arXiv subjects

Xiaoqing Pan

Publications and source records attributed to Xiaoqing Pan.

At least 37 records · Page 2Linked to original sources

arXiv2022

Compositionally Complex Perovskite Oxides as a New Class of Li-Ion Solid Electrolytes

Compositionally complex ceramics (CCCs), including high-entropy ceramics (HECs) as a subclass, offer new opportunities of materials discovery beyond the traditional methodology of searching new stoichiometric compounds. Herein, we establish new strategies of tailoring CCCs via a seamless combination of (1) non-equimolar compositional designs and (2) controlling microstructures and interfaces. Using oxide solid electrolytes for all-solid-state batteries as an exemplar, we validate these new strategies via discovering a new class of compositionally complex perovskite oxides (CCPOs) to show the possibility of improving ionic conductivities beyond the limit of conventional doping. As an example (amongst the 28 CCPOs examined), we demonstrate that the ionic conductivity can be improved by >60% in (Li0.375Sr0.4375)(Ta0.375Nb0.375Zr0.125Hf0.125)O3-δ, in comparison with the state-of-art (Li0.375Sr0.4375)(Ta0.75Zr0.25)O3-δ (LSTZ) baseline, via maintaining comparable electrochemical stability. Furthermore, the ionic conductivity can be improved by another >70% via grain boundary (GB) engineering, achieving >270% of the LSTZ baseline. This work suggests transformative new strategies for designing and tailoring HECs and CCCs, thereby opening a new window for discovering materials for energy storage and many other applications.

cond-mat.mtrl-sci↗

arXiv2022

Atomic-scale origin of the low grain-boundary resistance in perovskite solid electrolytes

Oxide solid electrolytes (OSEs) have the potential to achieve improved safety and energy density for lithium-ion batteries, but their high grain-boundary (GB) resistance is a general bottleneck. In the most well studied perovskite OSE, Li3xLa2/3-xTiO3 (LLTO), the ionic conductivity of GBs is about three orders of magnitude lower than that of the bulk. In contrast, the related Li0.375Sr0.4375Ta0.75Zr0.25O3 (LSTZ0.75) perovskite exhibits low GB resistance for reasons yet unknown. Here, we used aberration-corrected scanning transmission electron microscopy and spectroscopy, along with an active learning moment tensor potential, to reveal the atomic scale structure and composition of LSTZ0.75 GBs. Vibrational electron energy loss spectroscopy is applied for the first time to characterize the otherwise unmeasurable Li distribution in GBs of LSTZ0.75. We found that Li depletion, which is a major reason for the low GB ionic conductivity of LLTO, is absent for the GBs of LSTZ0.75. Instead, the low GB resistivity of LSTZ0.75 is attributed to the formation of a unique defective cubic perovskite interfacial structure that contained abundant vacancies. Our study provides insights into the atomic scale mechanisms of low GB resistivity and sheds light on possible paths for designing OSEs with high total ionic conductivity.

cond-mat.mtrl-sci↗

arXiv2022

Disconnection-Mediated Twin/Twin-Junction Migration in FCC metals

We present the results of novel, time-resolved, in situ HRTEM observations, molecular dynamics (MD) simulations, and disconnection theory that elucidate the mechanism by which the motion of grain boundaries (GBs) in polycrystalline materials are coupled through disconnection motion/reactions at/adjacent to GB triple junctions (TJs). We focus on TJs composed of a pair of coherent twin boundaries (CTBs) and a Σ9 GB. As for all GBs, disconnection theory implies that multiple modes/local mechanisms for CTB migration are possible and that the mode selection is affected by the nature of the driving force for migration. While we observe (HRTEM and MD) CTB migration through the motion of pure steps driven by chemical potential jump, other experimental observations (and our simulations) show that stress-driven CTB migration occurs through the motion of disconnections with a non-zero Burgers vector; these are pure-step and twinning-partial CTB migration mechanisms. Our experimental observations and simulations demonstrate that the motion of a GB drags its delimiting TJ and may force the motion of the other GBs meeting at the TJ. Our experiments and simulations focus on two types of TJs composed of a pair of CTBs and a Σ9 GB; a 107° TJ readily migrates while a 70° TJ is immobile (experiment, simulation) in agreement with our disconnection theory even though the intrinsic mobilities of the constituent GBs do not depend on TJ-type. We also demonstrate that disconnections may be formed at TJs (chemical potential jump/stress driven) and at GB/free surface junctions (stress-driven).

cond-mat.mtrl-sci↗

arXiv2021

Emergence of near-boundary segregation zones in face-centered cubic multi-principal element alloys

Grain boundaries have been shown to dramatically influence the behavior of relatively simple materials such as monatomic metals and binary alloys. The increased chemical complexity associated with multi-principal element alloys is hypothesized to lead to new grain boundary phenomena. To explore the relationship between grain boundary structure and chemistry in these materials, hybrid molecular dynamics/Monte Carlo simulations of a faceted Σ11 <110> tilt boundary, chosen to sample both high- and low-energy boundary configurations, are performed in face-centered cubic CrFeCoNiCu and CrFeCoNi equiatomic alloys. Unexpected enrichment of Fe is discovered in the face-centered cubic regions adjacent to the interface and found to be correlated with a structurally-distinct region of reduced atomic volume. Comparison with the boundary of the same type in monatomic Cu demonstrates that altered near-boundary regions exist in simpler systems as well, with the chemical complexity of the multi-principal element alloys highlighting its existence and importance.

cond-mat.mtrl-sci↗

arXiv2021

Experimental Observation of Localized Interfacial Phonon Modes

Interfaces impede heat flow in micro/nanostructured systems. Conventional theories for interfacial thermal transport were derived based on bulk phonon properties of the materials making up the interface without explicitly considering the atomistic interfacial details, which are found critical to correctly describing thermal boundary conductance (TBC). Recent theoretical studies predicted the existence of localized phonon modes at the interface which can play an important role in understanding interfacial thermal transport. However, experimental validation is still lacking. Through a combination of Raman spectroscopy and high-energy resolution electron energy-loss spectroscopy (EELS) in a scanning transmission electron microscope, we report the first experimental observation of localized interfacial phonon modes at ~12 THz at a high-quality epitaxial Si-Ge interface. These modes are further confirmed using molecular dynamics simulations with a high-fidelity neural network interatomic potential, which also yield TBC agreeing well with that measured from time-domain thermoreflectance (TDTR) experiments. Simulations find that the interfacial phonon modes have obvious contribution to the total TBC. Our findings may significantly contribute to the understanding of interfacial thermal transport physics and have impact on engineering TBC at interfaces in applications such as electronics thermal management and thermoelectric energy conversion.

cond-mat.mes-hall↗

arXiv2021

Capturing 3D atomic defects and phonon localization at the 2D heterostructure interface

The 3D local atomic structures and crystal defects at the interfaces of heterostructures control their electronic, magnetic, optical, catalytic and topological quantum properties, but have thus far eluded any direct experimental determination. Here we determine the 3D local atomic positions at the interface of a MoS2-WSe2 heterojunction with picometer precision and correlate 3D atomic defects with localized vibrational properties at the epitaxial interface. We observe point defects, bond distortion, atomic-scale ripples and measure the full 3D strain tensor at the heterointerface. By using the experimental 3D atomic coordinates as direct input to first principles calculations, we reveal new phonon modes localized at the interface, which are corroborated by spatially resolved electron energy-loss spectroscopy. We expect that this work will open the door to correlate structure-property relationships of a wide range of heterostructure interfaces at the single-atom level.

cond-mat.mtrl-sci↗

arXiv2020

Imaging real-time amorphization of hybrid perovskite solar cells under electrical biasing

Perovskite solar cells have drawn much attention in recent years, owing to its world-record setting photovoltaic performances. Despite its promising use in tandem applications and flexible devices, its practicality is still limited by its structural instability often arising from ion migration and defect formation. While it is generally understood that ion instability is a primary cause for degradation, there is still a lack of direct evidence of structural transformation at the atomistic scale. Such an understanding is crucial to evaluate and pin-point how such instabilities are induced relative to external perturbations such as illumination or electrical bias with time, allowing researchers to devise effective strategies to mitigate them. Here, we designed an in-situ TEM setup to enable real-time observation of amorphization in double cation mixed perovskite materials under electrical biasing at 1 V. It is found that amorphization occurs along the (001) and (002) planes, which represents the observation of in-situ facet-dependent amorphization of a perovskite crystal. To reverse the degradation, the samples were heated at 50 oC and was found to recrystallize, effectively regaining its performance losses. This work is vital toward understanding fundamental ion-migration phenomena and address instability challenges of perovskite optoelectronics.

cond-mat.mtrl-sci↗

arXiv2020

Giant Polarization and Abnormal Flexural Deformation in Bent Freestanding Perovskite Oxides

Recent realizations of ultrathin freestanding perovskite oxides offer a unique platform to probe novel properties in two-dimensional oxides. Here, we observed a giant flexoelectric response in freestanding BiFeO3 and SrTiO3 in their bent state arising from strain gradients up to 4x10e7/m, suggesting a promising approach for realizing extremely large polarizations. Additionally, a substantial reversible change in thickness was discovered in bent freestanding BiFeO3, which implies an unusual bending-expansion/shrinkage and thickness-dependence Poisson's ratios in this ferroelectric membrane that has never been seen before in crystalline materials. Our theoretical modeling reveals that this unprecedented flexural deformation within the membrane is attributable to a flexoelectricity-piezoelectricity interplay. The finding unveils intriguing nanoscale electromechanical properties and provides guidance for their practical applications in flexible nanoelectromechanical systems.

cond-mat.mtrl-sci↗

arXiv2020

Two superconducting components with different symmetries in Nd1-xSrxNiO2 films

The pairing mechanism in cuprates remains as one of the most challenging issues in the field of condensed matter physics. The unique 3d9 electron orbital of the Cu2+ ionic states in cuprates is supposed to be the major player for the occurrence of superconductivity. Recently, superconductivity at about 9-15 K was discovered in infinite layer thin films of nickelate Nd1-xSrxNiO2 (x=0.1-0.2) which is believed to have the similar 3d9 orbital electrons. The key issue concerned here is about the superconducting gap function. Here we report the first set data of single particle tunneling measurements on the superconducting nickelate thin films. We find predominantly two types of tunneling spectra, one shows a V-shape feature which can be fitted very well by a d-wave gap function with gap maximum of about 3.9 meV, another one exhibits a full gap of about 2.35 meV. Some spectra demonstrate mixed contributions of these two components. Our results suggest that the newly found Ni-based superconductors play as close analogs to cuprates, and thus demonstrate the commonality of unconventional superconductivity.

cond-mat.supr-con↗

arXiv2019

Epitaxial antiperovskite/perovskite heterostructures for materials design

We demonstrate fabrication of atomically sharp interfaces between nitride antiperovskite Mn$_{3}$GaN and oxide perovskites (La$_{0.3}$Sr$_{0.7}$)(Al$_{0.65}$Ta$_{0.35}$)O$_{3}$ (LSAT) and SrTiO$_{3}$ as paradigms of nitride-antiperovskite/oxide-perovskite heterostructures. Using a combination of scanning transmission electron microscopy (STEM), atomic-resolution spectroscopic techniques, and first-principle calculations, we investigated the atomic-scale structure, composition, and boding at the interface. We show that the epitaxial growth between the antiperovskite and perovskite compounds is mediated by a coherent interfacial monolayer that connects the two anti-structures. We anticipate our results to be a major step for the development of functional antiperovskite/perovskite heterostructures opening to harness a combination of their functional properties including topological properties for ultra low power applications.

cond-mat.mtrl-sci↗

arXiv2019

Spontaneous Hall Effect enhanced by local Ir moments in epitaxial Pr$_2$Ir$_2$O$_7$ thin films

Rare earth pyrochlore Iridates (RE2Ir2O7) consist of two interpenetrating cation sublattices, the RE with highly-frustrated magnetic moments, and the Iridium with extended conduction orbitals significantly mixed by spin-orbit interactions. The coexistence and coupling of these two sublattices create a landscape for discovery and manipulation of quantum phenomena such as the topological Hall effect, massless conduction bands, and quantum criticality. Thin films allow extended control of the material system via symmetry-lowering effects such as strain. While bulk Pr2Ir2O7 shows a spontaneous hysteretic Hall effect below 1.5K, we observe the effect at elevated temperatures up to 15K in epitaxial thin films on (111) YSZ substrates synthesized via solid phase epitaxy. Similar to the bulk, the lack of observable long-range magnetic order in the thin films points to a topological origin. We use synchrotron-based element-specific x-ray diffraction (XRD) and x-ray magnetic circular dichroism (XMCD) to compare powders and thin films to attribute the spontaneous Hall effect in the films to localization of the Ir moments. We link the thin film Ir local moments to lattice distortions absent in the bulk-like powders. We conclude that the elevated-temperature spontaneous Hall effect is caused by the topological effect originating either from the Ir or Pr sublattice, with interaction strength enhanced by the Ir local moments. This spontaneous Hall effect with weak net moment highlights the effect of vanishingly small lattice distortions as a means to discover topological phenomena in metallic frustrated magnetic materials.

cond-mat.mtrl-sci↗

arXiv2019

Observation of perfect Andreev reflection due to Klein paradox in a topological superconducting state

In 1928, P. Dirac proposed a new wave equation to describe relativistic electrons. Shortly afterwards, O. Klein solved a simple potential step problem for the Dirac equation and stumbled upon an apparent paradox - the potential becomes transparent when the height is larger than the electron energy. For massless particles, backscattering is completely forbidden in Klein tunneling, leading to perfect transmission through any potential barrier. Recent advent of condensed matter systems with Dirac-like excitations, such as graphene and topological insulators (TIs), has opened the possibility of observing the Klein tunneling experimentally. In the surface states of TIs, fermions are bound by spin-momentum locking, and are thus immune to backscattering due to time-reversal symmetry. Here we report the observation of perfect Andreev reflection in point contact spectroscopy - a clear signature of Klein tunneling and a manifestation of the underlying relativistic physics of a proximity-induced superconducting state in a topological Kondo insulator.

cond-mat.mes-hall↗

arXiv2018

Direct demonstration of the emergent magnetism resulting from the multivalence Mn in a LaMnO3 epitaxial thin film system

Atomically engineered oxide heterostructures provide a fertile ground for creating novel states. For example, a two-dimensional electron gas at the interface between two oxide insulators, giant thermoelectric Seebeck coefficient, emergent ferromagnetism from otherwise nonmagnetic components, and colossal ionic conductivity. Extensive research efforts reveal that oxygen deficiency or lattice strain play an important role in determining these unexpected properties. Herein, by studying the abrupt presence of robust ferromagnetism (up to 1.5 uB/Mn) in LaMnO3-based heterostructures, we find the multivalence states of Mn that play a decisive role in the emergence of ferromagnetism in the otherwise antiferromagnetic LaMnO3 thin films. Combining spatially resolved electron energy-loss spectroscopy, X-ray absorption spectroscopy and X-ray magnetic circular dichroism techniques, we determine unambiguously that the ferromagnetism results from a conventional Mn3+-O-Mn4+ double-exchange mechanism rather than an interfacial effect. In contrast, the magnetic dead layer of 5 unit cell in proximity to the interface is found to be accompanied with the accumulation of Mn2+ induced by electronic reconstruction. These findings provide a hitherto-unexplored multivalence state of Mn on the emergent magnetism in undoped manganite epitaxial thin films, such as LaMnO3 and BiMnO3, and shed new light on all-oxide spintronic devices.

cond-mat.mtrl-sci↗

arXiv2018

Robust memristors based on layered two-dimensional materials

Van der Waals heterostructure based on layered two-dimensional (2D) materials offers unprecedented opportunities to create materials with atomic precision by design. By combining superior properties of each component, such heterostructure also provides possible solutions to address various challenges of the electronic devices, especially those with vertical multilayered structures. Here, we report the realization of robust memristors for the first time based on van der Waals heterostructure of fully layered 2D materials (graphene/MoS2-xOx/graphene) and demonstrate a good thermal stability lacking in traditional memristors. Such devices have shown excellent switching performance with endurance up to 107 and a record-high operating temperature up to 340oC. By combining in situ high-resolution TEM and STEM studies, we have shown that the MoS2-xOx switching layer, together with the graphene electrodes and their atomically sharp interfaces, are responsible for the observed thermal stability at elevated temperatures. A well-defined conduction channel and a switching mechanism based on the migration of oxygen ions were also revealed. In addition, the fully layered 2D materials offer a good mechanical flexibility for flexible electronic applications, manifested by our experimental demonstration of a good endurance against over 1000 bending cycles. Our results showcase a general and encouraging pathway toward engineering desired device properties by using 2D van der Waals heterostructures.

cond-mat.mtrl-sci↗

arXiv2014

Composition-spread Growth and the Robust Topological Surface State of Kondo insulator SmB6 Thin Films

Topological insulators are a class of materials with insulating bulk but protected conducting surfaces due to the combination of spin-orbit interactions and time-reversal symmetry. The surface states are topologically non-trivial and robust against non-magnetic backscattering, leading to interesting physics and potential quantum computing applications1, 2. Recently there has been a fast growing interest in samarium hexboride (SmB6), a Kondo insulator predicted to be the first example of a correlated topological insulator3, 4. Here we fabricated smooth thin films of nanocrystalline SmB6 films. Their transport behavior indeed shows that SmB6 is a bulk insulator with topological surface states. Upon decreasing the temperature, the resistivity \r{ho} of Sm0.14B0.86 (SmB6) films display significant increase below 50 K due to hybridization gap formation, and it shows a saturation behavior below 10 K. The saturated resistance of our textured films is similar to that of the single crystals, suggesting that this conduction is from the surface and robust against grain boundary scatterings. Point contact spectroscopy (PCS) of the film using a superconducting tip displays both a Kondo Fano resonance and Andreev reflection, suggesting the existence of both an insulating Kondo lattice and metallic surface states.

cond-mat.mtrl-sci↗

arXiv2013

Some inequalities of linear combinations of independent random variables: II

Linear combinations of independent random variables have been extensively studied in the literature. However, most of the work is based on some specific distribution assumptions. In this paper, a companion of (J. Appl. Probab. 48 (2011) 1179-1188), we unify the study of linear combinations of independent nonnegative random variables under the general setup by using some monotone transforms. The results are further generalized to the case of independent but not necessarily identically distributed nonnegative random variables. The main results complement and generalize the results in the literature including (In Studies in Econometrics, Time Series, and Multivariate Statistics (1983) 465-489 Academic Press; Sankhyā Ser. A 60 (1998) 171-175; Sankhyā Ser. A 63 (2001) 128-132; J. Statist. Plann. Inference 92 (2001) 1-5; Bernoulli 17 (2011) 1044-1053).

math.ST↗

arXiv2013

Combinatorial search of superconductivity in Fe-B composition spreads

We have fabricated Fe-B thin film composition spreads in search of possible superconducting phases following a theoretical prediction by Kolmogorov et al.^1 Co-sputtering was used to deposit spreads covering a large compositional region of the Fe-B binary phase diagram. A trace of superconducting phase was found in the nanocrystalline part of the spread, where the film undergoes a metal to insulator transition as a function of composition in a region with the average composition of FeB_2. The resistance drop occurs at 4K, and a diamagnetic signal has also been detected at the same temperature. The superconductivity is suppressible in the magnetic field up to 2 Tesla.

cond-mat.supr-con↗

arXiv2011

Experimental Evidence of Ferroelectric Negative Capacitance in Nanoscale Heterostructures

We report a proof-of-concept demonstration of negative capacitance effect in a nanoscale ferroelectric-dielectric heterostructure. In a bilayer of ferroelectric, Pb(Zr0.2Ti0.8)O3 and dielectric, SrTiO3, the composite capacitance was observed to be larger than the constituent SrTiO3 capacitance, indicating an effective negative capacitance of the constituent Pb(Zr0.2Ti0.8)O3 layer. Temperature is shown to be an effective tuning parameter for the ferroelectric negative capacitance and the degree of capacitance enhancement in the heterostructure. Landau's mean field theory based calculations show qualitative agreement with observed effects. This work underpins the possibility that by replacing gate oxides by ferroelectrics in MOSFETs, the sub threshold slope can be lowered below the classical limit (60 mV/decade).

cond-mat.mes-hall↗