Hybridization Of Wave Functions Research Articles

Versatile Method of Engineering the Band Alignment and the Electron Wavefunction Hybridization of Hybrid Quantum Devices.

Hybrid devices that combine superconductors (S) and semiconductors (Sm) have attracted great attention due to the integration of the properties of both materials, which relies on the interface details and the resulting coupling strength and wavefunction hybridization. However, until now, none of the experiments have reported good control of the band alignment of the interface, as well as its tunability to the coupling and hybridization. Here, the interface is modified by inducing specific argon milling while maintaining its high quality, e.g., atomic connection, which results in a large induced superconducting gap and ballistic transport. By comparing with Schrödinger-Poisson calculations, it is proven that this method can vary the band bending/coupling strength and the electronic spatial distribution. In the strong coupling regime, the coexistence and tunability of crossed Andreev reflection and elastic co-tunneling-key ingredients for the Kitaev chain-are confirmed. This method is also generic for other materials and achieves a hard and huge superconducting gap in lead and indium antimonide nanowire (Pb-InSb) devices. Such a versatile method, compatible with the standard fabrication process and accompanied by the well-controlled modification of the interface, will definitely boost the creation of more sophisticated hybrid devices for exploring physics in solid-state systems.

Dynamically tunable moiré exciton Rydberg states in a monolayer semiconductor on twisted bilayer graphene.

Moiré excitons are emergent optical excitations in two-dimensional semiconductors with moiré superlattice potentials. Although these excitations have been observed on several platforms, a system with dynamically tunable moiré potential to tailor their properties is yet to be realized. Here we present a continuously tunable moiré potential in monolayer WSe2, enabled by its proximity to twisted bilayer graphene (TBG) near the magic angle. By tuning local charge density via gating, TBG provides a spatially varying and dynamically tunable dielectric superlattice for modulation of monolayer WSe2 exciton wave functions. We observed emergent moiré exciton Rydberg branches with increased energy splitting following doping of TBG due to exciton wave function hybridization between bright and dark Rydberg states. In addition, emergent Rydberg states can probe strongly correlated states in TBG at the magic angle. Our study provides a new platform for engineering moiré excitons and optical accessibility to electronic states with small correlation gaps in TBG.

Proximity-enhanced valley Zeeman splitting at the WS2/graphene interface

The valley Zeeman physics of excitons in monolayer transition metal dichalcogenides provides valuable insight into the spin and orbital degrees of freedom inherent to these materials. Being atomically-thin materials, these degrees of freedom can be influenced by the presence of adjacent layers, due to proximity interactions that arise from wave function overlap across the 2D interface. Here, we report 60 T magnetoreflection spectroscopy of the A- and B- excitons in monolayer WS2, systematically encapsulated in monolayer graphene. While the observed variations of the valley Zeeman effect for the A- exciton are qualitatively in accord with expectations from the bandgap reduction and modification of the exciton binding energy due to the graphene-induced dielectric screening, the valley Zeeman effect for the B- exciton behaves markedly different. We investigate prototypical WS2/graphene stacks employing first-principles calculations and find that the lower conduction band of WS2 at the valleys (the band) is strongly influenced by the graphene layer on the orbital level. Specifically, our detailed microscopic analysis reveals that the conduction band at the Q point of WS2 mediates the coupling between and graphene due to resonant energy conditions and strong coupling to the Dirac cone. This leads to variations in the valley Zeeman physics of the B- exciton, consistent with the experimental observations. Our results therefore expand the consequences of proximity effects in multilayer semiconductor stacks, showing that wave function hybridization can be a multi-step energetically resonant process, with different bands mediating the interlayer interactions. Such effects can be further exploited to resonantly engineer the spin-valley degrees of freedom in van der Waals and moiré heterostructures.

Evolution of the Nature of Excitons and Electronic Couplings in Hybrid 2D Perovskites as a Function of Organic Cation π‐Conjugation

Abstract2D perovskites have attracted much attention, due to their organic–inorganic hybrid nature and layered configuration. Multi‐quantum‐well structures then generally form since the inorganic frameworks and organic spacers have typically well‐separated frontier energy levels. Here, it is focused on the opposite picture where wavefunction hybridization occurs between the frontier orbitals of the two components. Such a hybridization emerges upon tuning the strength of electronic coupling between the inorganic and organic layers. A series of model diammonium organic spacers is theoretically designed with varying extent of π‐conjugation along their backbones. Wavefunction hybridization is realized in a Dion‐Jacobson 2D perovskite combining PbI4 inorganic layers with anthracene‐bis(ethan‐1‐ammonium) organic spacers. An analysis of the electronic band structures points to electronic couplings as high as 30–40 meV between the organic and inorganic components. Such couplings can lead to the formation of interfacial hybrid excitons or to the appearance of Dexter‐type energy transfer conducive to phosphorescence in the organic layers. Overall, the results highlight that a variety of excitonic behaviors could be observed by tuning the degree of conjugation of the organic cations and the structural proximity and electronic couplings between the organic and inorganic constituents.

Neck Barrier Engineering in Quantum Dot Dimer Molecules via Intraparticle Ripening.

Coupled colloidal quantum dot (CQD) dimers represent a new class of artificial molecules composed of fused core/shell semiconductor nanocrystals. The electronic coupling and wave function hybridization are enabled by the formation of an epitaxial connection with a coherent lattice between the shells of the two neighboring quantum dots where the shell material and its dimensions dictate the quantum barrier characteristics for the charge carriers. Herein we introduce a colloidal approach to control the neck formation at the interface between the two CQDs in such artificial molecular constructs. This allows the tailoring of the neck barrier in prelinked homodimers formed via fusion of multifaceted wurtzite CdSe/CdS CQDs. The effects of reaction time, temperature, and excess ligands are studied. The neck filling process follows an intraparticle ripening mechanism at relatively mild reaction conditions while avoiding interparticle ripening. The degree of surface ligand passivation plays a key role in activating the surface atom diffusion to the neck region. The degree of neck filling strongly depends also on the initial relative orientation of the two CQDs, where homonymous plane attachment allows for facile neck growth, unlike the case of heteronymous plane attachment. Upon neck filling, the observed red-shift of the absorption and fluorescence measured both for ensemble and single dimers is assigned to enhanced hybridization of the confined wave function in CQD dimer molecules, as supported by quantum calculations. The fine-tuning of the particle interface introduced herein provides therefore a powerful tool to further control the extent of hybridization and coupling in CQD molecules.

External Field-Tunable Internal Orbit-Orbit Interaction in Flexible Perovskites.

In hybrid metal halide perovskites, electrons carry both orbital and spin momenta through s-p wave function hybridization. This leads to a hypothesis that the orbit-orbit interaction between excitons can occur through orbital magnetic dipoles forming short-range interaction or through orbital polarizations forming long-range interaction to influence optoelectronic properties. This Letter reports an interesting phenomenon: the orbit-orbit interaction can be electrically switched between orbital magnetic dipoles and orbital polarizations in a flexible perovskite (MAPbI3-xClx) solar cell by scanning an external voltage between forward and reverse biases (0.2 and -0.2 V). Essentially, this phenomenon presents an external mechanism for electrically controlling the internal orbit-orbit interaction in hybrid perovskites. It was further observed that this bias-switchable orbit-orbit interaction is sensitive to temperature, becoming negligible when the temperature is decreased from 300 to 250 K. This observation indicates that the mobile ions driven by an external electrical field provide an intrinsic mechanism for electrically switching the orbit-orbit interaction through polarization and spin parameters while applying an external voltage between forward and reverse biases. These results provide a comprehensive understanding of tuning the orbit-orbit interaction in flexible perovskites toward developing orbitronic actions.

Spin-orbit-proximitized ferromagnetic metal by monolayer transition metal dichalcogenide: Atlas of spectral functions, spin textures, and spin-orbit torques in Co/MoSe2, Co/WSe2 , and Co/TaSe2 heterostructures

The bilayer heterostructures composed of an ultrathin ferromagnetic metal (FM) and a material hosting strong spin-orbit (SO) coupling are principal resource for SO torque and spin-to-charge conversion nonequilibrium effects in spintronics. We demonstrate how hybridization of wavefunctions of Co layer and a monolayer of transition metal dichalcogenides (TMDs)---such as semiconducting MoSe$_2$ and WSe$_2$ or metallic TaSe$_2$---can lead to dramatic transmutation of electronic and spin structure of Co within some distance away from its interface with TMD, when compared to the bulk of Co or its surface in contact with vacuum. This is due to proximity induced SO splitting of Co bands encoded in the spectral functions and spin textures on its monolayers, which we obtain using noncollinear density functional theory (ncDFT) combined with equilibrium Green function (GF) calculations. In fact, SO splitting is present due to structural inversion asymmetry of the bilayer even if SO coupling within TMD monolayer is artificially switched off in ncDFT calculations, but switching it on makes the effects associated with proximity SO coupling within Co layer about five times larger. Injecting spin-unpolarized charge current through SO-proximitized monolayers of Co generates nonequilibrium spin density over them, so that its cross product with the magnetization of Co determines SO torque. The SO torque computed via first-principles quantum transport methodology, which combines ncDFT with nonequilibrium GF calculations, can be used as the screening parameter to identify optimal combination of materials and their interfaces for applications in spintronics. In particular, we identify heterostructure two-monolayer-Co/monolayer-WSe$_2$ as the most optimal.

Structural effects on carrier doping in carbon nanotube thin-film transistors

Based on density functional theory, we studied the electronic properties of carbon nanotube (CNT) thin films under an external electric field. The carrier accumulation resulting from an electric field depends slightly on the CNT species that form the thin films and their arrangement with respect to the electrode. Although most of the carriers are accumulated in the CNTs located at the electrode side, wave function hybridization between semiconducting CNTs slightly enhances the carrier penetration into the opposite CNT layer. Metallic CNTs strongly depress or enhance the carrier penetration for the thin films when they are located at the electrode side or not, respectively.

Colloidal quantum dot molecules manifesting quantum coupling at room temperature

Coupling of atoms is the basis of chemistry, yielding the beauty and richness of molecules. We utilize semiconductor nanocrystals as artificial atoms to form nanocrystal molecules that are structurally and electronically coupled. CdSe/CdS core/shell nanocrystals are linked to form dimers which are then fused via constrained oriented attachment. The possible nanocrystal facets in which such fusion takes place are analyzed with atomic resolution revealing the distribution of possible crystal fusion scenarios. Coherent coupling and wave-function hybridization are manifested by a redshift of the band gap, in agreement with quantum mechanical simulations. Single nanoparticle spectroscopy unravels the attributes of coupled nanocrystal dimers related to the unique combination of quantum mechanical tunneling and energy transfer mechanisms. This sets the stage for nanocrystal chemistry to yield a diverse selection of coupled nanocrystal molecules constructed from controlled core/shell nanocrystal building blocks. These are of direct relevance for numerous applications in displays, sensing, biological tagging and emerging quantum technologies.

Strain-free GaN/InAlN chirped short-period superlattice electron-blocking layer for 450 nm InGaN laser diode

In this study, we optimized the lattice-matched GaN/In0.18Al0.82N chirped short-period superlattice (C-SPSL) electron-blocking layer for a laser diode emitting at 450 nm. The effective bandgap of C-SPSL depends upon the quantum well (QW) and quantum barrier (QB) thickness of C-SPSL. In this study the In0.18Al0.82N QB thickness is constant at 0.5112 nm (1 unit layer (UL) = 1 lattice constant thickness) and the GaN QW thickness is varied as 1 UL, 3 UL, and 5 UL. The estimated effective bandgap for 15 periods of 1 UL GaN/1 UL In0.18Al0.82N SPSL is ~4.2 eV, for four periods of 3 UL GaN/1 UL In0.18Al0.82N SPSL it is ~3.93 eV and for two periods of 5 UL GaN/1 UL In0.18Al0.82N SPSL it is 3.62 eV. Wave-function hybridization and the built-in electric field play an important role in the bandgap behavior of C-SPSL. The electron leakage decreased from 2534.6 A cm−2 to ~14 A cm−2 while hole transportation improved from 7.7 kA cm−2 to 10 kA cm−2 at 10 kA cm−2 injection current density. The light output power per facet improved from 146 mW to 255 mW. Slope efficiency increased from 0.548 W A−1 to 0.924 W A−1 with the C-SPSL design.

Wave-Function Hybridization in Yu-Shiba-Rusinov Dimers.

Magnetic adsorbates on superconductors induce local bound states within the superconducting gap. These Yu-Shiba-Rusinov (YSR) states decay slowly away from the impurity compared to atomic orbitals, even in 3D bulk crystals. Here, we use scanning tunneling spectroscopy to investigate their hybridization between two nearby magnetic Mn adatoms on a superconducting Pb(001) surface. We observe that the hybridization leads to the formation of symmetric and antisymmetric combinations of YSR states. We investigate how the structure of the dimer wave functions and the energy splitting depend on the shape of the underlying monomer orbitals and the orientation of the dimer with respect to the Pb lattice.

Few-layer Tellurium: one-dimensional-like layered elementary semiconductor with striking physical properties

Few-layer Tellurium, an elementary semiconductor, succeeds most of striking physical properties that black phosphorus (BP) offers and could be feasibly synthesized by simple solution-based methods. It is comprised of non-covalently bound parallel Te chains, among which covalent-like feature appears. This feature is, we believe, another demonstration of the previously found covalent-like quasi-bonding (CLQB) where wavefunction hybridization does occur. The strength of this inter-chain CLQB is comparable with that of intra-chain covalent bonding, leading to closed stability of several Te allotropes. It also introduces a tunable bandgap varying from nearly direct 0.31 eV (bulk) to indirect 1.17 eV (2L) and four (two) complex, highly anisotropic and layer-dependent hole (electron) pockets in the first Brillouin zone. It also exhibits an extraordinarily high hole mobility (∼105 cm2/Vs) and strong optical absorption along the non-covalently bound direction, nearly isotropic and layer-dependent optical properties, large ideal strength over 20%, better environmental stability than BP and unusual crossover of force constants for interlayer shear and breathing modes. All these results manifest that the few-layer Te is an extraordinary-high-mobility, high optical absorption, intrinsic-anisotropy, low-cost-fabrication, tunable bandgap, better environmental stability and nearly direct bandgap semiconductor. This “one-dimension-like” few-layer Te, together with other geometrically similar layered materials, may promote the emergence of a new family of layered materials.

Band gap engineering of In(Ga)N/GaN short period superlattices

Discussion of band gap behavior based on first principles calculations of the electronic band structures for several InN/GaN superlattices (SLs) (free-standing and pseudomorphic) grown along different directions (polar and nonpolar) is presented. Taking into account the dependence on internal strain and lattice geometry mainly two factors influence the dependence of the band gap, Eg on the layer thickness: the internal electric field and the hyb wells) is more important. We also consider mIn ridization of well and barrier wave functions. We illustrate their influence on the band gap engineering by calculating the strength of built-in electric field and the oscillator strength. It appears that there are two interesting ranges of layer thicknesses. In one the influence of the electric field on the gaps is dominant (wider wells), whereas in the other the wave function hybridization (narrow wells) is more important. We also consider mIn0.33Ga0.67N/nGaN SLs, which seem to be easier to fabricate than high In content quantum wells. The calculated band gaps are compared with recent experimental data. It is shown that for In(Ga)N/GaN superlattices it is possible to exceed by far the range of band gap values, which can be realized in ternary InGaN alloys.

Unusually high electron density in an intermolecular non-bonding region: Role of metal substrate

It has been demonstrated that intermolecular interaction, crucial in a plenty of chemical and physical processes, may vary in the presence of metal surface. However, such modification is yet to be quantitatively revealed. Here, we present a systematical density functional theory study on adsorbed bis(para-pyridyl)acetylene (BPPA) tetramer on Au(111) surface. We observed unusually high electron density between two head-to-head N atoms, an intermolecular “non-bonded” region, in adsorbed BPPA tetramer. This exceptional electron density originates from the wavefunction hybridization of the two compressed N lone-electron-pair states of two BPPA, as squeezed by a newly revealed N–Au–N three-center bonding. This bond, together with the minor contribution from N⋯H–C intermolecular hydrogen bonding, shortens the N–N distance from over 4Å to 3.30Å and offers an attractive lateral interacting energy of 0.60eV, effectively to a surface-confined in-plane pressure. The overlapped non-bonding wavefunction hybridization arising from the effective pressure induced by the N–Au–N three-center bonding, as not been fully recognized in earlier studies, was manifested in non-contact Atomic Force Microscopy.

Band gaps and built-in electric fields in InAlN/GaN short period superlattices: Comparison with (InAlGa)N quaternary alloys

The general trends in the behavior of the band gaps in short period superlattices (SLs) composed from InAlN and GaN layers and grown along the wurtzite $c$ axis have been analyzed for different alloy compositions and several thicknesses of quantum wells and barriers. The composition dependence of the gaps is compared to that of the quaternary alloys $\mathrm{I}{\mathrm{n}}_{y}\mathrm{A}{\mathrm{l}}_{1\ensuremath{-}x\ensuremath{-}y}\mathrm{G}{\mathrm{a}}_{x}\mathrm{N}$ with the same effective contents of In, Al, and Ga as the SLs. The differences in the gaps are explained mainly by the built-in electric fields in the SLs caused by spontaneous and piezoelectric polarizations. Other factors, such as internal strain caused by lattice mismatch between wells and barriers and wave function hybridization, are taken into account. A simplified approach to determine the built-in electric fields directly from the dielectric properties of the constituent materials has been applied and verified by comparison to ab initio calculations for selected SLs. The calculated band gaps are compared with existing experimental data.

Passivation of Molecular n‐Doping: Exploring the Limits of Air Stability

Molecular doping is a key technique for flexible and low‐cost organic complementary semiconductor technologies that requires both efficient and stable p‐ and n‐type doping. However, in contrast to molecular p‐dopants, highly efficient n‐type dopants are commonly sensitive to rapid degradation in air due to their low ionization energies (IEs) required for electron donation, e.g., IE = 2.4 eV for tetrakis(1,3,4,6,7,8‐hexahydro‐2H‐pyrimido[1,2‐a]pyrimidinato)ditungsten(II) (W2(hpp)4). Here, the air stability of various host:W2(hpp)4 combinations is compared by conductivity measurements and photoemission spectroscopy. A partial passivation of the n‐doping against degradation is found, with this effect identified to depend on the specific energy levels of the host material. Since host‐W2(hpp)4 electronic wavefunction hybridization is unlikely due to confinement of the dopant highest occupied molecular orbital (HOMO) to its molecular center, this finding is explained via stabilization of the dopant by single‐electron transfer to a host material whose energy levels are sufficiently low for avoiding further charge transfer to oxygen–water complexes. Our results show the feasibility of temporarily handling n‐doped organic thin films in air, e.g., during structuring of organic field effect transistors (OFETs) by lithography.

Probing the role of interlayer coupling and coulomb interactions on electronic structure in few-layer MoSe₂ nanostructures.

Despite the weak nature of interlayer forces in transition metal dichalcogenide (TMD) materials, their properties are highly dependent on the number of layers in the few-layer two-dimensional (2D) limit. Here, we present a combined scanning tunneling microscopy/spectroscopy and GW theoretical study of the electronic structure of high quality single- and few-layer MoSe2 grown on bilayer graphene. We find that the electronic (quasiparticle) bandgap, a fundamental parameter for transport and optical phenomena, decreases by nearly one electronvolt when going from one layer to three due to interlayer coupling and screening effects. Our results paint a clear picture of the evolution of the electronic wave function hybridization in the valleys of both the valence and conduction bands as the number of layers is changed. This demonstrates the importance of layer number and electron–electron interactions on van der Waals heterostructures and helps to clarify how their electronic properties might be tuned in future 2D nanodevices.

Magnetoelectric effect in topological insulator films beyond the linear response regime

We study the response of topological insulator films to strong magnetic and electric fields beyond the linear response theory. As a model, we use a three-dimensional lattice Wilson-Dirac Hamiltonian where we simultaneously introduce both magnetic field through the Peierls substitution and electric field as a potential energy depending on lattice coordinate. We compute the electron energy spectrum by numerically diagonalizing this Hamiltonian and obtain quantized magnetoelectric polarizability. In addition, we find that the magnetoelectric effect vanishes as the film width decreases due to the hybridization of surface wave functions. Furthermore, applying a gate voltage between the surfaces, we observe several quantized plateaus of $\ensuremath{\theta}$ term, which are mainly determined by the Landau level structures on the top and bottom surfaces.

Controlled Interaction of Surface Quantum-Well Electronic States

We report on the construction of well-defined surface quantum well arrangements by combining self-assembly protocols and molecular manipulation procedures. After the controlled removal of individual porphyrin molecules from dense-packed arrays on Ag(111), the surface state electrons are confined at the bare silver patches. These act as quantum wells that show well-defined unoccupied bound surface states. Scanning tunneling spectroscopy and complementary boundary element method calculations are performed to characterize the interaction between the bound states of adjacent quantum wells and reveal a hybridization of wave functions resulting in bonding and antibonding states. The interwell coupling can be tuned by the deliberate choice of the molecules acting as potential barriers. The fabrication method is shown to be ideally suited to engineer specific configurations as one-dimensional chains or two-dimensional artificial molecules.

Hybridization of wave functions in one-dimensional localization

A quantum particle can be localized in a disordered potential, the effect known as Anderson localization. In such a system, correlations of wave functions at very close energies may be described, due to Mott, in terms of a hybridization of localized states. We revisit this hybridization description and show that it may be used to obtain quantitatively exact expressions for some asymptotic features of correlation functions, if the tails of the wave functions and the hybridization matrix elements are assumed to have log-normal distributions typical for localization effects. Specifically, we consider three types of one-dimensional systems: a strictly one-dimensional wire and two quasi-one-dimensional wires with unitary and orthogonal symmetries. In each of these models, we consider two types of correlation functions: the correlations of the density of states at close energies and the dynamic response function at low frequencies. For each of those correlation functions, within our method, we calculate three asymptotic features: the behavior at the logarithmically large ``Mott length scale,'' the low-frequency limit at length scale between the localization length and the Mott length scale, and the leading correction in frequency to this limit. In the several cases, where exact results are available, our method reproduces them within the precision of the orders in frequency considered.