Conduction Band States Research Articles

Europium mixed-valence, long-range magnetic order, and dynamic magnetic response in EuCu2(SixGe1−x)2

In mixed-valence or heavy-fermion systems, the hybridization between local $f$ orbitals and conduction band states can cause the suppression of long-range magnetic order, which competes with strong spin fluctuations. Ce- and Yb-based systems have been found to exhibit fascinating physical properties (heavy-fermion superconductivity, non-Fermi-liquid states, etc.) when tuned to the vicinity of magnetic quantum critical points by use of various external control parameters (temperature, magnetic field, chemical composition). Recently, similar effects (mixed-valence, Kondo fluctuations, heavy Fermi liquid) have been reported to exist in some Eu-based compounds. Unlike Ce (Yb), Eu has a multiple electron (hole) occupancy of its $4f$ shell, and the magnetic Eu$^{2+}$ state ($4f^7$) has no orbital component in the usual $LS$ coupling scheme, which can lead to a quite different and interesting physics. In the EuCu$_{2}$(Si$_{x}$Ge$_{1-x}$)$_{2}$ series, where the valence can be tuned by varying the Si/Ge ratio, it has been reported that a significant valence fluctuation can exist even in the magnetic order regime. This paper presents a detailed study of the latter material using different microscopic probes (XANES, M\"ossbauer spectroscopy, elastic and inelastic neutron scattering), in which the composition dependence of the magnetic order and dynamics across the series is traced back to the change in the Eu valence state. In particular, the results support the persistence of valence fluctuations into the antiferromagnetic state over a sizable composition range below the critical Si concentration $x_c \approx 0.65$. The sequence of magnetic ground states in the series is shown to reflect the evolution of the magnetic spectral response.

An analysis of DSSC performance based on nanosphere, nanorod, and nanoparticle anode morphologies

The precise nature of dye-sensitized solar cell (DSSC) anodes plays a vital role in inter-particle contact, dye absorption, electrolyte diffusion, and distribution of sub conduction band states. This study compares the charge transfer dynamics at the oxide-dye-electrolyte interface in DSSC anodes composed of either nanoparticles (NPs), nanospheres (NSs), or nanorods (NRs). The crystallinity, morphology, visible light and dye absorption on the films were studied by XRD, SEM, and UV-Vis diffuse reflectance spectroscopy while the optoelectronic properties in the DSSC were evaluated by current–voltage, Incident photon to current conversion efficiency, and Electrochemical Impedance Spectroscopy (EIS) measurements. Visible light absorption was highest in NR films while NS films showed the highest light scattering. However, the DSSC with NP films showed the highest power conversion efficiency (PCE) that was attributed to increased dye adsorption amount. The DSSC with NS films had the least PCE but showed the highest Voc of 0.86 V. This high Voc was attributed to the high Fermi level, reduced charge recombination between the electrolyte and primary nanoparticles, and increased electrolyte diffusion within the nanospheres, as deducted from EIS measurements. The study suggests that the interparticle interaction and shape significantly influence the optoelectronic properties of DSSC anodes. The performance in this case was limited by dye absorption.

How disorder affects topological surface states in the limit of ultrathin Bi2Se3 films

We present a first-principles study of electronic properties of ultrathin films of topological insulators (TIs) and scrutinize the role of disorder on the robustness of topological surface states, which can be analysed through their spin textures. The presence of twin grain boundaries is found to increase the band gap of the film, while preserving the spin texture of states in first conduction and valence bands. Differently, partial hydrogenation of one surface not only results in some self-doping effect, but also provokes some alteration of the spin texture symmetry of the electronic states. The formation of a new Dirac cone at M-point of the Brillouin zone of the hydrogenated surface, together with a modified spin texture characteristics are consistent with a dominant Dresselhaus spin–orbit interaction type, more usually observed in 3D materials. Our findings indicate that defects can either be detrimental or beneficial for exploring spin transport of surface states in the limit of ultrathin films of TIs, which maximizes surface over bulk phenomena.

Synthesis of ZnSe and ZnSe:Cu quantum dots by a room temperature photochemical (UV-assisted) approach using Na2 SeO3 as Se source and investigating optical properties.

In this study, ZnSe and ZnSe:Cu quantum dots (QDs) were synthesized using Na2 SeO3 as the Se source by a rapid and room temperature photochemical (UV-assisted) approach. Thioglycolic acid (TGA) was employed as the capping agent and UV illumination activated the chemical reactions. Synthesized QDs were successfully characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), photoluminescence (PL) and UV-visible (UV-vis) spectroscopy, Fourier transform-infrared (FT-IR), and energy dispersive X-ray spectroscopy (EDX). XRD analysis demonstrated the cubic zinc blend phase QDs. TEM images indicated that round-shaped particles were formed, most of which had a diameter of about 4nm. The band gap of the ZnSe QDs was higher than that for ZnSe in bulk. PL spectra indicated an emission with three peaks related to the excitonic, surface trap states and deep level (DL) states. The band gap and QD emission were tunable only by UV illumination time during synthesis. ZnSe:Cu showed green emission due to transition of electrons from the Conduction band (CB) or surface trap states to the 2 T2 acceptor levels of Cu2+ . The emission was increased by increasing the Cu2+ ion concentration, such that the optimal value of PL intensity was obtained for the nominal mole ratio of Cu:Zn 1.5%.

A spectroscopic comparison of IGZO thin films and the parent In2O3, Ga2O3, and ZnO single crystals

We use resonant photoelectron spectroscopy at the Zn 2p, Ga 2p, In 3d, and O 1s absorption edges to report on the electronic properties of indium–gallium–zinc-oxide thin films. We also compare the data with the respective data of the corresponding single crystals In2O3, Ga2O3, and ZnO. We focus on the elemental composition and, in particular, find no evidence for oxygen deficiency. The In, Ga, and Zn absorption data at resonance can be used to analyze the conduction band states in detail. We deduce that a configuration interaction between d10s0 and d9s1states is of importance. We provided a novel mechanism in which configuration interaction induced gap states create both, extended unoccupied states around EF as well as localized occupied states within the gap.

Photoionization cross-section of isotropic defects or impurity centers in isolators

An analytical expression to calculate the photoionization cross-section of isotropic defects or impurity centers is being proposed by using the time-dependent perturbation theory. The ground-state wave function of the electron captured in the impurity state is described by a three-dimensional isotropic harmonic oscillator and the electron excited state in the continuum conduction band is described by a plane wave. The expression has been obtained considering all multipoles terms in the Hamiltonian, and that the radiation field which interacts with electrons is semi-classical and linearly polarized. This approximation is assumed because the effects of the linear contribution are dominant. The available data of the Al2O3:C and Lu2SiO5:Ce systems are in good agreement with our predictions. Such satisfactory comparison is a strong indication that the present model can be used to provide good predictions of the photoionization cross-section in several areas.

Hot-wall-epitaxy growth and electrical/optical characterization of epitaxial BaAl2S4/GaAs layers

The BaAl2S4 layers, which were identified to be a cubic structure in space group Pa3, were grown using the hot wall epitaxy method attached with the reservoir tail. Also, the coincidence lattice mismatch of the grown layers was shown to be −2.52% due to the influence of the compressive strain. The Hall effect measurement showed the different temperature-dependent decrease of mobility at a temperature above 100K. One was T−1/2 at the temperature range of 100<T<180K and the other was T−3/2 at the temperature of T>180K. The mobility decreased in proportion to T1 at a low temperature range of T<100 K. Three PC peaks obtained from the photocurrent (PC) spectra were corresponding to band-to-band transitions, which were observed over the temperature range. These PC peaks were caused by the transition of electrons from the three valence band states in order of increasing energy to the conduction band states, respectively. By analyzing absorption and PC results, the band gap variation has been compared and matched well with Eg(T)=Eg(0)−7.556×10−4T2/(T+523), where Eg(0) is estimated to be 4.0596, 4.1053, and 4.1094eV.

Suppression of Jahn-Teller Distortions and Origin of Piezochromism and Thermochromism in Cu-Cl Hybrid Perovskite.

While pressure-induced changes in the electronic, magnetic, and optical properties of Cu-Cl hybrid perovskites have been studied intensively, the correlation between these properties and pressure-induced structural changes is still vaguely understood. Here, by first-principles calculations on a model system (EDBE)[CuCl4] (EDBE = 2,2'-(ethylenedioxy)bis(ethylammonium)) (a Cu-Cl hybrid perovskite), we correlate the evolution of a series of exciting physical properties with pressure while resolving some of the long-standing debates on the fundamental electronic nature of this important class of material. The material shows two structural phase transitions and an anisotropy in compressibility with increasing pressure. After a critical pressure of 17 GPa, the structure becomes highly symmetric, thereby suppressing the Jahn-Teller distortions. At zero pressure, mapping the optical transitions with the Laporte selection rules, lower and higher energy excitations are found to be of Mott-Hubbard (MH) and charge transfer (CT) type, respectively, signifying the material to be a Mott insulator. The material shows a red shift in the charge transfer band edge with increasing pressure and temperature, demonstrating the piezochromism and the thermochromism, respectively. Piezochromism originates from the changes in mixing of Cl-Cu p-d states, while thermochromism is due to broadening of conduction band states, thereby showing different electronic and structural evolution with pressure and temperature. Furthermore, the magnetic ordering in the material was found to be stable up to higher pressures, making pressure a tool to tune the electronic property without perturbing the magnetic property.

Optical properties of group-3 metal hexaboride nanoparticles by first-principles calculations.

LaB6 nanoparticles are widely used as solar control materials for strong near-infrared absorption and high visible transparency. In order to elucidate the origin of this unique optical property, first-principles calculations have been made for the energy-band structure and dielectric functions of R(III)B6 (R(III) = Sc, Y, La, Ac). On account of the precise assessment of the energy eigenvalues of vacant states in conduction band by employing the screened exchange method, as well as to the incorporation of the Drude term, dielectric functions and various physical properties of LaB6 have been reproduced in excellent agreement with experimental values. Systematic examinations of dielectric functions and electronic structures of the trivalent metal hexaborides have clarified the origin of the visible transparency and the near-infrared plasmon absorption of R(III)B6 nanoparticles.

Electronic Structures of Free-Standing Nanowires made from Indirect Bandgap Semiconductor Gallium Phosphide.

We present a theoretical study of the electronic structures of freestanding nanowires made from gallium phosphide (GaP)—a III-V semiconductor with an indirect bulk bandgap. We consider [001]-oriented GaP nanowires with square and rectangular cross sections, and [111]-oriented GaP nanowires with hexagonal cross sections. Based on tight binding models, both the band structures and wave functions of the nanowires are calculated. For the [001]-oriented GaP nanowires, the bands show anti-crossing structures, while the bands of the [111]-oriented nanowires display crossing structures. Two minima are observed in the conduction bands, while the maximum of the valence bands is always at the Γ-point. Using double group theory, we analyze the symmetry properties of the lowest conduction band states and highest valence band states of GaP nanowires with different sizes and directions. The band state wave functions of the lowest conduction bands and the highest valence bands of the nanowires are evaluated by spatial probability distributions. For practical use, we fit the confinement energies of the electrons and holes in the nanowires to obtain an empirical formula.

The nonlinear absorption of graphene oxide water solution in femtosecond regime

The nonlinear absorption properties of graphene oxide water solution were investigated with femtosecond pulses using Z-scan and pump-probe techniques at 800 nm wavelength. The researching results indicated that the nonlinear absorption of graphene oxide water solution include three parts: two-photon absorption of bound electrons from valence band, excited state absorption of electrons from the low energy state in conduction band and the excited state absorption of electrons from the bottom of conduction band. By theoretically fitting the experimental results, we got the two-photon absorption coefficient about β = 3 × 10−14 m/W, and the two excited state absorption cross section in the order of 10−20 m2 and 10−21 m2 respectively. In addition, the excited state lifetime of electron on the low energy state of conduction band was obtained. The investigation indicated that graphene oxide water solution is a good nonlinear optical material.

First-Principles Study of Thermoelectric Properties of Covalent Organic Frameworks

Covalent organic frameworks (COFs) are new emerging functional porous materials. Strong covalent bonds result in molecular building blocks that can be arranged in layered two-dimensional (2D) or three-dimensional (3D) periodic networks. However, to the best of our knowledge, there have been no reports on experimental and theoretical studies of thermoelectrical properties of COFs to date. Therefore, density functional theory (DFT) and the Boltzmann transport equation have been applied in this work to calculate the semiclassical transport coefficients for phthalocyanine (Pc)-based NiPc, NiPc-benzothiadiazole (BTDA), and Pc COFs. Owing to the well-ordered stacking of the phthalocyanine units and linkers in these compounds, charge-carrier transport is facilitated in the stacking direction. In all studied compounds, the highly directional character of π-orbitals provides band-structure engineering and produces a type of low-dimensional hole transport along the stacking direction. All studied compounds are indirect semiconductors. The low-dimensional transport of holes and the localized states in both valence and conduction bands prevent the electron–hole compensation effect in the Seebeck coefficients, correlating with the large Seebeck coefficients of the studied compounds. Insertion of the electron-deficient building block benzothiadiazole in the NiPc-BTDA COF leads to positive Seebeck coefficients along the a-, b-, and c-directions. The relaxation time was estimated in our investigations from DFT band-structure calculations and the experimentally defined mobility, leading to determination of the electrical conductivity and electronic contribution to the thermal conductivity, as well as figure of merit (ZT) estimation. Ni atom provided greater electrical conductivity along the c-direction in comparison with metal-free Pc COF, and NiPc COF showed the highest thermoelectric performance among the studied COFs.

Electronic and optical properties of InN nanowires

We have employed a multiband envelope function method to study wurtzite [0001] InN nanowires of cylindrical cross section. The electronic subband structure and optical absorption spectrum are calculated as a function of the nanowire radius. The energies of the Γ-point conduction band states show a monotonous increase with decreasing radius. On the other hand, the size dispersion of the valence band states is more involved, showing various crossing and anticrossing effects due to the interplay between the confinement and band mixing effects. Thus, for small (R<2nm) nanowires the highest valence band state has dominant pz-symmetry, but for R>2nm the highest state has dominant p⊥-symmetry, although it is optically inactive. The optical absorption spectra polarized along or perpendicular to the nanowire axis are different on account of the different transitions involved. The spectra of the smaller nanowires display a distinguishable sequence of peaks reflecting the one-dimensional density-of-states. The absorption peaks become denser for larger nanowires, and for radii larger than 10nm the spectrum starts to ressemble that of bulk InN.

Spectroscopic properties of oxygen vacancies inLaAlO3

Oxygen vacancies in LaAlO3 (LAO) play an important role in the formation of the two-dimensional electron gas observed at the LaAlO3/SrTiO3 interface and affect the performance of MOSFETs using LAO as a gate dielectric. However, their spectroscopic properties are still poorly understood, which hampers their experimental identification. Here we predict the absorption spectra and ESR parameters of oxygen vacancies in LAO using periodic and embedded cluster methods and density functional theory (DFT). The structure, charge distribution, and spectroscopic properties of the neutral and charged (1+ and 2+) oxygen vacancies in cubic and rhombohedral LaAlO3 are investigated. The highest intensity optical transitions [calculated using time-dependent DFT (TDDFT)], from the oxygen vacancy states to the conduction-band states have onsets at 3.5 and 4.2 eV for the neutral vacancy and 3.6 eV for the 1+ charged vacancy in rhombohedral LAO and 3.3 and 4.0 eV for the neutral vacancy and 3.4 eV for the 1+ charged vacancy in cubic LAO, respectively. Also reported are the isotropic g value (2.004026) and hyperfine coupling constants of the 1+ charged oxygen vacancy, which are compared to the experimental data obtained using electron spin resonance (ESR) spectroscopy, and accurately predict both the position and the width (3 mT) of its ESR signature. These results may further facilitate the experimental identification of oxygen vacancies in LAO and help to establish their role at the LAO/STO interfaces and in nanodevices using LAO.

The 30-band k ⋅ p theory of valley splitting in silicon thin layers

The valley splitting of the conduction-band states in a thin silicon-on-insulator layer is investigated using the 30-band k ⋅ p theory. The system composed of a few nm thick layer embedded within thick SiO2 layers is analyzed. The valley split states are found to cross periodically with increasing quantum well width, and therefore the energy splitting is an oscillatory function of the quantum well width, with period determined by the wave vector K0 of the conduction band minimum. Because the valley split states are classified by parity, the optical transition between the ground hole state and one of those valley split conduction band states is forbidden. The oscillations in the valley splitting energy decrease with electric field and with smoothing of the composition profile between the well and the barrier by diffusion of oxygen from the SiO2 layers to the Si quantum well. Such a smoothing also leads to a decrease of the interband transition matrix elements. The obtained results are well parametrized by the effective two-valley model, but are found to disagree from previous 30-band calculations. This discrepancy could be traced back to the fact that the basis for the numerical solution of the eigenproblem must be restricted to the first Brillouin zone in order to obtain quantitatively correct results for the valley splitting.

Direct bandgap narrowing of TiO2/MoO3 heterostructure composites for enhanced solar-driven photocatalytic activity

TiO2 nanobelts/MoO3 nanosheets (TM) heterostructure composites have been synthesized via an in-situ growth method in which the TiO2–MoS2 was used as precursor. The whole fabrication process involved the preparation of MoS2 nanoparticles modified TiO2 nanobelts (TiO2 Nbs) and subsequently transformation of the MoS2 to MoO3 nanosheets. The properties of TM were characterized by XRD, FE-SEM, TEM, EDX, DRS, FT-IR, XPS and PL, respectively. The photocatalytic activity of TM was evaluated by photocatalytic degradation of Rhodamine B (Rh B) aqueous solution under simulated sunlight irradiation and its photoabsorption energy (PE, the energy required to excite valence band electrons of TiO2 nanobelts to conduction band states of MoO3 nanosheets (MoO3)) properties are related to the physical and chemical interaction between TiO2 Nbs and MoO3. The experimental results showed that TM exhibited a much better photocatalytic activity than that of pure TiO2, and showed an excellent recyclability property for its photocatalytic applications.

Petahertz optical drive with wide-bandgap semiconductor

Experiments showing that electron dynamics can be controlled on attosecond timescales suggest that wide-bandgap semiconductors could be exploited for petahertz signal processing technologies. High-speed photonic and electronic devices at present rely on radiofrequency electric fields to control the physical properties of a semiconductor1, which limits their operating speed to terahertz frequencies (1012 Hz; ref. 2). Using the electric field from intense light pulses, however, could extend the operating frequency into the petahertz regime (1015 Hz; ref. 3). Here we demonstrate optical driving at a petahertz frequency in the wide-bandgap semiconductor gallium nitride. Few-cycle near-infrared pulses are shown to induce electric interband polarization though a multiphoton process. Dipole oscillations with a periodicity of 860 as are revealed in the gallium nitride electron and hole system by using the quantum interference between the two transitions from the valence and conduction band states, which are probed by an extremely short isolated attosecond pulse with a coherent broadband spectrum. In principle, this shows that the conductivity of the semiconductor can be manipulated on attosecond timescales, which corresponds to instantaneous light-induced switching from insulator to conductor. The resultant dipole frequency reaches 1.16 PHz, showing the potential for future high-speed signal processing technologies based on wide-bandgap semiconductors.

Quasi-Direct Optical Transitions in Silicon Nanocrystals with Intensity Exceeding the Bulk.

Comparison of the measured absolute absorption cross section on a per Si atom basis of plasma-synthesized Si nanocrystals (NCs) with the absorption of bulk crystalline Si shows that while near the band edge the NC absorption is weaker than the bulk, yet above ∼ 2.2 eV the NC absorbs up to 5 times more than the bulk. Using atomistic screened pseudopotential calculations we show that this enhancement arises from interface-induced scattering that enhances the quasi-direct, zero-phonon transitions by mixing direct Γ-like wave function character into the indirect X-like conduction band states, as well as from space confinement that broadens the distribution of wave functions in k-space. The absorption enhancement factor increases exponentially with decreasing NC size and is correlated with the exponentially increasing direct Γ-like wave function character mixed into the NC conduction states. This observation and its theoretical understanding could lead to engineering of Si and other indirect band gap NC materials for optical and optoelectronic applications.

Intra-cavity photon-assisted tunneling collector-base voltage-mediated electron-hole spontaneous-stimulated recombination transistor laser

Optical absorption in a p-n junction diode for a direct-gap semiconductor can be enhanced by photon-assisted tunneling in the presence of a static or dynamic electrical field. In the transistor laser, the coherent photons generated at the base quantum-well interact with the collector field and “assist” optical cavity electron tunneling from the valence band of the base to the conduction band states of the collector. In the present work, we study the cavity coherent photon intensity effect on intra-cavity photon-assisted tunneling (ICPAT) in the transistor laser and realize photon-field enhanced optical absorption. This ICPAT in a transistor laser is the unique property of voltage (field) modulation and the basis for ultrahigh speed direct laser modulation and switching.

An Insight into the Various Defects-Induced Emission in MgAl2O4 and Their Tunability with Phase Behavior: Combined Experimental and Theoretical Approach

The present work describes various defects-induced tunable emission behavior of MgAl2O4 compounds obtained after annealing at different temperatures through a sol–gel combustion route. Multiple defect centers, such as F, F2, F+, and F22+ and different shallow and deep defects were found to be present inside the band gap, as confirmed by the lifetime and time-resolved emission spectroscopy (TRES) studies. The tunable emission characteristic at different annealing temperatures could be linked with the phase behavior of the spinel. Excitation wavelength variation suggested that a photoconversion process of F to F+ centers was involved with λex = 250 nm, followed by a trapping–de-trapping mechanism of the released electrons within different trap states. An exchange mechanism of electrons in between conduction band and shallow states was also observed at room temperature, which was absent at low temperature, as indicated by the emission profile. These observations render it to be a potential optical-based ther...