Electronic Band Structure Of Materials Research Articles

Low-Scaling GW Algorithm Applied to Twisted Transition-Metal Dichalcogenide Heterobilayers.

The GW method is widely used for calculating the electronic band structure of materials. The high computational cost of GW algorithms prohibits their application to many systems of interest. We present a periodic, low-scaling, and highly efficient GW algorithm that benefits from the locality of the Gaussian basis and the polarizability. The algorithm enables G0W0 calculations on a MoSe2/WS2 bilayer with 984 atoms per unit cell, in 42 h using 1536 cores. This is 4 orders of magnitude faster than a plane-wave G0W0 algorithm, allowing for unprecedented computational studies of electronic excitations at the nanoscale.

Toward first-principles approaches for mechanistic study of self-trapped exciton luminescence

In recent years, broadband photo-luminescence phenomena arising from self-trapped exciton (STE) in metal halides, including perovskites and various low-dimensional derivatives and variants, have attracted increasing attention for their potential diverse optoelectronic applications like lighting, display, radiation detection, and sensing. Despite great success in experimental discovery of many efficient STE emitters, the current understanding of the STE emission mechanism in metal halides is still immature, and often controversial, which calls for help urgently from predictive first-principles theoretical calculation. Although density-functional theory (DFT) based calculations are routinely used to provide electronic band structure of materials and have contributed greatly to qualitative analysis of luminescence mechanism, more in-depth and quantitative information is highly needed to provide guidelines for rational design of new luminescent materials with desirable features. However, due to the complicated nature of STE emission, involving in particular electron–phonon coupling in both ground and excited states, the usage of DFT is no longer a routine job as for ground state properties. While more sophisticated methods formulated in the framework of many-body perturbation theory like GW-Bethe–Salpeter equation are available and provide theoretically rigorous and accurate description of electronic transitions in extended systems, their application to real STE systems is still severely limited due to highly demanding computational cost. In practice, approximated DFT methods are employed, which have their own strengths and limitations. In this review, we focus on the theoretical approaches that have been heavily used in interpreting STE luminescence mechanism, with a particular emphasis on theoretical methods for exciton self-trapping structural optimization. It is hoped that this review, by summarizing the current status and limitations of theoretical research in the STE emission, will motivate more methodological development efforts in this important field, and push forward the frontiers of excited state electronic structure theory of materials in general.

Dirac Hierarchy in Acoustic Topological Insulators

Dirac cones are essential features of the electronic band structure of materials like graphene and topological insulators (TIs). Lately, this avenue has found a growing interest in classical wave physics by using engineered artificial lattices. Here, we demonstrate an acoustic 3D honeycomb lattice that features a Dirac hierarchy comprising an eightfold bulk Dirac cone, a 2D fourfold surface state Dirac cone, and a 1D twofold hinge state Dirac cone. The lifting of the Dirac degeneracy in each hierarchy authorizes the 3D lattice to appear as a first-order TI with 2D topological surface states, a second-order TI exhibiting 1D hinge states, and a third-order TI of 0D midgap corner states. Analytically we discuss the topological origin of the surface, hinge, and corner states, which are all characterized by out-of-plane and in-plane winding numbers. Our study offers new routes to control sound and vibration for acoustic steering and guiding, on-chip ultrasonic energy concentration, and filtering to name a few.

Electronic transitions and energy band structure of CuGaxAl1-xSe2 crystals

Optical reflectance spectra have been investigated at photon energies higher than the band gap of CuGa x Al 1-x Se solid solutions with x values varying from 0 to 1. The spectral dependence of the real ε 1 and imaginary ε 2 dielectric functions was calculated from experimental reflectivity spectra by means of Kramers–Kronig relations. The behavior of features observed in reflectivity spectra and in the spectral dependence of the dielectric functions was analyzed as a function of the solid solution composition. The experimentally observed peaks have been tabulated and related to the electronic band structure of materials computed in previous works. • Optical reflectance spectra of CuGa x Al 1-x Se 2 crystal measured in a wide spectral range. • Dielectric functions calculated on the basis of Kramers–Kronig relations. • Electronic transitions tabulated according to the energy band structure. • Trends in the behavior of band structure features with changing the composition established.

Harnessing Thermoelectric Puddles via the Stacking Order and Electronic Screening in Graphene.

Thermoelectricity has been investigated mostly on the macroscopic scale despite the fact that its origin is linked to the local electronic band structure of materials. While the role of thermopower from microscopic structures (e.g., surfaces or grain boundaries) increases for emerging thermoelectric materials, manipulating thermoelectric puddles, spatially varying levels of thermoelectric power on the nanometer scale, remains unexplored. Here, we illustrate thermoelectric puddles that can be harnessed via the stacking order and electronic screening in graphene. The local thermoelectric elements were investigated by gate-tunable scanning thermoelectric microscopy on the atomic scale, revealing the roles of local lattice symmetry, impurity charge scatterings, and mechanical strains in the thermopower system. The long-range screening of electrons at the Dirac point in graphene, which could be reached by in-operando spectroscopy, allowed us to unveil distinct thermoelectric puddles in the graphene that are susceptible to the stacking order and external strain. Thus, manipulating thermoelectric puddles via a lattice symmetry and electronic engineering will realize practical thermopower systems with low-dimensional materials.

Density-functional theory methods for electronic band structure properties of materials

Electronic band structure of a material plays a dominant role for its application in photoelectronic energy conversion. The development of highly accurate and efficient first-principles approaches to electronic band structure of materials has been a long-standing challenge in computational materials science. Density-functional theory (DFT) in local density approximation (LDA) or generalized gradient approximation (GGA), currently “the standard model” for first-principles computational materials science, suffers from the so-called band gap problem, i.e ., systematic underestimation of band gaps of insulating systems. There have been active developments in the field of DFT that aim at improving the description of the band gap prediction. In this work, an overview is given on the conceptual foundation for theoretical treatment of electronic band structure in the DFT framework. A systematic review is presented on various approaches that have been recently developed to overcome the DFT band problem. Some personal perspectives are also presented regarding remaining issues and possible solutions to them in the future. In addition, a concise review is also presented on the recent developments in the field of GW -based quasi-particle theoretical approaches to electronic band structure of materials.

Effective mass path integral simulations of quasiparticles in condensed phases

The quantum many-body problem in condensed phases is often simplified using a quasiparticle description, such as effective mass theory for electron motion in a periodic solid. These approaches are often the basis for understanding many fundamental condensed phase processes, including the molecular mechanisms underlying solar energy harvesting and photocatalysis. Despite the importance of these effective particles, there is still a need for computational methods that can explore their behavior on chemically relevant length and time scales. This is especially true when the interactions between the particles and their environment are important. We introduce an approach for studying quasiparticles in condensed phases by combining effective mass theory with the path integral treatment of quantum particles. This framework incorporates the generally anisotropic electronic band structure of materials into path integral simulation schemes to enable modeling of quasiparticles in quantum confinement, for example. We demonstrate the utility of effective mass path integral simulations by modeling an exciton in solid potassium chloride and electron trapping by a sulfur vacancy in monolayer molybdenum disulfide.

Time-resolved\xa0XUV ARPES with tunable 24\u201333\u2009eV laser pulses at 30\u2009meV resolution

High harmonic generation of ultrafast laser pulses can be used to perform angle-resolved photoemission spectroscopy (ARPES) to map the electronic band structure of materials with femtosecond time resolution. However, currently it is difficult to reach high momenta with narrow energy resolution. Here, we combine a gas phase extreme ultraviolet (XUV) femtosecond light source, an XUV monochromator, and a time-of-flight electron analyzer to develop XUV-based time-resolved ARPES. Our technique can produce tunable photon energy between 24–33 eV with an unprecedented energy resolution of 30 meV and time resolution of 200 fs. This technique enables time-, energy- and momentum-resolved investigation of the nonequilibrium dynamics of electrons in materials with a full access to their first Brillouin zone. We evaluate the performance of this setup through exemplary measurements on various quantum materials, including WTe2, WSe2, TiSe2, and Bi2Sr2CaCu2O8+δ.

Superstructure-Induced Splitting of Dirac Cones in Silicene.

Atomic scale engineering of two-dimensional materials could create devices with rich physical and chemical properties. External periodic potentials can enable the manipulation of the electronic band structures of materials. A prototypical system is (3×3)-silicene/Ag(111), which has substrate-induced periodic modulations. Recent angle-resolved photoemission spectroscopy measurements revealed six Dirac cone pairs at the Brillouin zone boundary of Ag(111), but their origin remains unclear [Proc. Natl. Acad. Sci. USA 113, 14656 (2016)]. We used linear dichroism angle-resolved photoemission spectroscopy, the tight-binding model, and first-principles calculations to reveal that these Dirac cones mainly derive from the original cones at the K (K^{'}) points of free-standing silicene. The Dirac cones of free-standing silicene are split by external periodic potentials that originate from the substrate-overlayer interaction. Our results not only confirm the origin of the Dirac cones in the (3×3)-silicene/Ag(111) system, but also provide a powerful route to manipulate the electronic structures of two-dimensional materials.

Visualizing the Effect of an Electrostatic Gate with Angle-Resolved Photoemission Spectroscopy.

Electrostatic gating is pervasive in materials science, yet its effects on the electronic band structure of materials has never been revealed directly by angle-resolved photoemission spectroscopy (ARPES), the technique of choice to noninvasively probe the electronic band structure of a material. By means of a state-of-the-art ARPES setup with submicron spatial resolution, we have investigated a heterostructure composed of Bernal-stacked bilayer graphene (BLG) on hexagonal boron nitride and deposited on a graphite flake. By voltage biasing the latter, the electric field effect is directly visualized on the valence band as well as on the carbon 1s core level of BLG. The band gap opening of BLG submitted to a transverse electric field is discussed and the importance of intra layer screening is put forward. Our results pave the way for new studies that will use momentum-resolved electronic structure information to gain insight on the physics of materials submitted to the electric field effect.

A Perspective on the Application of Spatially Resolved ARPES for 2D Materials.

In this paper, a perspective on the application of Spatially- and Angle-Resolved PhotoEmission Spectroscopy (ARPES) for the study of two-dimensional (2D) materials is presented. ARPES allows the direct measurement of the electronic band structure of materials generating extremely useful insights into their electronic properties. The possibility to apply this technique to 2D materials is of paramount importance because these ultrathin layers are considered fundamental for future electronic, photonic and spintronic devices. In this review an overview of the technical aspects of spatially localized ARPES is given along with a description of the most advanced setups for laboratory and synchrotron-based equipment. This technique is sensitive to the lateral dimensions of the sample. Therefore, a discussion on the preparation methods of 2D material is presented. Some of the most interesting results obtained by ARPES are reported in three sections including: graphene, transition metal dichalcogenides (TMDCs) and 2D heterostructures. Graphene has played a key role in ARPES studies because it inspired the use of this technique with other 2D materials. TMDCs are presented for their peculiar transport, optical and spin properties. Finally, the section featuring heterostructures highlights a future direction for research into 2D material structures.

Doubly Screened Hybrid Functional: An Accurate First-Principles Approach for Both Narrow- and Wide-Gap Semiconductors.

First-principles prediction of electronic band structures of materials is crucial for rational material design, especially in solar-energy-related materials science. Hybrid functionals that mix the Hartree-Fock exact exchange with local or semilocal density functional approximations have proven to be accurate and efficient alternatives to more sophisticated Green's function-based many-body perturbation theory. The optimal fraction of the exact exchange, previously often treated as an empirical parameter, is closely related to the screening strength of the system under study. From a physical point of view, the screening has two extreme forms: the dielectric screening [1/ϵM] that is dominant in wide-gap materials and the Thomas-Fermi metallic screening [exp(-ζ r) ] that is important in narrow-gap semiconductors. In this work, we have systematically investigated the performances of a nonempirical doubly screened hybrid (DSH) functional that considers both screening mechanisms and found that it excels all other existing hybrid functionals and describes the band gaps of narrow-, medium-, and wide-gap insulating systems with comparably good performances.

Experimental realization and characterization of an electronic Lieb lattice.

Geometry, whether on the atomic or nanoscale, is a key factor for the electronic band structure of materials. Some specific geometries give rise to novel and potentially useful electronic bands. For example, a honeycomb lattice leads to Dirac-type bands where the charge carriers behave as massless particles [1]. Theoretical predictions are triggering the exploration of novel 2D geometries [2–10], such as graphynes, Kagomé and the Lieb lattice. The latter is the 2D analogue of the 3D lattice exhibited by perovskites [2]; it is a square-depleted lattice, which is characterised by a band structure featuring Dirac cones intersected by a flat band. Whereas photonic and cold-atom Lieb lattices have been demonstrated [11–17], an electronic equivalent in 2D is difficult to realize in an existing material. Here, we report an electronic Lieb lattice formed by the surface state electrons of Cu(111) confined by an array of CO molecules positioned with a scanning tunneling microscope (STM). Using scanning tunneling microscopy, spectroscopy and wave-function mapping, we confirm the predicted characteristic electronic structure of the Lieb lattice. The experimental findings are corroborated by muffin-tin and tight-binding calculations. At higher energies, second-order electronic patterns are observed, which are equivalent to a super-Lieb lattice.

Ab initio study of the energy loss near sulfur K and L2,3 edges of layered MS2 (M = Ta, Nb and V) in trigonal prismatic and octahedral structures

This study set out to calculate the full-potential linearized augmented plane wave (FPLAPW)-based energy loss near sulfur K and L2,3 edge structures of group V layered transition metal disulfides MS2 (M=Ta, Nb, and V) in octahedral (1T) as well as trigonal prismatic (2H) structures. The calculations showed that, consistent with other calculations, all the studied materials were metallic due to the partially filled d bands in their configurations. Furthermore, the calculated ELNES spectra revealed a good agreement with the available experimental XANES analogues. The d-like and p-like transitions of M and sulfur atoms were the dominant electron transitions in K edge spectra. Spectrum characteristics of the sulfur L2,3 edge of ELNES indicated the transition of sulfur-p electrons to the unoccupied s or d states. These spectra reflect the electronic band structures of materials, as well. As the focus shifts from bulk to monolayer, substrate hybridization becomes stronger. In 2H phases, the dominant peaks of sulfur K edge spectra originate from unoccupied d bands. Further, the broad peaks at higher energy ranges are due to the transitions to sulfur p hybridized with M-s and p states. For energies below 7eV, M-d state is the target state of most of the transitions in both 1T and 2H phases. For above 10eV energies, however, sulfur-d is the target state. Moreover, density of states of sulfur-p (d) is very similar in shape to that of sulfur K (L2,3) edges spectra. For the sulfur L2,3 edges, from 2H-TaS2 to 2H-VS2 and also from bulk to monolayer, the number of transitions to M-d state increases.

Evidencing the need for high spatial resolution in angle-resolved photoemission experiments

Angle-resolved photoemission spectroscopy (ARPES) provides direct access to the electronic band structure of materials. Very recently, the spatial resolution of ARPES setups has dramatically increased, with a spot size at the sample shrinking from 50$\ifmmode\times\else\texttimes\fi{}$50 $\ensuremath{\mu}$m${}^{2}$, typical of most synchrotron-based setups, down to 100$\ifmmode\times\else\texttimes\fi{}$100 nm${}^{2}$ or less. In this work, the authors demonstrate the impact of increased spatial resolution by evidencing faint spatial inhomogeneity in the ARPES signal of a graphene sample that would go undetected in ARPES setups possessing lower spatial resolution.

Optical properties of NbCl5 and ZnMg intercalated graphite compounds

We studied NbCl5 and ZnMg alloy intercalated graphite compounds using an optical spectroscopy technique. These intercalated metallic graphite samples were quite challenging to obtain optical reflectance spectra since they were not flat and quite thin. By using both a new method and an in situ gold evaporation technique we were able to obtain reliable reflectance spectra of our samples in the far and mid infrared range (80–7000 cm−1). We extracted the optical constants including the optical conductivity and the dielectric function from the measured reflectance spectra using a Kramers–Kronig analysis. We also extracted the dc conductivity and the plasma frequencies from the optical conductivity and dielectric functions. NbCl5 intercalated graphite samples show similar optical conductivity spectra as bare highly oriented pyrolytic graphite even though there are some differences in detail. ZnMg intercalated samples show significantly different optical conductivity spectra from the bare graphite. Optical spectroscopy is one of the most reliable experimental techniques to obtain the electronic band structures of materials. The obtained optical conductivities support the recent theoretically calculated electronic band structures of NbCl5 and ZnMg intercalated graphite compounds. Our results also provide important information of electronic structures and charge carrier properties of these two new intercalated materials for applications.

Study of the annealing kinetic effect and implantation energy on phosphorus-implanted silicon wafers using spectroscopic ellipsometry

In this work, we have studied the changes in the optical properties on crystalline silicon implanted wafers (1×1013–1×1016P+∕cm2) using an extensive ellipsometric analysis. The effects of implantation energy (20–180KeV) and subsequent isochronical annealing temperature (300–1100°C) on the electronic band structure of material are investigated. The evolution of pseudodielectric functions is studied using a temperature dependent multilayer model for each implantation dose and energy. The temperature evolution of integrated damage depth profile for each wafer is presented depicting the amorphous/crystalline transition temperatures. Finally, the critical implantation dose and energy of crystalline to amorphous silicon phase are given.