Experimental Band Structure Research Articles

Photoelectron spectroscopy on single crystals of organic semiconductors: experimental electronic band structure for optoelectronic properties

Methodologies and experimental achievements for exploration into electronic band structures of organic semiconductor and hybrid perovskite single crystals are reviewed.

Role of Ce 4f-conduction band on-site hybridisation in the nature of magnetism in Ce5MGe2, where M is d-electron-type metal

ABSTRACTA combined experimental study and band structure calculations indicate a mixed valence of Ce in the series of CeGe compounds ( Ru, Rh, Pd, and Ag), due to strong on-site hybridisation () between Ce states and conduction band, which is a reason for their complex magnetic structure. It has been shown that energy is meV and does not significantly depend on metal M. In effect, the Curie temperatures of these compounds are very similar ( K). However, is strongly modified by local atomic environment of Ce ions. The same, exchange interaction between various Ce ions depends on random occupation in the vicinity of Ce sites, which can be cause of spin glass-like state () in the CeGe series. On the basis of Schrieffer–Wolff transformation, ab initio calculations and x-ray photoelectron spectroscopy (XPS) data, we estimated coupling constants for a CeGe series, which are dependent on Wyckoff position of Ce and its atomic environment. We argue that various are a reason of spin glass-like state in each compound. For CeRuGe, CeRhGe and CePdGe, the interband hybridisation forms a pseudogap in density of states (DOS) at the Fermi level, which could be reason of a Mott variable-range hoping behaviour.

Experimental band structure spectroscopy along a synthetic dimension

There has been significant recent interest in synthetic dimensions, where internal degrees of freedom of a particle are coupled to form higher-dimensional lattices in lower-dimensional physical structures. For these systems, the concept of band structure along the synthetic dimension plays a central role in their theoretical description. Here we provide a direct experimental measurement of the band structure along the synthetic dimension. By dynamically modulating a resonator at frequencies commensurate with its mode spacing, we create a periodically driven lattice of coupled modes in the frequency dimension. The strength and range of couplings can be dynamically reconfigured by changing the modulation amplitude and frequency. We show theoretically and demonstrate experimentally that time-resolved transmission measurements of this system provide a direct readout of its band structure. We also realize long-range coupling, gauge potentials and nonreciprocal bands by simply incorporating additional frequency drives, enabling great flexibility in band structure engineering.

A WO3-CuWO4 nanostructured heterojunction for enhanced n-butanol sensing performance

Herein, a WO3-CuWO4 nanostructured heterojunction was prepared by a facile two-step hydrothermal method. It is composed of a WO3 square microplate and CuWO4 nanoparticles. Then, the gas sensing properties were investigated under optimal operating temperature (120 °C). The WO3-CuWO4 heterostructure shows good sensing performance towards n-butanol, with a response value up to 9.4 to towards 30 ppm n-butanol, and the response value is about 3 times higher than that of pristine WO3. Its detection limit for n-butanol is 0.1 ppm, which indicates a potential application in lower concentration detection. Moreover, the response time of WO3-CuWO4 nanostructured heterojunction and the pristine WO3 are 21 s and 240 s respectively, revealing that there is a faster gas sensing process in the heterostructure. A possible sensing mechanism was then proposed on the basis of experimental data and band structure analysis. The significant enhancement of WO3-CuWO4 heterostructure could be attributed to the formation of heterojunction, which brings electronic sensitization and electron transport pathway modulation. The work offered a kind of novel and cost-effective sensing materials, and inspired more novel devices based on nanostructured heterojunction mechanism.

Helium-Surface Interaction and Electronic Corrugation of Bi2Se3(111).

We present a study of the atom–surface interaction potential for the He–Bi2Se3(111) system. Using selective adsorption resonances, we are able to obtain the complete experimental band structure of atoms in the corrugated surface potential of the topological insulator Bi2Se3. He atom scattering spectra show several selective adsorption resonance features that are analyzed, starting with the free-atom approximation and a laterally averaged atom–surface interaction potential. Based on quantum mechanical calculations of the He–surface scattering intensities and resonance processes, we are then considering the three-dimensional atom–surface interaction potential, which is further refined to reproduce the experimental data. Following this analysis, the He–Bi2Se3(111) interaction potential is best represented by a corrugated Morse potential with a well depth of D = (6.54 ± 0.05) meV, a stiffness of κ = (0.58 ± 0.02) Å–1, and a surface electronic corrugation of (5.8 ± 0.2)% of the lattice constant. The experimental data may also be used as a challenging benchmark system to analyze the suitability of several van der Waals approaches: the He–Bi2Se3(111) interaction captures the fundamentals of weak adsorption systems where the binding is governed by long-range electronic correlations.

Electronic properties of GaAsBi(001) alloys at low Bi content

Despite its potential in the fields of optoelectronics and topological insulators, experimental electronic band structure studies of Bi-doped GaAs are scarce. The reason is the complexity of growth which tends to leave bulk and in particular surface properties in an undefined state. Here we present an in depth investigation of structural and electronic properties of GaAsBi epilayers grown by molecular beam epitaxy with high (001) crystalline order and well-defined surface structures evident from low-energy electron diffraction. X-ray and ultraviolet photoemission spectrocopy as well as angle-resolved photoemission data at variable photon energies allows to disentangle a Bi-rich surface layer with $(1\times3)$ symmetry from the effects of Bi atoms incorporated in the GaAs bulk matrix. The influence of Bi concentrations up to $\approx 1$\% integrated in the GaAs bulk are visible in angle-resolved photoemission spectra after mild ion bombardment and subsequent annealing steps. Interpretation of our results is obtained via density functional theory simulations of bulk and $\beta 2(2\times 4)$ reconstructed slab geometries with and without Bi. Bi-induced energy shifts in the dispersion of GaAs heavy and light hole bulk bands are evident both in experiment and theory, which are relevant for modulations in the optical band gap and thus optoelectronic applications.

Two-kind boson mixture honeycomb Hamiltonian of Bloch exciton-polaritons

The electronic bandstructure of a solid is a collection of allowed bands separated by forbidden bands, revealing the geometric symmetry of the crystal structures. Comprehensive knowledge of the bandstructure with band parameters explains intrinsic physical, chemical and mechanical properties of the solid. Here we report the artificial polaritonic bandstructures of two-dimensional honeycomb lattices for microcavity exciton-polaritons using GaAs semiconductors in the wide-range detuning values, from cavity-photon-like (red-detuned) to exciton-like (blue-detuned) regimes. In order to understand the experimental bandstructures and their band parameters, such as gap energies, bandwidths, hopping integrals and density of states, we originally establish a polariton band theory within an augmented plane wave method with two-kind-bosons, cavity photons trapped at the lattice sites and freely moving excitons. In particular, this two-kind-band theory is absolutely essential to elucidate the exciton effect in the bandstructures of blue-detuned exciton-polaritons, where the flattened exciton-like dispersion appears at larger in-plane momentum values captured in our experimental access window. We reach an excellent agreement between theory and experiments in all detuning values.

Structural correlation with the Griffiths phase in disordered magnetic systems

In this work we report detailed experimental results and band structure calculations to establish a subtle link between the crystal structure and Griffiths phase (GP) behavior for the geometrically frustrated intermetallic $\mathrm{Gd}{\mathit{M}}_{x}{\mathrm{Sn}}_{2\ensuremath{-}\ensuremath{\delta}}$ (M = Co, Ni, Cu; $0l\mathit{x}l1,0\ensuremath{\le}\ensuremath{\delta}\ensuremath{\le}0.22$) compounds. The crystal structure analysis through powder x-ray diffraction patterns reveals that the atomic positions of the M atoms in the GP analogs are slightly displaced in comparison to those of non-GP members of this series. Further, the band structure calculation shows that this slightly differing atomic position of M atoms results in narrowing in M d bands and the ferromagnetic clusters centered on the T atoms are responsible for GP behavior. This effect is insignificant in non-GP members.

High response and selectivity of single crystalline ZnO nanorods modified by In2O3 nanoparticles for n-butanol gas sensing

In2O3-nanoparticle-modified single crystalline ZnO nanorods with enhanced gas-sensing performance were prepared using a facile sol-gel and chemical precipitation process. In2O3 nanoparticles obtained good dispersibility and were modified on the surface ZnO nanorods. One-dimensional ZnO nanorods served as a matrix for In2O3 nanoparticles, which effectively restrained the agglomeration of the In2O3 nanoparticles and increased the active sites for the sensing reaction. The sensing performance of as-prepared In2O3/ZnO and ZnO sensors was systematically tested using n-butanol as the probe analyte. Test results revealed the In2O3/ZnO sensor response was 104.3 at a concentration of 100 ppm, 3.5 and 5.3 times higher than that of the pure ZnO and In2O3 sensor, respectively. The influence of added In2O3 on sensing performance of the In2O3/ZnO nanocomposites was discussed. Test results showed that the optimal atomic ratio of indium was 3.3%. The response of the In2O3/ZnO sensor reached 6.1 at a concentration of 1 ppm, suggesting good detection of n-butanol. The In2O3/ZnO sensor displayed rapid response-recovery speed along with good selectivity and stability. A possible sensing mechanism for In2O3/ZnO was thus proposed based on experimental data and band structure analysis.

The band structure of the quasi-one-dimensional layered semiconductor TiS3(001)

The experimental mapping of the band structure of TiS3(001), by momentum resolution nanospot angle resolved photoemission, is presented. The experimental band structure, derived from angle-resolved photoemission, confirms that the top of the valence band is at the center of the Brillouin zone. This trichalcogenide has a rectangular surface Brillouin zone where the effective hole mass along the chain direction is −0.95 ± 0.09 me, while perpendicular to the chain direction, the magnitude of the effective hole mass is much lower at −0.37 ± 0.1 me. The placement of the valence band well below the Fermi level suggests that this is an n-type semiconductor.

Optical Transitions and Excitonic Properties of Ge1–xSnx Alloy Quantum Dots

Using hybrid functional calculations and experimental characterization, we analyze optical properties of 2–3 nm Ge1–xSnx alloy quantum dots, synthesized by colloidal chemistry methods. Hybrid functional theory, tuned to yield experimental bulk band structure of germanium, reproduces directly measured properties of Ge1–xSnx quantum dots, such as lattice constants, energy gaps, and absorption spectra. Time-dependent hybrid functional calculations yield optical absorption in good agreement with experiments, and allow probing the nature of the dark excitons in quantum dots. Calculations suggest a spin-forbidden dark exciton ground state, which is supported by the changes in the photoluminescence lifetimes with temperature and tin concentrations. The synthesis and theoretical understanding of Ge1–xSnx alloy quantum dots will add to the overall toolbox of low to nontoxic, silicon-compatible group IV semiconductors with potential application in visible to near-infrared optoelectronics.

Indium selenide: an insight into electronic band structure and surface excitations

We have investigated the electronic response of single crystals of indium selenide by means of angle-resolved photoemission spectroscopy, electron energy loss spectroscopy and density functional theory. The loss spectrum of indium selenide shows the direct free exciton at ~1.3 eV and several other peaks, which do not exhibit dispersion with the momentum. The joint analysis of the experimental band structure and the density of states indicates that spectral features in the loss function are strictly related to single-particle transitions. These excitations cannot be considered as fully coherent plasmons and they are damped even in the optical limit, i.e. for small momenta. The comparison of the calculated symmetry-projected density of states with electron energy loss spectra enables the assignment of the spectral features to transitions between specific electronic states. Furthermore, the effects of ambient gases on the band structure and on the loss function have been probed.

Electronic structure and optical properties of noncentrosymmetric LiGaSe2: Experimental measurements and DFT band structure calculations

We report on measurements of X-ray photoelectron (XP) spectra for pristine and Ar+ ion-irradiated surfaces of LiGaSe2 single crystal grown by Bridgman-Stockbarger method. Electronic structure of the LiGaSe2 compound is studied from a theoretical and experimental viewpoint. In particular, total and partial densities of states of LiGaSe2 are investigated by density functional theory (DFT) calculations employing the augmented plane wave + local orbitals (APW + lo) method and they are verified by data of X-ray spectroscopy measurements. The DFT calculations indicate that the main contributors to the valence band of LiGaSe2 are the Se 4p states, which contribute mainly at the top and in the upper portion of the valence band, with also essential contributions of these states in the lower portion of the band. Other substantial contributions to the valence band of LiGaSe2 emerge from the Ga 4s and Ga 4p states contributing mainly at the lower ant upper portions of the valence band, respectively. With respect to the conduction band, the calculations indicate that its bottom is composed mainly from contributions of the unoccupied Ga s and Se p states. The present calculations are confirmed experimentally when comparing the XP valence-band spectrum of the LiGaS2 single crystal on a common energy scale with the X-ray emission bands representing the energy distribution of the Ga 4p and Se 4p states. Measurements of the fundamental absorption edges at room temperature reveal that bandgap value, Eg, of LiGaSe2 is equal to 3.47 eV and the Eg value increases up to 3.66 eV when decreasing temperature to 80 K. The main optical characteristics of the LiGaSe2 compound are clarified by the DFT calculations.

Evidence of metal-semimetal-transition from Cu2TlSe2 to Cu2TlTe2

Transition metal compounds with quasi-two-dimensional structure demonstrate a series of un-precedent quantum phases, such as topological insulator, topological phase transition under thermal/pressure stimuli, which is attributed to delicate interplay among interlayer coupling, spin-orbit coupling and stoichiometry. Here, Cu2TlSe2 and Cu2TlTe2 crystals were successfully synthesized by Bridgeman method. Highly crystalline quality of these samples is verified by X-ray diffraction and microstructural characterization. Temperature-dependent-Hall-resistivity shows that Cu2TlSe2 is hole-like and Hall resistivity is in-sensitive to temperature; while Hall resistivity of Cu2TlTe2 is positive at room temperature and change to negative at 30K. Combined experimental results and electronic band structures calculated by first-principles method, it is revealed that Cu2TlSe2 is a metal, but Cu2TlTe2 is a semi-metal. This work demonstrates the rich physical phases of layered transition metal compounds under the interplay among interlayer coupling, spin-orbit coupling and stoichiometry.

Direct observation of site-selective hydrogenation and spin-polarization in hydrogenated hexagonal boron nitride on Ni(111).

We report the structural analysis and spin-dependent band structure of hydrogenated boron nitride adsorbed on Ni(111). The atomic displacement studied by using the normal incidence X-ray standing wave (NIXSW) technique supports the H-B(fcc):N(top) model, in which hydrogen atoms are site-selectively chemisorbed on boron atoms and N atoms remain on top of Ni atoms. The distance between the Ni plane and nitrogen plane did not change after hydrogenation, which implies that the interaction between Ni and N is 3d-π orbital mixing (donation and back-donation) even after hydrogenation of boron. The remaining π* peaks in near-edge X-ray absorption fine structure (NEXAFS) spectra are a manifestation of the rehybridization of sp2 into sp3 states, which is consistent with the N-B-N bonding angle derived from NIXSW measurement. The SPMDS measurement revealed the spin asymmetry appearing on hydrogenated h-BN, which was originated from a π related orbital with back donation from the Ni 3d state. Even though the atomic displacement is reproduced by the density functional theory (DFT) calculation with the H-B(fcc):N(top) model, the experimental spin-dependent band structure was not reproduced by DFT possibly due to the self-interaction error (SIE). These results reinforce the site-selective hydrogenation of boron and pave the way for efficient design of BN nanomaterials for hydrogen storage.

Experimental determination of excitonic band structures of single-walled carbon nanotubes using circular dichroism spectra.

Experimental band structure analyses of single-walled carbon nanotubes have not yet been reported, to the best of our knowledge, except for a limited number of reports using scanning tunnelling spectroscopy. Here we demonstrate the experimental determination of the excitonic band structures of single-chirality single-walled carbon nanotubes using their circular dichroism spectra. In this analysis, we use gel column chromatography combining overloading selective adsorption with stepwise elution to separate 12 different single-chirality enantiomers. Our samples show higher circular dichroism intensities than the highest values reported in previous works, indicating their high enantiomeric purity. Excitonic band structure analysis is performed by assigning all observed Eii and Eij optical transitions in the circular dichroism spectra. The results reproduce the asymmetric structures of the valence and conduction bands predicted by density functional theory. Finally, we demonstrate that an extended empirical formula can estimate Eij optical transition energies for any (n,m) species.

Surface Electronic Structure of Hybrid Organo Lead Bromide Perovskite Single Crystals

The electronic structure and band dispersion of methylammonium lead bromide, CH3NH3PbBr3, has been investigated through a combination of angle-resolved photoemission spectroscopy (ARPES) and inverse photoemission spectroscopy (IPES), as well as theoretical modeling based on density functional theory. The experimental band structures are consistent with the density functional calculations. The results demonstrate the presence of a dispersive valence band in MAPbBr3 that peaks at the M point of the surface Brillouin zone. The results also indicate that the surface termination of the CH3NH3PbBr3 is the methylammonium bromide (CH3NH3Br) layer. We find our results support models that predict a heavier hole effective mass in the region of −0.23 to −0.26 me, along the Γ (surface Brillouin center) to M point of the surface Brillouin zone. The surface appears to be n-type as a result of an excess of lead in the surface region.

Angle-resolved spectroscopy study of Ni-based superconductorSrNi2As2

We performed an angle-resolved photoemission spectroscopy study of the Ni-based superconductor SrNi$_2$As$_2$. Electron and hole Fermi surface pockets are observed, but their different shapes and sizes lead to very poor nesting conditions. The experimental electronic band structure of SrNi$_2$As$_2$ is in good agreement with first-principles calculations after a slight renormalization (by a factor 1.1), confirming the picture of Hund's exchange-dominated electronic correlations decreasing with increasing filling of the $3d$ shell in the Fe-, Co- and Ni-based compounds. These findings emphasize the importance of Hund's coupling and $3d$-orbital filling as key tuning parameters of electronic correlations in transition metal pnictides.

Electronic structure and magnetic anisotropy of L1-FePt thin film studied by hard x-ray photoemission spectroscopy and first-principles calculations

We have studied the electronic structure of the L10 ordered FePt thin film by hard x-ray photoemission spectroscopy (HAXPES), cluster model, and first-principles calculations to investigate the relationship between the electronic structure and perpendicular magneto-crystalline anisotropy (MCA). The Fe 2p core-level HAXPES spectrum of the ordered film revealed the strong electron correlation in the Fe 3d states and the hybridization between the Fe 3d and Pt 5d states. By comparing the experimental valence band structure with the theoretical density of states, the strong electron correlation in the Fe 3d states modifies the valence band electronic structure of the L10 ordered FePt thin film through the Fe 3d-Pt 5d hybridization. These results strongly suggest that the strong electron correlation effect in the Fe 3d states and the Fe 3d-Pt 5d hybridization as well as the spin-orbit interaction in the Pt 5d states play important roles in the perpendicular MCA for L10-FePt.

The symmetry-resolved electronic structure of 2H-WSe2(0 0 0 1)

The orbital symmetry of the band structure of 2H-WSe2(0 0 0 1) has been investigated by means of angle-resolved photoelectron spectroscopy (ARPES) and density functional theory (DFT). The WSe2(0 0 0 1) experimental band structure is found, by ARPES, to be significantly different for states of even and odd reflection parities along both the – and – lines, in good agreement with results obtained from DFT. The light polarization dependence of the photoemission intensities from the top of the valence band for bulk WSe2(0 0 0 1) is explained by the dominance of W 5 states around the -point and W 5dxy states around the -point, thus dominated, respectively, by states of even and odd symmetry, with respect to the – line. The splitting of the topmost valence band at , due to spin–orbit coupling, is measured to be 0.49 ± 0.01 eV, in agreement with the 0.48 eV value from DFT, and prior measurements for the bulk single crystal WSe2(0 0 0 1), albeit slightly smaller than the 0.513 ± 0.01 eV observed for monolayer WSe2.