Evolution Of Electronic States Research Articles

An investigation of the Behaviour of Copper Electronic State Evolution on the Failure of Oil-paper Insulation Systems

Abstract Copper, as one of the most hazardous metals to transformer insulation systems, has attracted a great deal of interest from scholars at home and abroad. Unfortunately, the specific type of copper that causes catalytic aging of oil-paper insulation is still controversial. Therefore, in this paper, the effect of the electronic state evolution of copper in different oxidation states on the aging performance of the insulation systems was investigated by characterization techniques and performance evaluation. Cu2O has a stronger catalytic oxidizing effect on insulation system than CuO. This study elucidates the electronic state evolution of different oxidation states of copper and its influence on the insulation performance, which lays a good foundation for the advancement of transformer fault warning technology.

Revealing electronic state evolution of Co(II)/Co(III) in CoO (111) plane during OER process through magnetic measurement

Revealing electronic state evolution of Co(II)/Co(III) in CoO (111) plane during OER process through magnetic measurement

High-pressure-induced electronic and structural transition of superatoms.

High pressure has been recognized as an important tool in molecule and materials research, and thus, it is expected to be used to understand the evolution of electronic states and geometric structures in superatoms. In this work, by studying three characteristic axial compressions on a typical endohedral metallofullerene superatom U@C28 with Td symmetry, we find that the triplet ground electronic state is preserved when the compression moves along the direction that reduces the symmetry to D2d, but the electronic state of the structure compressed along the direction of symmetry reduction to C2v or Cs is transformed into a singlet. The transition is attributed to the distinction in the response of electron spin to different axial compressions, which results in a change in the electron occupation mode of the system. Furthermore, we also confirm the gradual evolution from stereo to near-plane superatoms and the connection between their electron structures. This is reflected in the fact that the electron density distributions of the superatomic molecular orbitals (SAMOs) with extension along the restricted degrees of freedom (Dz2, Fz3 SAMOs) gradually contract, and the delocalization destruction of special orbitals is associated with this freedom. In addition, Raman and ultraviolet-visible spectra show a hyperchromic effect and redshift of characteristic peaks during axial compression, which are expected to be used for fingerprinting the superatomic planarization. Therefore, our work provides new insights based on high pressure for future research toward the discovery of physical properties and applications of superatoms.

Density of Avoided Crossings and Diabatic Representation.

Electronic structure theory describes the properties of solids using Bloch states that correspond to highly symmetrical nuclear configurations. However, nuclear thermal motion destroys translation symmetry. Here, we describe two approaches relevant to the time evolution of electronic states in the presence of thermal fluctuations. On the one hand, the direct solution of the time-dependent Schrodinger equation for a tight-binding model reveals the diabatic nature of time evolution. On the other hand, because of random nuclear configurations, the electronic Hamiltonian falls into the class of random matrices, which have universal features in their energy spectra. In the end, we discuss combining two approaches to obtain new insights into the influence of thermal fluctuations on electronic states.

Tunable electronic structure of heterosite FePO4: an in-depth structural study and polaron transport.

The development of better electrode materials for lithium-ion batteries has been intensively investigated both due to their fundamental scientific aspects as well as their usefulness in technological applications. The present technological development of rechargeable batteries is hindered by fundamental challenges, such as low energy and power density, short lifespan, and sluggish charge transport kinetics. Among the various anode materials proposed, heterosite FePO4 (h-FP) has been found to intercalate lithium and sodium ion hosts to obtain novel rechargeable batteries. The h-FP has been obtained via the delithiation of triphylite LiFePO4 (LFP), and its structural and electronic properties have been investigated with different crystallite sizes. The synchrotron XRD measurements followed by Rietveld refinement analysis reveal lattice expansion upon the reduction of crystallite size of h-FP. In addition, the decrease in the crystallite size enhances surface energy contributions, thereby creating more oxygen vacancies up to 2% for 21 nm crystallite size. The expansion in the lattice parameters is reflected in the vibrational properties of the h-FP structure, where the red-shift has been observed in the characteristic modes upon the reduction of crystallite size. The local environment of the transition metal ion and its bonding characteristics have been elucidated through soft X-ray absorption spectroscopy (XAS) with the effect of crystallite size. XAS unequivocally reveals the valence state of iron 3d electrons near the Fermi level, which is susceptible to local lattice distortion and uncovers the detailed information on the evolution of electronic states with crystallite size. The observed local lattice distortion has been considered to be as a result of the decrease in the level of covalency between the Fe-3d and O-2p states. Further, we demonstrate the structural advantages of nanosized h-FP on the transport properties, where an enhancement in the polaronic conductivity with decreasing crystallite size has been observed. The polaronic conduction mechanism has been analyzed and discussed on the basis of the Mott model of polaron conduction along with an insightful analysis on the role of the electronic structure. The present study provides spectroscopic results on the anode material that reveal the evolution of electronic states for fingerprinting, understanding, and optimizing it for advanced rechargeable battery operations.

Electronic state evolution of oxygen-doped monolayer WSe2 assisted by femtosecond laser irradiation.

Electronic states are significantly correlated with chemical compositions, and the information related to these factors is especially crucial for the manipulation of the properties of matter. However, this key information is usually verified by after-validation methods, which could not be obtained during material processing, for example, in the field of femtosecond laser direct writing inside materials. Here, critical evolution stages of electronic states for monolayer tungsten diselenide (WSe2) around the modification threshold (at a Mott density of ∼1013 cm-2) are observed by broadband femtosecond transient absorption spectroscopy, which is associated with the intense femtosecond-laser-assisted oxygen-doping mechanism. First-principles calculations and control experiments on graphene-covered monolayer WSe2 further confirm this modification mechanism. Our findings reveal a photochemical reaction for monolayer WSe2 under the Mott density condition and provide an electronic state criterion to in situ monitor the degrees of modification in monolayer transition metal dichalcogenides during the femtosecond laser modification.

Surface Reconstruction for Tin-Based Perovskite Solar Cells

Open-circuit voltage loss and instability from surface Sn(II) oxidation and high-density Sn vacancies pose great hurdles for developing high-performance Sn-based perovskite solar cells (PSCs). Turning attention from the bulk microstructure to surface reconstruction is promising to push the performance enhancement of Sn-based PSCs. Herein, a surface-modulation strategy based on 6-maleimidohexanehydrazide trifluoroacetate is rationally designed to reconstruct the surface structure of FASnI3 films to manage the Fermi level and passivate defects. The electronic state evolution results in an n-type Fermi level shift of the shallow surface, thereby forming an extra back-surface field for electron extraction. Meanwhile, the ion-pairing agent affords passivating cationic and anionic defects, thereby nullifying the charged-defect-rich surface. In particular, the reductive hydrazide group and carboxyl groups alleviate superficial Sn(IV) and inhibit Sn(IV) formation, homogenizing surface potential and prolonging carrier lifetime. Accordingly, devices deliver a champion power conversion efficiency (PCE) of 13.64% and an elongated lifespan, with over 75% of the original PCE after 1000 h of illumination (O2 < 50 ppm). This work presents a new insight on the surface reconstruction strategy for developing high-performance Sn-based PSCs.

Combined spectroscopy and electrical characterization of La:BaSnO3 thin films and heterostructures

For La-doped BaSnO3 thin films grown by pulsed laser deposition, we combine chemical surface characterization and electronic transport studies to probe the evolution of electronic states in the band structure for different La-doping contents. Systematic analyses of spectroscopic data based on fitting the core electron line shapes help to unravel the composition of the surface as well as the dynamics associated with increasing doping. These dynamics are observed with a more pronounced signature in the Sn 3d core level, which exhibits an increasing asymmetry to the high binding energy side of the peak with increasing electron density. The present results expand the current understanding of the interplay between the doping concentration, electronic band structure, and transport properties of epitaxial La:BaSnO3 films.

Topological Lifshitz transition and one-dimensional Weyl mode in HfTe5.

Landau band crossings typically stem from the intra-band evolution of electronic states in magnetic fields and enhance the interaction effect in their vicinity. Here in the extreme quantum limit of topological insulator HfTe5, we report the observation of a topological Lifshitz transition from inter-band Landau level crossings using magneto-infrared spectroscopy. By tracking the Landau level transitions, we demonstrate that band inversion drives the zeroth Landau bands to cross with each other after 4.5 T and forms a one-dimensional Weyl mode with the fundamental gap persistently closed. The unusual reduction of the zeroth Landau level transition activity suggests a topological Lifshitz transition at 21 T, which shifts the Weyl mode close to the Fermi level. As a result, a broad and asymmetric absorption feature emerges due to the Pauli blocking effect in one dimension, along with a distinctive negative magneto-resistivity. Our results provide a strategy for realizing one-dimensional Weyl quasiparticles in bulk crystals.

Enhanced d−p hybridization intertwined with anomalous ground state formation in the van der Waals itinerant magnet Fe5GeTe2

${\mathrm{Fe}}_{5}{\mathrm{GeTe}}_{2}$ is a van der Waals (vdW)-coupled unconventional ferromagnetic metal with a high Curie temperature (${T}_{\mathrm{C}}$) exceeding 300 K. The formation of an anomalous ground state significantly below ${T}_{\mathrm{C}}$ has received considerable attention, resulting in increased interest in understanding the spin-polarized electronic state evolution near the Fermi energy (${E}_{\mathrm{F}}$) as a function of temperature. Despite recent extensive studies, a microscopic understanding of the spin-polarized electronic structure around ${E}_{\mathrm{F}}$ has not yet been established owing to the intrinsic complexity of both the crystal and band structures. In this study, we investigate the temperature dependence of element-specific soft x-ray magnetic circular dichroism (XMCD). A systematic temperature evolution in the XMCD signal from both magnetic Fe and its ligand Te is clearly observed. More importantly, the enhancement in the hybridization between the Fe $3d$ and Te $5p$ states at low temperature in the zero-magnetic field limit is revealed. We discuss the implications of our observation in line with possible emergence of an exotic magnetic ground state in ${\mathrm{Fe}}_{5}{\mathrm{GeTe}}_{2}$.

Visualizing the evolution from Mott insulator to Anderson insulator in Ti-doped 1T-TaS2

The electronic evolution of doped Mott insulators has been extensively studied for decades in search of exotic physical phases. The proposed Mott insulator 1T-TaS2 provides an intriguing platform to study the electronic evolution via doping. Here we apply scanning tunneling microscopy (STM) to study the evolution in Ti-doped 1T-TaS2 at different doping levels. The doping Ti atom locally perturbs the electronic and spin state inside the doped star of David and induces a clover-shaped orbital texture at low-doping levels (x < 0.01). The insulator to metal transition occurs around a critical point x = 0.01, in which small metallic and large insulating domains coexist. The clover-shaped orbital texture emerges at a broader energy range, revealing a competition with the electron correlation. It transforms to a disorder-induced Anderson insulating behavior as doping increases. We directly visualize the trapped electrons in dI/dV conductance maps. The comprehensive study of the series of Ti-doped 1T-TaS2 deepens our understanding of the electronic state evolution in a doped strong-correlated system.

Electronic states of gallium oxide epitaxial thin films and related atomic arrangement

Amorphous, crystallized, and Mg-doped β-Ga2O3 thin films are investigated to understand the evolution of electronic states and the related atomic arrangement. In the process from the amorphous to crystallized phase of Ga2O3 films, disordered atoms transform into six-fold GaO6 octahedra. The denser structure creates more electron density. The crystallized phase widens the band gap, because of the conduction band changes attributed to the Ga 4s states hybridized with O 2s states. The Mg dopants create four-fold GaO4 tetrahedron deficiency. Moreover, the distances between Ga atoms become shorter for the doped film; however, the Ga–O distance is independent of the dopant. Mg dopants affect the oxygen states in valence band and Ga–O interaction at conduction band, which results in a slightly smaller band gap. The electronic evolution of the amorphous, crystallized and doped films is confirmed by the calculated density of states results. These results will be beneficial for the design of more effective semiconductive films.

Phonon Magnetic Moment from Electronic Topological Magnetization.

The traditional theory of magnetic moments for chiral phonons is based on the picture of the circular motion of the Born effective charge, typically yielding a small fractional value of the nuclear magneton. Here we investigate the adiabatic evolution of electronic states induced by the lattice vibration of a chiral phonon and obtain an electronic orbital magnetization in the form of a topological second Chern form. We find that the traditional theory needs to be refined by introducing a k resolved Born effective charge, and identify another contribution from the phonon-modified electronic energy together with the momentum-space Berry curvature. The second Chern form can diverge when there is a Yang's monopole near the parameter space of interest as illustrated by considering a phonon at the Brillouin zone corner in a gapped graphene model. We also find large magnetic moments for the optical phonon in bulk topological materials where nontopological contribution is also important. Our results agree with recent observations in experiments.

Evolution of Electronic State and Properties of Silver Nanoparticles during Their Formation in Aqueous Solution.

The electron density of a nanoparticle is a very important characteristic of the properties of a material. This paper describes the formation of silver nanoparticles (NPs) and the variation in the electronic state of an NP’s surface upon the reduction in Ag+ ions with oxalate ions, induced by UV irradiation. The calculations were based on optical spectrophotometry data. The NPs were characterized using Transmission electron microscopy and Dynamic light scattering. As ~10 nm nanoparticles are formed, the localized surface plasmon resonance (LSPR) band increases in intensity, decreases in width, and shifts to the UV region from 402 to 383 nm. The interband transitions (IBT) band (≤250 nm) increases in intensity, with the band shape and position remaining unchanged. The change in the shape and position of the LSPR band of silver nanoparticles in the course of their formation is attributable to an increasing concentration of free electrons in the particles as a result of a reduction in Ag+ ions on the surface and electron injection by radicals. The ζ-potential of colloids increases with an increase in electron density in silver nuclei. A quantitative relationship between this shift and electron density on the surface was derived on the basis of the Mie–Drude theory. The observed blue shift (19 nm) corresponds to an approximately 10% increase in the concentration of electrons in silver nanoparticles.

Pb/Bi heterostructure as a versatile platform to realize topological superconductivity

Abstract Realization of topological superconductors (TSCs) hosting Majorana fermions is an exciting challenge in materials science. Majorana fermions are predicted to emerge at vortex cores of two-dimensional (2D) TSCs and at both ends of one-dimensional (1D) TSCs; these two types of TSCs have been explored independently in different materials. Here, a system which has a potential to access both 1D and 2D TSCs in a single platform, Pb(111)/Bi(111) heterostructure, is proposed. One to twenty bilayers (BLs) of Bi(111) ultra-thin films are epitaxially fabricated on TlBiSe$_2$, and an intriguing evolution of electronic states upon variation of Bi-layer thickness is revealed by angle-resolved photoemission spectroscopy. The metallic quantum-well states at 1–2BLs are found to turn into the Rashba states at 5–20BLs, via the semiconducting states at 3BL. Fabrication of a Pb(111) film on 20BL Bi(111) enables observation of the proximity-induced superconductivity in Bi(111) as evident from a 1 meV energy gap at 5 K; these energy and temperature scales are considerably larger than those of Rashba superconductors. The Pb/Bi heterostructure serves as a versatile platform to study the interplay among proximity-induced superconductivity, band structure, and topology.

Site substitution in GdMnO3 : Effects on structural, electronic, and magnetic properties

We report on detailed structural, electronic and magnetic studies of GdMn$_{1-x}$Cr$_x$O$_3$ for Cr doping levels 0 $\le$ $x$ $\le$ 1. In the solid solutions, the Jahn-Teller distortion associated with Mn$^{3+}$ ions gives rise to major changes in the ${bc}$-plane sub-lattice and also the effective orbital ordering in the ${ab}$-plane, which persist up to the compositions $x$ $\sim$ 0.35. These distinct features in the lattice and orbital degrees of freedom are also correlated with $bc$-plane anisotropy of the local Gd environment. A gradual evolution of electronic states with doping is also clearly seen in O $K$-edge x-ray absorption spectra. Evidence of magnetization reversal in field-cooled-cooling mode for $x$ $\ge$ 0.35 coinciding the Jahn-Teller crossover, suggests a close correlation between magnetic interaction and structural distortion. These observations indicate a strong entanglement between lattice, spin, electronic and orbital degrees of freedom. The nonmonotonic variation of remnant magnetization can be explained by doping induced modification of magnetic interactions. Density functional theory calculations are consistent with a layer-by-layer type doping with ferromagnetic (antiferomagnetic) coupling between Mn (Cr) ions for intermediate compound ($x$ = 0.5), which is distinct from that observed for the end members GMnO$_3$ and GdCrO$_3$.

Spectroscopy of buried states in black phosphorus with surface doping

Electrostatic gating or alkali metal evaporation can be successfully employed to tune the interface of layered black phosphorus (BP) from a semiconductor to a 2D Dirac semimetal. Although Angle Resolved Photoelectron Spectroscopy (ARPES) experiments have captured the collapse of the band gap in the inversion layer, a quantitative estimation of band structure evolution has been hindered by the short escape depth and matrix elements of the probed photoelectrons. Here, we precisely monitor the evolution of electronic states using time-resolved ARPES at a photon energy of 6.3 eV. The probing depth of laser-based ARPES is long enough to observe the buried electronic states originating from the valence band maximum. Our data shows that the band gap has a maximal value of 0.32 eV in the pristine sample, and that it shrinks down monotonically by increasing the carrier concentration in the topmost layer. Most interestingly, the band velocity of the valence band increases by a factor of two along the armchair direction, surpassing the value reported in graphene on silicon carbide (SiC). This control of band structure via external gating will be of interest with regard to the design of optoelectronic devices.

Electronic and nuclear dynamics in one

Chemical Physics Because of the complex, ultrafast interplay between nuclear and electronic degrees of freedom, probing both nuclear and electronic dynamics in excited electronic states within a single time-resolved experiment is a great challenge. Yang et al. used ultrafast electron diffraction in combination with ab initio nonadiabatic molecular dynamics and diffraction simulations to study the relaxation dynamics of isolated pyridine molecules after photoexcitation to the S1 state (see the Perspective by Domcke and Sobolewski). They showed that electronic state evolution and molecular structural changes can be recorded simultaneously and independently by tracing a transient signal in small-angle inelastic scattering and large-angle elastic diffraction, respectively. Science , this issue p. [885][1]; see also p. [820][2] [1]: /lookup/doi/10.1126/science.abb2235 [2]: /lookup/doi/10.1126/science.abb9937

Evolution of Electronic States and Emergence of Superconductivity in the Polar Semiconductor GeTe by Doping Valence-Skipping Indium

GeTe is a chemically simple IV-VI semiconductor which bears a rich plethora of different physical properties induced by doping and external stimuli. Here, we report a superconductor-semiconductor-superconductor transition controlled by finely-tuned In doping. Our results reveal the existence of a critical doping concentration x_{c}=0.12 in Ge_{1-x}In_{x}Te, where various properties, including structure, resistivity, charge carrier type, and the density of states, take either an extremum or change their character. At the same time, we find indications of a change in the In-valence state from In^{3+} to In^{1+} with increasing x by core-level photoemission spectroscopy, suggesting that this system is a new promising playground to probe valence fluctuations and their possible impact on structural, electronic, and thermodynamic properties of their host.

Real-Space Approach for the Electronic Calculation of Twisted Bilayer Graphene Using the Orthogonal Polynomial Technique

We discuss technical issues involving the implementation of a computational method for the electronic structure of material systems of arbitrary atomic arrangement. The method is based on the analysis of time evolution of electron states in the real lattice space. The Chebyshev polynomials of the first kind are used to approximate the time evolution operator. We demonstrate that the developed method is powerful and efficient since the computational scaling law is linear. We invoked the method to study the electronic properties of special twisted bilayer graphene whose atomic structure is quasi-crystalline. We show the density of states of an electron in this graphene system as well as the variation of the associated time auto-correlation function. We find the fluctuation of electron density on the lattice nodes forming a typical pattern closely related to the typical atomic pattern of the quasi-crystalline bilayer graphene configuration.