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We report device concepts that exploit spin-orbit coupling for creating spin polarized current sources using nonmagnetic semiconductor resonant tunneling heterostructures, without external magnetic fields. The resonant interband tunneling psin filter exploits large valence band spin-orbit interaction to provide strong spin selectivity.
A mid-wavelength infrared (MWIR) barrier photodetector is capable of operating at higher temperature than the prevailing MWIR detectors based on InSb. The standard high-operating-temperature barrier infrared detector (HOT-BIRD) is made with an InAsSb infrared absorber that is lattice-matched to a GaSb substrate, and has a cutoff wavelength of approximately 4 microns. To increase the versatility and utility of the HOT-BIRD, it is implemented with IR absorber materials with customizable cutoff wavelengths. The HOT-BIRD can be built with the quaternary alloy GaInAsSb as the absorber, GaAlSbAs as the barrier, on a lattice-matching GaSb substrate. The cutoff wavelength of the GaInAsSb can be tailored by adjusting the alloy composition. To build a HOT-BIRD requires a matching pair of absorber and barrier materials with the following properties: (1) their valence band edges must be approximately the same to allow unimpeded hole flow, while their conduction band edges should have a large difference to form an electron barrier; and (2) the absorber and the barrier must be respectively lattice-matched and closely lattice-matched to the substrate to ensure high material quality and low defect density. To make a HOT-BIRD with cutoff wavelength shorter than 4 microns, a GaInAsSb quaternary alloy was used as the absorber, and a matching GaAlSbAs quaternary alloy as the barrier. By changing the alloy composition, the band gap of the quaternary alloy absorber can be continuously adjusted with cutoff wavelength ranging from 4 microns down to the short wavelength infrared (SWIR). By carefully choosing the alloy composition of the barrier, a HOT-BIRD structure can be formed. With this method, a HOT-BIRD can be made with continuously tailorable cutoff wavelengths from 4 microns down to the SWIR. The HOT-BIRD detector technology is suitable for making very-large-format MWIR/SWIR focal plane arrays that can be operated by passive cooling from low Earth orbit. High-operating temperature infrared with reduced cooling requirement would benefit space missions in reduction of size, weight, and power, and an increase in mission lifetime.
Excitonic Bose-Einstein condensation (EBEC) has drawn increasing attention recently with the emergence of 2D materials. A general criterion for EBEC, as expected in an excitonic insulator (EI) state, is to have negative exciton formation energies in a semiconductor. Here, using exact diagonalization of a multiexciton Hamiltonian modeled in a diatomic kagome lattice, we demonstrate that the negative exciton formation energies are only a prerequisite but insufficient condition for realizing an EI. By a comparative study between the cases of both conduction and valence flat bands (FBs) versus that of a parabolic conduction band, we further show that the presence and increased FB contribution to exciton formation provide an attractive avenue to stabilize the excitonic condensate, as confirmed by calculations and analyses of multiexciton energies, wave functions, and reduced density matrices. In conclusion, our results warrant a similar many-exciton analysis for other known and/or new candidates of EIs and demonstrate the FBs of opposite parity as a unique platform for studying exciton physics, paving the way to material realization of spinor BEC and spin superfluidity.
The performance of various spin-component-scaled parameterisations is examined for the second-order many-body Green's-function [MBGF(2)] calculations of valence energy bands, taking three of the experimentally well-characterised polymers as examples: polyethylene, polytetrafluoroethylene, and polyacetylene. The parameterisations considered are Grimme's original SCS parameter set, Jung et al.'s original SOS set (retaining the opposite-spin component only), Śmiga et al.'s SCS(IP) set (calibrated specifically for ionization energies), and Śmiga et al.'s SOS(IP) set (calibrated for ionization energies with the opposite-spin component only; implicit in the os-D2 model of Opoku et al.). The SCS(IP) and SOS(IP) parameterisations are found to shift both outer and inner valence bands by up to a few electronvolts away from the experimental data. The original SCS and SOS parameter sets do not improve upon, but largely maintain the accuracy of the unscaled MBGF(2) methods. Given that the SOS-MBGF(2) method can be implemented in a quartic-scaling algorithm (for all roots), it is most promising for solid-state applications. Furthermore this observation is consistent with the success of the quartic-scaling GW methods without the vertex correction based on a density-functional theory reference.
Although surface ligands of colloidal nanocrystals are known to adjust the absolute energy levels of valence and conduction bands of semiconductor nanocrystals, they typically have only minor influence on the band gap or effective masses. This changes in nanoplatelets. Ligand exchange of CdSe colloidal nanoplatelets induces large (up to 300 meV) bathochromic shifts of both interband and intersubband transitions. Here, three families of ligands-halides, thiolates, and phosphonates-are used to tune interband transitions, reflecting electron and hole confinement, across visible wavelengths and intersubband transitions, reflecting electron confinement, across the near-infrared spectral window. Furthermore, careful examination shows that delocalization from expansion of the nanoplatelet short axis, which was reported previously, cannot alone explain observed red shifts. Instead, comparison of intersubband, interband, and hole energy levels shows that ligand head group chemistry confers specific, idiosyncratic adjustments of the contribution of conduction and valence bands to the observed bathochromic shifts. Phosphonate ligands show the largest band gap reductions but the smallest red shift of intersubband transition energies; halide-exchanged samples displayed smaller reductions in band gap but large red shifts of intersubband transitions; thiolates fall in between. A related specificity is observed in hole states, which implicates ligand-responsive valence band curvature as an additional contribution driving optical changes. For nanoplatelets, surface ligand chemistry offers not only a tool to adjust the absolute energy level of conduction and valence bands but also an alternative route to preferential electron or hole band engineering that is normally achieved with inorganic shells.
The ability of materials to convert charge current into spin current is fundamental to many spintronics applications. One means of realizing this conversion is via Rashba-Edelstein effect (REE). Using density functional theory simulations, we predict that REE can be induced in the recently discovered family of semiconducting ferroelectrics, CsGe𝑋 3 (𝑋 = I, Br, Cl). The effect is quantified through Rashba-Edelstein coefficients, 𝜒 𝑥𝑦 =−𝜒 𝑦𝑥 , which are nonzero in valence and conduction bands. The largest values, obtained for CsGeI 3 , are 3.45 × 10 10 $\frac{ℏ}{Λ cm}$ and 0.97 × 10 10 $\frac{ℏ}{Λ cm}$ in the conduction and valence bands, respectively. The values are comparable to, and sometimes exceed, those of other inorganic materials, although the maximal values occur away from the band edges. The coefficients' sign couples to the direction of spontaneous polarization, offering opportunities for nonvolatile spin current manipulation via external electric field. Furthermore, these coefficients are highly tunable through strain engineering owing to strain-induced variations in spin textures and energy isosurfaces. Specifically, 𝜒 in the valence band of CsGeI 3 is enhanced to 3.61 × 10 10 $\frac{ℏ}{Λ cm}$ under 5% biaxial strain. Given this potential, we synthesized CsGeI 3 to validate our simulation structure and found excellent agreement between experiment and simulation, thereby allowing extrapolation of our findings to practically significant temperatures. Furthermore, our study identifies promising materials for nonvolatile, multifunctional spintronic applications.
Zinc-blende (ZB) cadmium selenide (CdSe) nanoplatelets (NPLs) have drawn increasing attention as an ideal condensed-phase material for facilitating photon-to-spin transduction in quantum networks. Yet, a systematic investigation of their fidelity in converting circularly polarized light (CPL) to exciton spin polarization as a function of excitation wavelength is lacking. Here, this work demonstrates using time-resolved transient absorption (TA) spectroscopy combined with density functional theory calculations that ZB CdSe NPLs exhibit wavelength-dependent CPL-induced spin polarization. The capacity of CPL to inject spin polarization is maximized for resonant excitation of band-edge valence-to-conduction band (VB/CB) transitions, and the degree to which CPL induces spin polarization can be modified for non-resonant excitation wavelengths as excitation occurs at k-points away from the Γ point from VB states with varying degrees of mixed heavy-hole (HH) and light-hole (LH) characters. Furthermore, it is highlighted that spin polarization within the LH exciton (LX) population created from resonant LH/CB excitation is retained upon LX → HH exciton (HX) relaxation due to the slow electron spin-flip rate (~1.1 ps) compared to the LH → HH inter-band relaxation rate (~200 fs).
Proton-coupled electron transfer (PCET) reactions on metal oxides require coupling between proton transfer at the solid-liquid interface and electron transfer involving defects at or near the band edge. Herein, hybrid functional periodic density functional theory is used to elucidate the impact of proton-coupled defects on the bond dissociation free energies (BDFEs) of O-H bonds on anatase TiO 2 surfaces. These O-H BDFEs are directly related to interfacial PCET thermochemistry. Comparison between geometrically similar O-H bonds associated with different defect types, namely conduction d-band electrons or valence p-band holes, reveals that the BDFEs differ by ~81 kcal/mol (3.50 eV), comparable to the wide TiO 2 band gap. These differences are shown to be determined primarily by differences in electron transfer driving forces, which are analyzed by using band energies and inner-sphere reorganization energies within a Marcus theory framework. Furthermore, these fundamental insights about the impact of proton-coupled defects on PCET thermochemistry at semiconductor surfaces have broad implications for electrocatalysis.
Hybrid organic-inorganic halides containing Bi and Sb generally exhibit higher stability and lower toxicity compared to Pb analogues. Here, in this work, synthesis, crystal and electronic structures and optical properties of a brand-new methylammonium bismuth iodide, (MA) 4 Bi 6 I 22 (MA + = CH 3 NH 3 + ), are reported. Interestingly, we find that the presence of the HgI2 is necessary for the targeted preparation of (MA) 4 Bi 6 I 22 . (MA) 4 Bi 6 I 22 contains isolated [Bi 6 I 22 ] 4- clusters made of six edge-sharing octahedral BiI6 units, which are separated by MA + cations in its 0D crystal structure. A relatively low optical band gap of 1.9 eV was estimated for (MA) 4 Bi 6 I 22 based on diffuse reflectance measurements. An intense photoluminescence peak emerges at 636 nm at low temperatures that supports the assigned band gap value. Electronic structure calculations show the presence of flat bands in the valence and conduction bands, consistent with the low-dimensional structure of (MA) 4 Bi 6 I 22 , and slightly indirect nature of the bandgap. Our findings suggest that the use of facilitator moieties such as HgI 2 may provide a pathway to obtaining alternative methylammonium bismuth iodides to (MA) 3 Bi 2 I 9 .
When an extrinsic, direct band-gap semiconductor sample is irradiated by photons of an energy higher than the energy of the band gap between valence and conduction bands, excess electron-hole pairs are generated which, while diffusing through the sample, produce luminescence via radiative recombination. If, furthermore, the intensity of the impinging beam of photons is modulated sinusoidally, the luminescence radiation escaping from the sample will be phase shifted with respect to the original photon beam in a characteristic way. It will be shown that by measuring the phase shift at different modulation frequencies, the Shockley-Read-Hall lifetime of minority carriers may be ascertained. The method is nondestructive inasmuch as there is no need to fabricate p-n junctions or Ohmic contacts, nor is it necessary to remove already existing Ohmic contacts of angle lap the surface, etc., procedures often needed when determining lifetimes with the scanning electron microscope (in which case a p-n junction must be present).
The transition metal chalcogenide Ta 2 NiSe 5 undergoes a second-order phase transition at T c = 328 K involving a small lattice distortion. Below T c , a band gap at the center of its Brillouin zone increases up to about 0.35 eV. In this work, we study the electronic structure of Ta 2 NiSe 5 in its low-temperature semiconducting phase, using resonant inelastic x-ray scattering (RIXS) at the Ni L 3 -edge. In addition to a weak fluorescence response, we observe a collection of intense Raman-like peaks that we attribute to electron-hole excitations. Using density functional theory calculations of its electronic band structure, we identify the main Raman-like peaks as interband transitions between valence and conduction bands. Further, by performing angle-dependent RIXS measurements, we uncover the dispersion of these electron-hole excitations that allows us to extract the low-energy boundary of the electron-hole continuum. From the dispersion of the valence band measured by angle-resolved photoemission spectroscopy, we derive the effective mass of the lowest unoccupied conduction band.
Femtosecond carrier cooling in the organohalide perovskite semiconductor CH 3 NH 3 PbI 3 is measured using extreme ultraviolet (XUV) and optical transient absorption spectroscopy. XUV absorption between 44 and 58 eV measures transitions from the I 4d core to the valence and conduction bands and gives distinct signals for hole and electron dynamics. The core-to-valence-band signal directly maps the photoexcited hole distribution and provides a quantitative measurement of the hole temperature. The combination of XUV and optical probes reveals that upon excitation at 400 nm, the initial hole distribution is 3.5 times hotter than the electron distribution. At an initial carrier density of 1.4 × 10 20 cm –3 both carriers are subject to a hot phonon bottleneck, but at 4.2 × 10 19 cm –3 the holes cool to less than 1000 K within 400 fs. Finally, this result places significant constraints on the use of organohalide perovskites in hot-carrier photovoltaics.
Recent investigations into the effects of dimensional reduction on halide double perovskites have revealed an intriguing change in band structure when the three-dimensional (3D) perovskite is reduced to a two-dimensional (2D) perovskite with inorganic sheets of monolayer thickness (n = 1). The indirect bandgap of 3D Cs 2 AgBiBr 6 becomes direct in the n = 1 perovskite whereas the direct bandgap of 3D Cs 2 AgTlBr 6 becomes indirect at the n = 1 limit. Here, we apply a linear combination of atomic orbitals approach to uncover the orbital basis for this bandgap symmetry transition with dimensional reduction. We adapt our previously established method for predicting band structures of 3D double perovskites for application to their 2D congeners, emphasizing new considerations required for the 2D lattice. In particular, we consider the inequivalence of the terminal and bridging halides and the consequences of applying translational symmetry only along two dimensions. The valence and conduction bands of the layered perovskites can be derived from symmetry adapted linear combinations of halide p orbitals propagated across the 2D lattice. The dispersion of each band is then determined by the bonding and antibonding interactions of the metal and halide orbitals, thus affording predictions of the essential features of the band structure. We demonstrate this analysis for 2D Ag–Bi and Ag–Tl perovskites with sheets of mono- and bilayer thickness, establishing a detailed understanding of their band structures, which enables us to identify the key factors that drive the bandgap symmetry transitions observed at the n = 1 limit. Importantly, these insights also allow us to make the general prediction that direct → indirect or indirect → direct bandgap transitions in the monolayer limit are most likely in double perovskite compositions that involve participation of metal d orbitals at the band edges or that have no metal-orbital contributions to the valence band, laying the groundwork for the targeted realization of this phenomenon.
Chalcopyrites are a demonstrated material platform for realizing efficient thin-film photovoltaics, with the most well known Cu(In,Ga)Se 2 (CIGS)-based solar cells exceeding 23%. Several factors, including flexibility in tuning the absorber bandgap, enhanced surface treatments, and the electrically benign nature of common defects are responsible for the existing high performance and future promise in chalcopyrite-based photovoltaic devices. The introduction of Cu-poor phases (also known as ordered-vacancy compounds or OVCs) between the absorber and buffer layers in CIGS solar cells is known to enhance device performance; however, the overall properties and role of OVCs remain poorly understood. Using first principles calculations based on the density functional theory with screened hybrid functionals, here we explore the electronic structure and stability of OVCs and their band offsets with defect-free chalcopyrite layers in Cu- and Ag-based compounds (ABX 2 where A=Cu, Ag; B=In, Ga, Al; and X=S, Se). Using AB 3 X 5 and AB 5 X 8 stoichiometries as model OVC systems, we report on the variation of the bandgap with the A/B ratio and discuss the trends in other Cu- and Ag-based chalcopyrites beyond CuInSe 2 . We find that the valence and conduction bands are lower in energy in OVCs with respect to the parent ABX 2 chalcopyrite owing to a reduced p–d interaction between X and A atoms. We additionally perform device-level simulations to assess the implications of the results, finding that the valence band offsets of OVCs are favorable, while the conduction band offsets of chalcopyrites beyond CuInSe 2 -based absorbers may be detrimental in conventional solar cell device designs.
In this work, we studied the bulk band structure of a topological insulator (TI) Bi 2 Se 3 and determined the contributions of the Bi and Se orbital states to the valence bands using standing-wave excited hard x-ray photoemission spectroscopy (SW-HAXPES). This SW technique can provide the element-resolved information and extract individual Bi and Se contributions to the Bi2Se3 valence band. Comparisons with density-functional theory calculations (local density approximation and GW) reveal that the Bi 6s, Bi 6p, and Se 4p states are dominant in the Bi 2 Se 3 HAXPES valence band. Furthermore, these findings pave a way for studying the element-resolved band structure and orbital contributions of this class of TIs.
Kramers-Kronig analysis is applied to measured values of spectral reflectance at near-normal incidence to determine the real and the imaginary parts of the complex index of refraction for methane, ethane, propane, n-butane, n-hexane, n-heptane, and n-decane in the liquid state. The results indicate that the strengths of the characteristic bands as measured by the integral of the imaginary part are roughly constant for all the liquid alkanes except for methane. The intensity of the CH valence vibration bands in the spectra of the alkanes except methane is directly proportional to the number of CH groups per unit volume. The relations for the intensity of the bands due to CH2 and CH3 deformations are examined. Characteristic band intensities of the type established for NH4(+) and SO4(2-) groups in solutions and crystals cannot be extended to the more closely coupled CH2 and CH3 groups in alkane molecules.
Nodal-line semimetals feature topologically protected band crossings between the bulk valence and conduction bands that extend along a finite dimension in the form of a line or a loop. While ZrSiS and similar materials have attracted extensive research as hosts for the nodal-line semimetallic phase, an alternative avenue has emerged in the form of isostructural rare-earth (RE)-based RESbTe materials. Such systems possess intriguing potentialities for harboring elements of magnetic ordering and electronic correlations owing to the presence of 4f electrons intrinsic to the RE elements. In this study, we have carried out angle-resolved photoemission spectroscopy (ARPES) and thermodynamic measurements in conjunction with first-principles computations on PrSbTe to elucidate its electronic structure and topological characteristics. Magnetic and thermal characterizations indicate the presence of well-localized 4f states with the absence of any discernible phase transition down to 2 K. The ARPES results reveal the presence of gapless Dirac crossings that correspond to a nodal-line along the X-R direction in the three-dimensional Brillouin zone. Furthermore, Dirac crossing that makes up the nodal line, which forms a diamond-shaped nodal plane centered at the center of the Brillouin zone, is also identified within the experimental resolution. In conclusion, this study on the electronic structure of PrSbTe contributes to the understanding of the pivotal role played by spin-orbit coupling in the context of the RESbTe family of materials.
The long-wavelength moiré superlattices in twisted 2D structures have emerged as a highly tunable platform for strongly correlated electron physics. We study the moiré bands in twisted transition metal dichalcogenide homobilayers, focusing on WSe 2 , at small twist angles using a combination of first principles density functional theory, continuum modeling, and Hartree-Fock approximation. We reveal the rich physics at small twist angles θ < 4°, and identify a particular magic angle at which the top valence moiré band achieves almost perfect flatness. In the vicinity of this magic angle, we predict the realization of a generalized Kane-Mele model with a topological flat band, interaction-driven Haldane insulator, and Mott insulators at the filling of one hole per moiré unit cell. The combination of flat dispersion and uniformity of Berry curvature near the magic angle holds promise for realizing fractional quantum anomalous Hall effect at fractional filling. We also identify twist angles favorable for quantum spin Hall insulators and interaction-induced quantum anomalous Hall insulators at other integer fillings.