In-gap States Research Articles

Transport properties of multilayer NbxMo1−xS2/MoS2 in-plane heterostructure tunnel FETs on hexagonal boron nitride substrate

In-plane heterostructures based on transition metal dichalcogenides are promising for applications in tunnel field-effect transistors (TFETs). However, the transport properties of the in-plane heterostructures have not been fully understood due to the presence of generation current derived from the in-gap state of the heterointerface. For further performance improvement, it is important to identify and suppress the origin of the in-gap states at the heterointerface. In this work, we investigated the transport properties of TFETs based on multilayer NbxMo1−xS2/MoS2 in-plane heterostructures on atomically flat hexagonal boron nitride substrate. We observed a transition from staggered gap to broken gap band alignment by electron doping to MoS2 and that band-to-band tunneling current was dominant below 80 K, a higher temperature compared with the heterostructure on an SiO2 surface. These results indicate that the use of atomically flat substrates helps reduce generation current from strain-derived in-gap states in NbxMo1−xS2/MoS2 in-plane heterostructures.

Exact counterdiabatic driving in finite topological lattice models

Adiabatic protocols are often employed in state preparation schemes but require the system to be driven by a slowly varying Hamiltonian so that transitions between instantaneous eigenstates are exponentially suppressed. Counterdiabatic driving is a technique to speed up adiabatic protocols by including additional terms calculated from the instantaneous eigenstates that counter diabatic excitations. However, this approach requires knowledge of the full eigenspectrum meaning that the exact analytical form of counterdiabatic driving is only known for a subset of problems, e.g., the harmonic oscillator and transverse field Ising model. We extend this subset of problems to include the general family of one-dimensional noninteracting lattice models with open boundary conditions and arbitrary onsite potential, tunneling terms, and lattice size. We will derive a general analytical form for the counterdiabatic term for all states of lattice models, including bound and in-gap states which appear, e.g., in topological insulators. We also derive the general analytical form of targeted counterdiabatic driving terms which are tailored to enforce the dynamical state to remain in a specific state. As an example of the use of the derived analytical forms, we consider state transfer using the topological edge states of the Su-Schrieffer-Heeger model. The derived analytical counterdiabatic driving Hamiltonian can be utilized to inform control protocols in many-body lattice models or to probe the nonequilibrium properties of lattice models. Published by the American Physical Society 2024

Comparative study of photo-induced electronic transport along ferroelectric domain walls in lithium niobate single crystals

Ferroelectric domain wall conductivity (DWC) is an intriguing and promising functional property that can be elegantly controlled and steered through a variety of external stimuli such as electric and mechanical fields. Optical-field control, as a noninvasive and flexible tool, has rarely been applied so far, but it significantly expands the possibility for both tuning and probing DWC. On the one hand, as known from second-harmonic or Raman micro-spectroscopy, the optical approach provides information on DW distribution and inclination, while simultaneously probing the DW vibrational modes; on the other hand, photons might be applied to directly generate charge carriers, thereby acting as a functional and spectrally tunable probe to deduce the local absorption properties and bandgaps of conductive DWs. Here, we report on investigating the photo-induced DWC (PI-DWC) of three lithium niobate crystals, containing a very different number of DWs, namely: (A) none, (B) one, and (C) many conductive DWs. All three samples are inspected for their current–voltage behavior in darkness and for different illumination wavelengths swept from 500 nm down to 310 nm. All samples show their maximum PI-DWC at 310 nm; moreover, sample (C) reaches PI-DWCs of several microampere. Interestingly, a noticeable PI-DWC is also observed for sub-bandgap illumination, hinting toward the existence and decisive role of electronic in-gap states that contribute to the electronic charge transport along DWs. Finally, complementary conductive atomic force microscopy investigations under illumination proved that the PI-DWC indeed is confined to the DW area and does not originate from photo-induced bulk conductivity.

Plasma etching promoting the saturable absorption of BiOI

Materials exhibiting exceptional saturable absorption performance and etching compatibility are significant in the context of advanced optical devices. Our study demonstrates that plasma etching can effectively promote the saturable absorption of BiOI nanosheets because of defect formation. Remarkably, the BiOI nanosheet subjected to the optimized H2/Ar-plasma treatment manifests a substantial nonlinear absorption coefficient (βeff) of (−5.5 ± 0.7) × 103 cm GW−1 under laser excitation at 800 nm, while the pristine BiOI sample exhibits no discernible nonlinear optical response. The βeff of plasma-treated BiOI samples is (−4.2 ± 0.9) × 103 cm GW−1 at 515 nm, surpassing that of the untreated counterpart by more than fourfold. A comprehensive structural and spectroscopic analysis indicates that oxygen vacancies serve to increase the density of in-gap states, thereby narrowing the bandgap of the BiOI. This reduced bandgap effectively facilitates the Pauli-blocking effect and, in turn, augments the saturable absorption properties of the samples. In contrast to oxygen vacancies, iodine vacancies make a negligible contribution to the performance enhancement of BiOI. Our result would provide a promising way to improve the nonlinear optical response of materials.

Temperature and pressure dependencies of Sm valence in SmB[formula omitted] Kondo insulator probed by x-ray absorption spectroscopy

Pressure and temperature induced valence changes in the Kondo insulator SmB6 have been investigated using x-ray absorption spectroscopy (XAS) along several isobaric cooling runs and one isothermal compression. The average valence of Sm at various pressure and temperature conditions is extracted from high quality XAS data by peak fitting procedures. The temperature dependence of the Sm valence at ambient pressure shows changes of slope near the known characteristic temperatures of gap formation (120 K) and the in-gap state (50 K). At higher pressures the average valence also shows similar temperature dependent trends upon cooling but the slope changes are less pronounced. This behavior is discussed in relation to the possible existence of an underlying first order valence transition and its critical end point. At constant temperature (T=20 K), the Sm valence increases rapidly with pressure; however, it remains far below the expected integer value (3+) near the onset of the magnetic ordering and gap closure. In addition, the local structure of SmB6 at ambient conditions has been analyzed using extended x-ray absorption fine structure.

Observation of edge states derived from topological helix chains.

Introducing the concept of topology has revolutionized materials classification, leading to the discovery of topological insulators and Dirac-Weyl semimetals1-3. One of the most fundamental theories underpinning topological materials is the Su-Schrieffer-Heeger (SSH) model4,5, which was developed in 1979-decades before the recognition of topological insulators-to describe conducting polymers. Distinct from the vast majority of known topological insulators with two and three dimensions1-3, the SSH model predicts a one-dimensional analogue of topological insulators, which hosts topological bound states at the endpoints of a chain4-8. To establish this unique and pivotal state, it is crucial to identify the low-energy excitations stemming from bound states, but this has remained unknown in solids because of the absence of suitable platforms. Here we report unusual electronic states that support the emergent bound states in elemental tellurium, the single helix of which was recently proposed to realize an extended version of the SSH chain9,10. Using spin- and angle-resolved photoemission spectroscopy with a micro-focused beam, we have shown spin-polarized in-gap states confined to the edges of the (0001) surface. Our densityfunctional theory calculations indicate that these states are attributed to the interacting bound states originating from the one-dimensional array of SSH tellurium chains. Helices in solids offer a promising experimental platform for investigating exotic properties associated with the SSH chain and exploring topological phases through dimensionality control.

Unconventional Band Structure via Combined Molecular Orbital and Lattice Symmetries in a Surface-Confined Metallated Graphdiyne Sheet.

Graphyne (GY) and graphdiyne (GDY)-based monolayers represent the next generation 2D carbon-rich materials with tunable structures and properties surpassing those of graphene. However, the detection of band formation in atomically thin GY/GDY analogues has been challenging, as both long-range order and atomic precision have to be fulfilled in the system. The presentwork reports direct evidence of band formation in on-surface synthesized metallated Ag-GDY sheets with mesoscopic (≈1µm) regularity. Employing scanning tunneling and angle-resolved photoemission spectroscopies, energy-dependent transitions of real-space electronic states above the Fermi level and formation of the valence band are respectively observed. Furthermore, density functional theory (DFT) calculations corroborate the observations and reveal that doubly degenerate frontier molecular orbitals on a honeycomb lattice give rise to flat, Dirac and Kagome bands close to the Fermi level. DFT modeling also indicates an intrinsic band gap for the pristine sheet material, which is retained for a bilayer with h-BN, whereas adsorption-induced in-gap electronic states evolve at the synthesis platform with Ag-GDY decorating the (111) facet of silver. These results illustrate the tremendous potential for engineering novel band structures via molecular orbital and lattice symmetries in atomically precise 2D carbon materials.

Topologically Protected Photovoltaics in Bi Nanoribbons.

Photovoltaic efficiency in solar cells is hindered by many unwanted effects. Radiative channels (emission of photons) sometimes mediated by nonradiative ones (emission of phonons) are principally responsible for the decrease in exciton population before charge separation can take place. One such mechanism is electron-hole recombination at surfaces or defects where the in-gap edge states serve as the nonradiative channels. In topological insulators (TIs), which are rarely explored from an optoelectronics standpoint, we show that their characteristic surface states constitute a nonradiative decay channel that can be exploited to generate a protected photovoltaic current. Focusing on two-dimensional TIs, and specifically for illustration purposes on a Bi(111) monolayer, we obtain the transition rates from the bulk excitons to the edge states. By breaking the appropriate symmetries of the system, one can induce an edge charge accumulation and edge currents under illumination, demonstrating the potential of TI nanoribbons for photovoltaics.

Deep-Level Structure of the Spin-Active Recombination Center in Dilute Nitrides.

A gallium interstitial defect is thought to be responsible for the spectacular spin-dependent recombination in GaAs_{1-x}N_{x} dilute nitrides. Current understanding associates this defect with at least two in-gap levels corresponding to the (+/0) and (++/+) charge-state transitions. Using a spin-sensitive photoinduced current transient spectroscopy, the in-gap electronic structure of a x=0.021 alloy is revealed. The (+/0) state lies ≈0.27 eV below the conduction band edge, and an anomalous, negative activation energy reveals the presence of not one but two other in-gap states. The observations are consistent with a (++/+) state ≈0.19 eV above the valence band edge, and a (+++/++) state ≈25 meV above the valence band edge.

Theoretical study of the influence of GaOx interfacial layer on the GaN/SiO2 interface property

The spontaneous formation of a Ga-oxide (GaOx) intermediate layer at the GaN/SiO2 interface has been reported during the SiO2 deposition on the GaN substrate. In this study, we have performed first-principles calculations and unveiled atomic and electronic structures of the GaN/SiO2 interface with 1-nm thick GaOx intermediate layer. Our calculations show that the top-layer Ga atoms on the GaN side are terminated with the O atoms on the GaOx side, leading to the clean GaN/GaOx interface and the absence of the electronic state in the midgap region. However, strongly localized states, which are originated from O atoms lone-pair orbitals in the –GaOSi– local structures, emerge in the gap near the valence-band maximum of GaN. These in-gap states become hole traps in GaN MOS devices, leading to a degradation in device controllability and operational speed.

Emergent two-band conduction at Ti delta-doped LaAlO3/KTaO3 (111) heterointerface

Recently, several intriguing interfacial phenomena have been discovered at the KTaO3 (111)-based heterointerfaces, such as the two-dimensional electron gas, superconductivity, anisotropic conductivity, etc. However, the available techniques to systematically manipulate such interfacial states are quite limited. Here, we devise a delta-doping strategy by inserting a sub-nanometer Ti layer with distinct reducibilities to the LaAlO3/KTaO3 (111) interface. In the delta-doped samples, we observe an unforeseen two-band conduction, evidenced by the emergence of a new type of electron carrier with an order-of-magnitude enhancement of mobility (∼1800 cm2V−1s−1) than the original carriers. Moreover, the appearance of the high-mobility carriers causes a sharp transition between the non-Fermi-liquid superconducting state and the Fermi-liquid state with reduced spin–orbit scattering. Further evidence shows that the new type of carriers stems from another in-gap state with a shallower energy level compared to the original carriers. Our study broadens the spectrum of interfacial carrier manipulation by introducing an extra band/channel for carrier conduction, which not only opens up new possibilities in device applications but also shines a light on the underlying physics of interfacial superconductivity.

Orbital hybridization and defective states of vacancy defects in AlN

Intrinsic atomic defects pose a great effect in wide-bandgap semiconductors owing to the high tendency of forming in-gap defective states. Utilizing density-functional theory, the atomic vacancy defects of Al and N vacancies in hexagonal wurtzite aluminum nitride (AlN) are investigated. We find that the most energetically favorable form of vacancies is predicted to be negatively trivalent charged Al vacancy (VAl−3) in n-type AlN and positively monovalent charged N vacancy (VN+1) in p-type AlN, respectively. N vacancy generally has a low formation energy and could be either an acceptor or a donor: Under p-type conduction, it is a deep donor with a positively monovalent charge of +1, acting as a compensating center for holes; Under n-type conduction, it is a deep acceptor carrying charge of −3, acting as a compensating center for electrons. For the Al vacancy, it tends to be a shallow acceptor in p-type AlN but a high formation energy or a deep acceptor in n-type AlN with low formation energy, most possibly at a negatively trivalent charged state. Our orbital hybridization analysis shows that these vacancies can be facilely generated which are rooted in the antibonding coupling Al3 s-N2p states in valence band. The above finding is independent of the chemical potential of nitrogen and aluminum and holds true under both nitrogen rich and poor conditions. Our work provides a guide to experimental works by providing the energetics and atomic-scale mechanism of doping nature of atomic vacancies in AlN.

Tuneable Current Rectification Through a Designer Graphene Nanoribbon.

Unimolecular current rectifiers are fundamental building blocks in organic electronics. Rectifying behavior has been identified in numerous organic systems due to electron-hole asymmetries of orbital levels interfaced by a metal electrode. As a consequence, the rectifying ratio (RR) determining the diode efficiency remains fixed for a chosen molecule-metal interface. Here, a mechanically tunable molecular diode exhibiting an exceptionally large rectification ratio (>105) and reversible direction is presented. The molecular system comprises a seven-armchair graphene nanoribbon (GNR) doped with a single unit of substitutional diboron within its structure, synthesized with atomic precision on a gold substrate by on-surface synthesis. The diboron unit creates half-populated in-gap bound states and splits the GNR frontier bands into two segments, localizing the bound state in a double barrier configuration. By suspending these GNRs freely between the tip of a low-temperature scanning tunneling microscope and the substrate, unipolar hole transport is demonstrated through the boron in-gap state's resonance. Strong current rectification is observed, associated with the varying widths of the two barriers, which can be tuned by altering the distance between tip and substrate. This study introduces an innovative approach for the precise manipulation of molecular electronic functionalities, opening new avenues for advanced applications in organicelectronics.

Higher-Order Topological In-Bulk Corner State in Pure Diffusion Systems.

Compared with conventional topological insulator that carries topological state at its boundaries, the higher-order topological insulator exhibits lower-dimensional gapless boundary states at its corners and hinges. Leveraging the form similarity between Schrödinger equation and diffusion equation, research on higher-order topological insulators has been extended from condensed matter physics to thermal diffusion. Unfortunately, all the corner states of thermal higher-order topological insulator reside within the band gap. Another kind of corner state, which is embedded in the bulk states, has not been realized in pure diffusion systems so far. Here, we construct higher-dimensional Su-Schrieffer-Heeger models based on sphere-rod structure to elucidate these corner states, which we term "in-bulk corner states." Because of the anti-Hermitian properties of diffusive Hamiltonian, we investigate the thermal behavior of these corner states through theoretical calculation, simulation, and experiment. Furthermore, we study the different thermal behaviors of in-bulk corner state and in-gap corner state. Our results would open a different gate for diffusive topological states and provide a distinct application for efficient heat dissipation.

Atomic-scale visualization of the interlayer Rydberg exciton complex in moiré heterostructures

Excitonic systems, facilitated by optical pumping, electrostatic gating or magnetic field, sustain composite particles with fascinating physics. Although various intriguing excitonic phases have been revealed via global measurements, the atomic-scale accessibility towards excitons has yet to be established. Here, we realize the ground-state interlayer exciton complexes through the intrinsic charge transfer in monolayer YbCl3/graphite heterostructure. Combining scanning tunneling microscope and theoretical calculations, the excitonic in-gap states are directly profiled. The out-of-plane excitonic charge clouds exhibit oscillating Rydberg nodal structure, while their in-plane arrangements are determined by moiré periodicity. Exploiting the tunneling probe to reflect the shape of charge clouds, we reveal the principal quantum number hierarchy of Rydberg series, which points to an excitonic energy-level configuration with unusually large binding energy. Our results demonstrate the feasibility of mapping out the charge clouds of excitons microscopically and pave a brand-new way to directly investigate the nanoscale order of exotic correlated phases.

Mott Gap Filling by Doping Electrons through Depositing One Sub-Monolayer Thin Film of Rb on Ca2CuO2Cl2

Understanding the doping evolution from a Mott insulator to a superconductor probably holds the key to resolve the mystery of unconventional superconductivity in copper oxides. To elucidate the evolution of the electronic state starting from the Mott insulator, we dose the surface of the parent phase Ca2CuO2Cl2 by depositing Rb atoms, which are supposed to donate electrons to the CuO2 planes underneath. We successfully achieved the Rb sub-monolayer thin films in forming the square lattice. The scanning tunneling microscopy or spectroscopy measurements on the surface show that the Fermi energy is pinned within the Mott gap but close to the edge of the charge transfer band. In addition, an in-gap state appears at the bottom of the upper Hubbard band (UHB), and the Mott gap will be significantly diminished. Combined with the Cl defect and the Rb adatom/cluster results, the electron doping is likely to increase the spectra weight of the UHB for the double occupancy. Our results provide information to understand the electron doping to the parent compound of cuprates.

First-Principles Studies of the Electronic and Optical Properties of Zinc Titanium Nitride: The Role of Cation Disorder.

Cation disorder is an established feature of heterovalent ternary nitrides, a promising class of semiconductor materials. A recently synthesized wurtzite-family ternary nitride, ZnTiN2, shows potential for durable photoelectrochemical applications with a measured optical absorption onset of 2 eV, which is 1.4 eV lower than previously predicted, a large difference attributed to cation disorder. Here, we use first-principles calculations based on density functional theory to establish the role of cation disorder in the electronic and optical properties of ZnTiN2. We compute antisite defect arrangement formation energies for one hundred 128-atom supercells and analyze their trends and their effect on electronic structures, rationalizing experimental results. We demonstrate that charge imbalance created by antisite defects in Ti and N local environments, respectively, broadens the conduction and valence bands near the band edges, reducing the band gap relative to the cation-ordered limit, a general mechanism relevant to other multivalent ternary nitrides. Charge-imbalanced antisite defect arrangements that lead to N-centered tetrahedral motifs fully coordinated by Zn are the most energetically costly and introduce localized in-gap states; cation arrangements that better preserve local charge balance have smaller formation energies and have less impact on the electronic structure. Our work provides insights into the nature of cation disorder in the newly synthesized semiconductor ZnTiN2, with implications for its performance in energy applications, and provides a baseline for the future study of controlling cation order in ZnTiN2 and other ternary nitrides.

Spin-orbital Jahn-Teller bipolarons

Polarons and spin-orbit (SO) coupling are distinct quantum effects that play a critical role in charge transport and spin-orbitronics. Polarons originate from strong electron-phonon interaction and are ubiquitous in polarizable materials featuring electron localization, in particular 3d transition metal oxides (TMOs). On the other hand, the relativistic coupling between the spin and orbital angular momentum is notable in lattices with heavy atoms and develops in 5d TMOs, where electrons are spatially delocalized. Here we combine ab initio calculations and magnetic measurements to show that these two seemingly mutually exclusive interactions are entangled in the electron-doped SO-coupled Mott insulator Ba2Na1−xCaxOsO6 (0 < x < 1), unveiling the formation of spin-orbital bipolarons. Polaron charge trapping, favoured by the Jahn-Teller lattice activity, converts the Os 5d1 spin-orbital Jeff = 3/2 levels, characteristic of the parent compound Ba2NaOsO6 (BNOO), into a bipolaron 5d2 Jeff = 2 manifold, leading to the coexistence of different J-effective states in a single-phase material. The gradual increase of bipolarons with increasing doping creates robust in-gap states that prevents the transition to a metal phase even at ultrahigh doping, thus preserving the Mott gap across the entire doping range from d1 BNOO to d2 Ba2CaOsO6 (BCOO).

Photocarrier generation mechanism of graphene-based field effect device

The carrier generation in a photodetecting device plays a critical role in the enhancement of photocurrent. Here we perform photocurrent measurements on graphene-based photodetecting device and unveil three carrier generation mechanisms, namely, (I) thermally assisted- and (II) optically induced- excitation of in-gap defect state electron, and (III) inter-band optical absorption of bulk Si. We further determine their carrier supply strength defined as P = dn/dt, which are P(I) = 2.09×1010 /cm⋅2 s, P(II) = 2.15×1010 /cm⋅2s, and P(III) = 3.55×1011 /cm⋅2s, respectively. In addition, we show that the characteristic IV behavior induced by the gate voltage cycling can be interpreted in terms of the three carrier generation mechanisms. This study provides a useful guide to designing practical graphene-based photodetecting devices.

Optical Modulation of MoTe2/Ferroelectric Heterostructure via Interface Doping.

Optical modulation through interface doping offers a convenient and efficient way to control ferroelectric polarization, thereby advancing the utilization of ferroelectric heterostructures in nanoelectronic and optoelectronic devices. In this work, we fabricated heterostructures of MoTe2/BaTiO3/La0.7Sr0.3MnO3 (MoTe2/BTO/LSMO) and demonstrated opposite ultraviolet (UV) light-induced polarization switching behaviors depending on the varied thicknesses of MoTe2. The thickness-dependent band structure of MoTe2 film results in interface doping with opposite polarity in the respective heterostructures. The polarization field of BTO interacts with the interface charges, and an enhanced effective built-in field (Ebi) can trigger the transfer of massive UV light-induced carriers in both MoTe2 and BTO films. As a result, the interplay among the contact field of MoTe2/BTO, the polarization field, and the optically excited carriers determines the UV light-induced polarization switching behavior of the heterostructures. In addition, the electric transport characteristics of MoTe2/BTO/LSMO heterostructures reveal the interface barrier height and Ebi under opposite polarization states, as well as the presence of inherent in-gap trap states in MoTe2 and BTO films. These findings represent a further step toward achieving multifield modulation of the ferroelectric polarization and promote the potential applications in optoelectronic, logic, memory, and synaptic ferroelectric devices.