelectric Sn2P2S6 as an example, we show that visible light exposure induces the appearance and vanishing of striped, labyrinthine or curled domains and changes in the polarization switching hysteresis loop shape from paraelectric curves to double, pinched and single loops, as well as the shifting in the position of the tricritical point. Furthermore, we demonstrate that an ensemble of non-interacting photo-ferroelectric NPs may exhibit superparaelectric-like features at the tricritical point, such as strongly frequency-dependent giant piezoelectric and dielectric responses, which can potentially be exploited for piezoelectric applications.

cond-mat.mtrl-sci↗

arXiv2023

Hall Coefficient and Resistivity in the Doped Bilayer Hubbard Model

Finding and understanding non-Fermi liquid transport behaviors are at the core of condensed matter physics. Most of the existing studies were devoted to the monolayer Hubbard model, which is the simplest model that captures essential features of high-temperature superconductivity. Here we discover a new type of non-Fermi liquid behavior emergent in the hole-doped bilayer Hubbard model, using dynamical mean-field theory with a full consideration of the short-range interlayer electron correlation. We find that at low temperatures, the Hall coefficient has a strong nonmonotonic dependence on temperature, leading to a double or quadruple reversal of its sign depending on the doping level. At the same time, the resistivity exhibits two plateaus rather than linearity in its temperature dependence. We show that these intriguing transport behaviors stem from the formation of coherent interlayer singlets, which scatter off gapped collective modes arising from short-range interlayer antiferromagnetic fluctuations.

cond-mat.str-el↗

arXiv2023

Large Enhancements in Optical and Piezoelectric Properties in Ferroelectric Zn1-xMgxO Thin Films through Engineering Electronic and Ionic Anharmonicities

Multifunctionality as a paradigm requires materials exhibiting multiple superior properties. Integrating second-order optical nonlinearity and large bandgap with piezoelectricity could, for example, enable broadband, strain-tunable photonics. Though very different phenomena at distinct frequencies, both second-order optical nonlinearity and piezoelectricity are third-rank polar tensors present only in acentric crystal structures. However, simultaneously enhancing both phenomena is highly challenging since it involves competing effects with tradeoffs. Recently, a large switchable ferroelectric polarization of ~ 80 uC cm-2 was reported in Zn1-xMgxO films. Here, ferroelectric Zn1-xMgxO is demonstrated to be a platform that hosts simultaneously a 30% increase in the electronic bandgap, a 50% enhancement in the second harmonic generation coefficients, and a near 200% improvement in the piezoelectric coefficients over pure ZnO. These enhancements are shown to be due to a 400% increase in the electronic anharmonicity and a ~200% decrease in the ionic anharmonicity with Mg substitution. Precisely controllable periodic ferroelectric domain gratings are demonstrated down to 800 nm domain width, enabling ultraviolet quasi-phase-matched optical harmonic generation as well as domain-engineered piezoelectric devices.

cond-mat.mtrl-sci↗

arXiv2023

Landau-Ginzburg theory of charge density wave formation accompanying lattice and electronic long-range ordering

We propose an analytical Landau-Ginzburg theory of the charge density waves coupled with lattice and electronic long-range order parameters. Examples of long-range order include electronic wave function of superconducting Cooper pairs, structural distortions, electric polarization, and magnetization. We formulate the Landau-Ginzburg free energy density as power expansion with respect to the charge density and other long-range order parameters, as well as their spatial gradients, and biquadratic coupling terms. We introduced a biquadratic coupling between the charge density gradient and long-range order parameters, as well as nonlinear higher gradients of the long-range order parameters. The biquadratic gradient coupling is critical to the appearance of different spatially-modulated phases in charge-ordered ferroics and high-temperature superconductors. We derived the thermodynamic conditions for the stability of the spatially-modulated phases, which are the intertwined spatial waves of charge density and lattice/electronic long-range order. The analytical expressions for the energies of different phases, corresponding order parameters, charge density waves amplitudes and modulation periods, obtained in this work, can be employed to guide the comprehensive physical explanation, deconvolution and Bayesian analysis of experimental data on quantum materials ranging from charge-ordered ferroics to high-temperature superconductors.

cond-mat.mtrl-sci↗

arXiv2023

Thermodynamically consistent non-isothermal phase-field modelling of elastocaloric effect: indirect vs direct method

Modelling elastocaloric effect (eCE) is crucial for the design of environmentally friendly and energy-efficient eCE based solid-state cooling devices. Here, a thermodynamically consistent non-isothermal phase-field model (PFM) coupling martensitic transformation with mechanics and heat transfer is developed and applied for simulating eCE. The model is derived from a thermodynamic framework which invokes the microforce theory and Coleman--Noll procedure. To avoid the numerical issue related to the non-differentiable energy barrier function across the transition point, the austenite-martensite transition energy barrier in PFM is constructed as a smooth function of temperature. Both the indirect method using isothermal PFM with Maxwell relations and the direct method using non-isothermal PFM are applied to calculate the elastocaloric properties. The former is capable of calculating both isothermal entropy change and adiabatic temperature change ($ΔT_{\text{ad}}$), but induces high computation cost. The latter is computationally efficient, but only yields $ΔT_{\text{ad}}$. In a model Mn-22Cu alloy, the maximum $ΔT_{\text{ad}}$ ($ΔT_{\text{ad}}^{\text{max}}$) under a compressive stress of 100 MPa is calculated as 9.5 and 8.5 K in single crystal (3.5 and 3.8 K in polycrystal) from the indirect and direct method, respectively. It is found that the discrepancy of $ΔT_{\text{ad}}^{\text{max}}$ by indirect and direct method is within 10% at stress less than 150 MPa, confirming the feasibility of both methods in evaluating eCE at low stress. The results demonstrate the developed PFM herein, combined with both indirect and direct method for eCE calculations, as a practicable toolkit for the computational design of elastocaloric devices.

cond-mat.mtrl-sci↗

arXiv2023

Emergent chirality in a polar meron to skyrmion phase transition

Polar skyrmions are predicted to emerge from the interplay of elastic, electrostatic and gradient energies, in contrast to the key role of the anti-symmetric Dzyalozhinskii-Moriya interaction in magnetic skyrmions. With the discovery of topologically-stable polar skyrmions, it is of both fundamental and practical interest to understand the microscopic nature and the possibility of temperature- and strain-driven phase transitions in ensembles of such polar skyrmions. Here, we explore the reversible transition from a skyrmion state (topological charge of -1) to a two-dimensional, tetratic lattice of merons (with topological charge of -1/2) upon varying the temperature and elastic boundary conditions in [(PbTiO3)16/(SrTiO3)16]8 lifted-off membranes. This topological phase transition is accompanied by a change in chirality, from zero-net chirality (in meronic phase) to net-handedness (in skyrmionic phase). To map these changes microscopically required developing new imaging methods. We show how scanning convergent beam electron diffraction provides a robust measure of the local polarization simultaneously with the strain state at sub-nm resolution, while also directly mapping the chirality of each skyrmion. Using this, we demonstrate strain as a crucial order parameter to drive isotropic-to-anisotropic structural transitions of chiral polar skyrmions to non-chiral merons, validated with X-ray reciprocal space mapping and theoretical phase-field simulations. These results revealed by our new measurement methods provide the first illustration of systematic control of rich variety of topological dipole textures by altering the mechanical boundary conditions, which may offer a promising way to control their functionalities in ferroelectric nanodevices using the local and spatial distribution of chirality and order.

cond-mat.mes-hall↗

arXiv2022

Temperature-dependent Multi-well Free-energy Landscape for Phase Transitions: PbTiO3 as a Prototype

It has been a long challenge to analytically construct the quantitative temperature-dependent multi-well free-energy landscape over the space of order parameters describing phase transitions and associated critical phenomena. Here we propose a simple analytical model for the free energy landscape based on a priori concept of Boltzmann thermal mixing among multiple parabolic potentials representing different energetically degenerated ground states in contrast to the popular Landau theory using the high-temperature disordered state as a reference. The model recovers both the Weiss molecular field theory and the temperature dependent behaviors of the second order Landau coefficient. It is rather remarkable that such a simple analytical expression can describe a wide variety of properties across the ferroelectric phase transition in PbTiO3, including the temperature dependences of the spontaneous polarization, the heat capacities, the permittivity tensor, and the lattice parameters. The approach also allows parametrization of the free energy function across phase transitions based directly on the 0 K thermodynamics data that can be obtained from DFT calculations. We anticipate that the approach can be equally applied to other types of critical phenomena, e.g., the superconducting phase transition, the metal-insulator transition, and the magnetic transitions.

cond-mat.mtrl-sci↗

arXiv2022

Lorenz Number and Electronic Thermoelectric Figure of Merit: Thermodynamics and Direct DFT Calculations

The Lorenz number (L) contained in the Wiedemann-Franz law represents the ratio of two kinetic parameters of electronic charge carriers: the electronic contribution to the thermal conductivity (K_el) and the electrical conductivity (sigma), , and can be expressed as LT=K_el/sigma where T is temperature. We demonstrate that the Lorenz number simply equals to the ratio of two thermodynamic quantities: the electronic heat capacity (c_el) and the electrochemical capacitance (c_N) through LT=c_el/c_N , a purely thermodynamic quantity, and thus it can be calculated solely based on the electron density of states of a material. It is shown that our thermodynamic formulation for the Lorenz number leads to: i) the well-known Sommerfeld value L=pi^2/3(k_B/e)^2 at the low temperature limit, ii) the Drude value L=3/2(k_B/e)^2 at the high temperature limit with the free electron gas model, and iii) possible higher values than the Sommerfeld limit for semiconductors. It is also demonstrated that the purely electronic contribution to the thermoelectric figure-of-merit can be directly computed using high-throughput DFT calculations without resorting to the computationally more expensive Boltzmann transport theory to the electronic thermal conductivity and electrical conductivity.

cond-mat.mtrl-sci↗