arXiv subjects

Qingqing Ke

Publications and source records attributed to Qingqing Ke.

16 recordsLinked to original sources

arXiv2023

Abnormal behavior of preferred formation of cationic vacancy from the interior in γ-GeSe monolayer with the stereo-chemical antibonding lone-pair state

Two-dimensional (2D) materials tend to have the preferably formation of vacancies at the outer surface. Here, contrary to the normal notion, we reveal a type of vacancy that thermodynamically initiates from the interior part of the 2D backbone of germanium selenide (γ-GeSe). Interestingly, the Ge-vacancy (VGe) in the interior part of γ-GeSe possesses the lowest formation energy amongst the various types of defects considered. We also find a low diffusion barrier (1.04 eV) of VGe which is a half of those of sulfur vacancy in MoS2. The facile formation of mobile VGe is rooted in the antibonding coupling of the lone-pair Ge 4s and Se 4p states near the valence band maximum, which also exists in other gamma-phase MX (M=Sn, Ge; X=S, Te). The VGe is accompanied by a shallow acceptor level in the band gap and induces strong infrared light absorption and p-type conductivity. The VGe located in the middle cationic Ge sublattice is well protected by the surface Se layers-a feature that is absent in other atomically thin materials. Our work suggests that the unique well-buried inner VGe, with the potential of forming structurally protected ultrathin conducting filaments, may render the GeSe layer an ideal platform for quantum emitting, memristive, and neuromorphic applications.

cond-mat.mtrl-sci↗

arXiv2022

Phonon anharmonicity and thermal conductivity of two-dimensional van der Waals materials: A review

Two-dimensional (2D) van der Waals (vdW) materials have extraordinary thermal properties due to the effect of quantum confinement, making them promising for thermoelectric energy conversion and thermal management in microelectronic devices. In this review, the mechanism of phonon anharmonicity originating from three- and four-phonon interactions is derived. The phonon anharmonicity of 2D vdW materials, involving the Grüneisen parameter, phonon lifetime, and thermal conductivity, is summarized and derived in detail. The size-dependent thermal conductivity of representative 2D vdW materials is discussed experimentally and theoretically. This review will present fundamental and advanced knowledge on how to evaluate the phonon anharmonicity in 2D vdW materials, which will aid the design of new structures and materials for applications related to energy transfer and conversion.

cond-mat.mtrl-sci↗

arXiv2022

Versatile van der Waals Heterostructures of Gamma-GeSe with h-BN/Graphene/MoS2

Recent discovery of a novel hexagonal phase of GeSe (Gamma-GeSe) has triggered great interests in nanoelectronics applications owing to its electrical conductivity of bulk phase even higher than graphite while its monolayer is a semiconductor. For potential applications, construction of functional two-dimensional (2D) contacts is indispensable. Herein, via first-principles calculations, we propose the design of van der Waals heterostructures (vdWHs) of Gamma-GeSe contacting respectively with graphene, 2D h-BN and MoS2, as representatives of metallic, insulator, and semiconductor partners. Our work shows that the h-BN or graphene layer donates electrons to the Gamma-GeSe layer, resulting in n doping in Gamma-GeSe, while the MoS2 layer accepts electrons from the Gamma-GeSe layer leading to p doping of the latter. The Gamma-GeSe/BN heterostructure has a type-I band alignment with large band offsets, indicating that BN can be used as an effective passivating layer to protect Gamma-GeSe from its environmental disturbance while maintaining its major electronic and optical characteristics. For Gamma-GeSe/graphene heterostructure, it is prone to have a very low-Schottky barrier down to tens of meV, easily overcome by thermal excitation, which can be tunable by strain and external electric field. The Gamma-GeSe/MoS2 vdWH forms a Z-scheme interface, which is beneficial for carriers splitting and photon utilization. Our work indicates that Gamma-GeSe can be well passivated by BN, and form intimate contact with graphene for high charge injection efficiency and with MoS2 for efficient carriers splitting for redox reactions.

cond-mat.mtrl-sci↗

arXiv2022

Highly Modulated Dual Semimetal and Semiconducting Gamma-GeSe with Strain Engineering

Layered hexagonal Gamma--GeSe, a new polymorph of GeSe synthesized recently, shows strikingly high electronic conductivity in its bulk form (even higher than graphite) while semiconducting in the case of monolayer (1L). In this work, by using first-principles calculations, we demonstrate that, different from its orthorhombic phases of GeSe, the Gamma--GeSe shows a small spatial anisotropic dependence and a strikingly thickness-dependent behavior with transition from semimetal (bulk, 0.04 eV) to semiconductor (1L, 0.99 eV), and this dual conducting characteristic realized simply with thickness control in Gamma-GeSe has not been found in other 2D materials before. The lacking of d-orbital allows charge carrier with small effective mass (0.16 m0 for electron and 0.23 m0 for hole) which is comparable to phosphorene. Meanwhile, 1L Gamma--GeSe shows a superior flexibility with Young's modulus of 86.59 N/m, only one-quarter of that of graphene and three-quarters of that of MoS2, and Poisson's ratio of 0.26, suggesting a highly flexible lattice. Interestingly, 1L Gamma-GeSe shows an in-plane isotropic elastic modulus inherent with hexagonal symmetry while an anisotropic in-plane effective mass owing to shifted valleys around the band edges. We demonstrate the feasibility of strain engineering in inducing indirect-direct and semiconductor-metal transitions resulting from competing bands at the band edges. Our work shows that the free 1L Gamma-GeSe shows a strong light absorption (~106 cm-1) and an indirect bandgap with rich valleys at band edges, enabling high carrier concentration and a low rate of direct electron-hole recombination which would be promising for nanoelectronics and solar cell applications.

cond-mat.mtrl-sci↗

arXiv2022

Oxygen Deficient α-MoO3 with Promoted Adsorption and State-Quenching of H2O for Gas Sensor: A DFT Study

Semiconducting oxides with reducible cations are ideal platforms for various functional applications in nanoelectronics and catalysts. Here we report an ultrathin monolayer alpha-MoO3 where tunable electronic properties and different gas adsorbing behaviors upon introducing the oxygen vacancies (VO). The unique property of alpha-MoO3 is that it contains three different types of oxygen atoms occupying three Wyckoff sites that are absent in other low-dimensional oxides and provides rich electronic hybridized states. The presence of VO triggers intermediate state in the gap at ~0.59 eV below the conduction band minimum and reduces the work function dramatically, together with new excitations at near infrared. The realigned Fermi level associated with the dangling state of VO reduces the neighboring Mo atoms and affects the gas adsorption thereafter. The binding energy of H2O molecules above VO is 2.5 times up to -0.75 eV compared with that of perfect lattice site and trends of transfer of electrons also reverse. The latter is related with the shallow localized state in the band gap due to H2O adsorbed above perfect MoO3 which becomes quenched upon adsorbing at the VO site. Those rich in-gap defective states in oxygen deficient MoO3, broadening the light absorption and promoting the uptake of water, are conductive to the application of alpha-MoO3 for optoelectronics, photothermal therapy, and sensor of moisture.

cond-mat.mtrl-sci↗

arXiv2019

Design of Phosphorene for Hydrogen Evolution Performance Comparable to Platinum

Phosphorene, a monolayer of bulk black phosphorus, is promising for light harvest owing to its high charge mobility and tunable direct band gap covering a broad spectral range of light. Here, via atomic-scale first-principles simulations, we report a ultrahigh activity of hydrogen evolution reaction (HER) of phosphorene originated from defective activation. Quantitative evaluation of the Gibbs free energy of the ad desorption of hydrogen (H) to from phosphorene (delta_GH) reveals that atomic vacancies and edges play a dominant role in activating the reaction. We find that the defective states, empty and well-localized around the defect core, are compensated by H species. This induces a proper hydrogen interaction complying with the thermoneutral condition of the free energy (delta_GH=0) comparable to platinum. Our findings of the highly activating defective states suggest the design of non-metal HER catalysts with structural engineering of earth-abundant phosphorus structures.

cond-mat.mtrl-sci↗

arXiv2019

Surface-charge-mediated Formation of H-TiO2@Ni(OH)2 Heterostructures for High-Performance Supercapcitors

Supercapacitors or ultracapacitors are promising for efficient energy storage applications, owing to their high power density, high charge-discharge rates, and long cycle life performance. To achieve this goal, a large specific surface area, an high electronic conductivity and a fast cation intercalation de-intercalation process are generally required in the design and preparation of materials for high-performance supercapacitors. Recently, core-shell heterostructures with multifunctionalities are regarded as one of promising materials for supercapacitors or ultracapacitors applications. In particular, one-dimensional (1D) core-shell heterostructures have sparked great scientific and technological interests due to their high versatility and applicability as the essential components in nanoscale electronics, catalysis, chemical sensing, and energy conversion storage devices. Various metal metal oxide, metal metal, metal oxide metal oxide and metal oxide conductive polymers so far have been investigated. Transition metal hydroxide oxide Co3O4, Co(OH)2, MnO2, Mn(OH)2, NiO, Ni(OH)2 and their compounds storing energy by surface faradaic (redox) reactions were generally integrated with conducting scaffold to build core-shell structure. Intensive studies show that an enlarged active surface area of transition metal hydroxide oxide enables a promoted surface redox reaction and enhanced electrochemical performance. Therefore, controllable synthesis of a hierarchically porous construction with high surface areas is critically important for energy storage.

cond-mat.mtrl-sci↗

arXiv2019

Utilization of Strong Charge Transfer Efficiency at 2H-1T Phase Boundary of MoS2 for Superb High-Performance Charge Storage

Transition metal dichalcogenides like MoS2 can exist many phases like the semiconducting 2H and the metallic 1T phases which have shown intriguing properties for energy and electrocatalytic applications. However, the 2H and 1T phases normally distribute coherently in a single-layered MoS2 sheet which is accompanied with ubiquitous hetero-phase boundaries. In this work, by using density functional theory and electrochemical measurement, we report strong charge transfer ability between 2H/1T phase boundary of MoS2 and graphene which accounts for a superb coexistence of gravimetric and volumetric capacitances of 272 F g-1 and 685 F cm-3. As a proof-of-concept application, a flexible solid-state asymmetric supercapacitor based on MoS2/graphene is fabricated, showing a remarkable energy and power densities (46.3 mWh cm-3 and 3.013 Wcm-3). Our work shows the promise of promoting the efficiency of charge flow and energy storage through engineering phase boundary and interface in phase-change materials.

physics.app-ph↗

arXiv2016

Highly Itinerant Atomic Vacancies in Phosphorene

Using detailed first-principles calculations, we investigate the hopping rate of vacancies in phosphorene, an emerging elemental 2D material besides graphene. Our work predicts that a direct observation of these mono-vacancies (MVs), showing a highly mobile and anisotropic motion, is possible only at low temperatures around 70 K or below where the thermal activity is greatly suppressed. At room temperature, the motion of a MV is sixteen orders faster than that in graphene, because of the low diffusion barrier of 0.3 eV. Built-in strain associated with the vacancies extends far along the zigzag direction while attenuating rapidly along the armchair direction. We reveal new features of the motion of di-vacancies (DVs) in phosphorene via multiple dissociation-recombination processes of vacancies owing to a small energy cost of ~ 1.05 eV for the splitting of a DV into two MVs. Furthermore, we find that uniaxial tensile strain along the zigzag direction can promote the motion of MVs, while the tensile strain along the armchair direction has the opposite effect. These itinerant features of vacancies, rooted in the unique puckering structure facilitating bond reorganization, enable phosphorene to be a bright new opportunity to broaden the knowledge of the evolution of vacancies, and a proper control of the exceedingly active and anisotropic movement of the vacancies should be critical for applications based on phosphorene.

cond-mat.mtrl-sci↗

arXiv2015

Giant Phononic Anisotropy and Unusual Anharmonicity of Phosphorene: Interlayer Coupling and Strain Engineering

Phosphorene, an emerging elemental two-dimensional (2D) direct band gap semiconductor with fascinating structural and electronic properties distinctively different from other 2D materials such as graphene and MoS2, is promising for novel nanoelectronic and optoelectronic applications. Phonons, as one of the most important collective excitations, are at the heart for the device performance, as their interactions with electrons and photons govern the carrier mobility and light-emitting efficiency of the material. Here, through a detailed first-principles study, it is demonstrated that monolayer phosphorene exhibits a giant phononic anisotropy, and remarkably, this anisotropy is squarely opposite to its electronic counterpart and can be tuned effectively by strain engineering. By sampling the whole Brillouin zone for the mono-layer phosphorene, several "hidden" directions are found, along which small-momentum phonons are "frozen" with strain and possess the smallest degree of anharmonicity. Unexpectedly, these "hidden" directions are intrinsically different from those usually studied armchair and zigzag directions. Light is also shed on the anisotropy of interlayer coupling of few-layer phosphorene by examining the rigid-layer vibrations. These highly anisotropic and strain-tunable characteristics of phosphorene offer new possibilities for its applications in thermal management, thermoelectronics, nanoelectronics and phononics.

cond-mat.mtrl-sci↗

arXiv2015

Energetics, Charge Transfer and Magnetism of Small Molecules Physisorbed on Phosphorene

First-principles calculations are performed to investigate the interaction of physisorbed small molecules, including CO, H2, H2O, NH3, NO, NO2, and O2, with phosphorene, and their energetics, charge transfer, and magnetic moment are evaluated on the basis of dispersion corrected density functional theory. Our calculations reveal that CO, H2, H2O and NH3 molecules act as a weak donor, whereas O2 and NO2 act as a strong acceptor. While NO molecule donates electrons to graphene, it receives electrons from phosphorene. Among all the investigated molecules, NO2 has the strongest interaction through hybridizing its frontier orbitals with the 3p orbital of phosphorene. The nontrivial and distinct charge transfer occurring between phosphorene and these physisorbed molecules not only renders phosphorene promising for application as a gas sensor, but also provides an effective route to modulating the polarity and density of carriers in phosphorene. In addition, the binding energy of H2 on phosphorene is found to be 0.13 eV/H2, indicating that phosphorene is suitable for both stable room-temperature hydrogen storage and its subsequent facile release.

cond-mat.mtrl-sci↗

arXiv2014

Microstructural Evolution of Charged Defects in the Fatigue Process of Polycrystalline BiFeO3 Thin Films

Fatigue failure in ferroelectrics has been intensively investigated in the past few decades. Most of the mechanisms discussed for ferroelectric fatigue have been built on the "hypothesis of variation in charged defects", which however are rarely evidenced by experimental observation. Here, using a combination of complex impedance spectra techniques, piezoresponse force microscopy and first-principles theory, we examine the microscopic evolution and redistribution of charged defects during the electrical cycling in BiFeO3 thin films. The dynamic formation and melting behaviors of oxygen vacancy (VO) order are identified during the fatigue process. It reveals that the isolated VO tend to self-order along grain boundaries to form a planar-aligned structure, which blocks the domain reversals. Upon further electrical cycling, migration of VO within vacancy clusters is accommodated with a lower energy barrier (~0.2 eV) and facilitates the formation of nearby-electrode layer incorporated with highly concentrated VO. The interplay between the macroscopic fatigue and microscopic evolution of charged defects clearly demonstrates the role of ordered VO cluster in the fatigue failure of BiFeO3 thin films.

cond-mat.mtrl-sci↗

arXiv2012

Oxygen-vacancy-mediated Negative Differential Resistance in La and Mg co-substituted BiFeO3 Thin Film

The conductive characteristics of Bi0.9La0.1Fe0.96Mg0.04O3(BLFM) thin film are investigated at various temperatures and a negative differential resistance (NDR) is observed in the thin film, where a leakage current peak occurs upon application of a downward electric field above 80 oC. The origin of the NDR behavior is shown to be related to the ionic defect of oxygen vacancies (VO..) present in the film. On the basis of analyzing the leakage mechanism and surface potential behavior, the NDR behavior can be understood by considering the competition between the polarized distribution and neutralization of VO...

cond-mat.mtrl-sci↗

arXiv2012

Origin of the Enhanced Polarization in La and Mg Co-substituted BiFeO3 Thin Film during the Fatigue Process

We have studied the polarization fatigue of La and Mg co-substituted BiFeO3 thin film, where a polarization peak is observed during the fatigue process. The origin of such anomalous behavior is analyzed on the basis of the defect evolution using temperature-dependent impedance spectroscopy. It shows that the motion of oxygen vacancies (VO..) is associated with a lower energy barrier, accompanied by the injection of electrons into the film during the fatigue process. A qualitative model is proposed to explain the fatigue behavior, which involves the modification of the Schottky barrier upon the accumulation of VO.. at the metal-dielectric interface.

cond-mat.mtrl-sci↗

arXiv2012

Oxygen-vacancy-related relaxation and scaling behaviors of Bi0.9La0.1Fe0.98Mg0.02O3 (La,Mg-codoped BiFeO3) ferroelectric thin film

Oxygen-vacancies-related dielectric relaxation and scaling behaviors of Bi0.9La0.1Fe0.98Mg0.02O3 (BLFM) thin film have been investigated by temperature-dependent impedance spectroscopy from 40 oC up to 200 oC. We found that hopping electrons and single-charged oxygen vacancies (VO.) coexist in the BLFM thin film and make contribution to dielectric response of grain and grain boundary respectively. The activation energy for VO. is shown to be 0.94 eV in the whole temperature range investigated, whereas the distinct activation energies for electrons are 0.136 eV below 110oC and 0.239 eV above 110oC in association with hopping along the Fe2+- VO.-Fe3+ chain and hopping between Fe2+-Fe3+, respectively, indicating different hopping processes for electrons. Moreover, it has been found that hopping electrons is in form of long rang movement, while localized and long range movement of oxygen vacancies coexist in BLFM film. The Cole-Cole plots in modulus formalism show a poly-dispersive nature of relaxation for oxygen vacancies and a unique relaxation time for hopping electrons. The scaling behavior of modulus spectra further suggests that the distribution of relaxation times for oxygen vacancies is temperature independent.

cond-mat.mtrl-sci↗

arXiv2012

Highly (111)-orientated BiFeO3 thin film deposited on La0.67Sr0.33MnO3 buffered Pt/TiO2/SiO2/Si (100) substrate

Multiferroic BiFeO3 (BFO) thin film exhibiting desired ferroelectric and enhanced magnetic properties was grown on La0.67Sr0.33MnO3 (LSMO) buffered Pt/TiO2/SiO2/Si substrates by off-axis RF magnetic sputtering, where a highly (111)-oriented texture was obtained. The BFO/LSMO thin film exhibits excellent ferroelectric and dielectric behaviors (2Pr ~210.7 μC/cm2, 2Ec~435 kV/cm, εr ~116.8, and tanδ ~ 2.7% at 1 kHz), together with a long fatigue endurance up to 1010 switching cycles at amplitude of 300 kV/cm. An enhancement in magnetic behavior was also observed with Ms=89.5 emu/cm3, which is largely contributed from the magnetic layer of LSMO. The coexistence of ferroelectric and ferromagnetic properties in the double layered BFO/LSMO thin film makes it a promising candidate system for applications where the magnetoelectric behavior is required.

cond-mat.mtrl-sci↗