Dynamic Doping of Nickelates with Lithium Reveals a Widely Tunable Insulator-Metal Transition with Charge Filling and Band Renormalization Regimes.

The insertion of electron-donating ions has emerged as a powerful technique to manipulate the electronic structure of correlated oxides. However, the resulting electronic structure remains poorly understood, with challenges in quantifying dopant concentration, unexplained differences with substitutionally doped films, and a poor understanding of how dopant atoms interact with insulator-metal transitions (IMTs). Here, these issues are addressed in the context of the rare earth nickelates, a prototypical correlated oxide family with widely tunable electronic behavior under the insertion of protons and alkali metals as interstitial dopants.

Lithography-Defined Semiconductor Moirés with Anomalous In-Gap Quantum Hall States.

Quantum materials and phenomena have attracted great interest for their potential applications in next-generation microelectronics and quantum-information technologies. In one especially interesting class of quantum materials, moiré superlattices (MSLs) formed by twisted bilayers of 2D materials, a wide range of novel phenomena are observed. However, there exist daunting challenges such as reproducibility and scalability of utilizing 2D MSLs for microelectronics and quantum technologies due to their exfoliate-tear-stack method.

Topological Phenomena in Artificial Quantum Materials Revealed by Local Chern Markers.

A striking example of frustration in physics is Hofstadter's butterfly, a fractal structure that emerges from the competition between a crystal's lattice periodicity and the magnetic length of an applied field. Current methods for predicting the topological invariants associated with Hofstadter's butterfly are challenging or impossible to apply to a range of materials, including those that are disordered or lack a bulk spectral gap. Here, we demonstrate a framework for predicting a material's local Chern markers using its position-space description and validate it against experimental observations of quantum transport in artificial graphene in a semiconductor heterostructure, inherently accounting for fabrication disorder strong enough to close the bulk spectral gap.

Tuning the Spin Transition and Carrier Type in Rare-Earth Cobaltates via Compositional Complexity.

There is growing interest in material candidates with properties that can be engineered beyond traditional design limits. Compositionally complex oxides (CCO), often called high entropy oxides, are excellent candidates, wherein a lattice site shares more than four cations, forming single-phase solid solutions with unique properties. However, the nature of compositional complexity in dictating properties remains unclear, with characteristics that are difficult to calculate from first principles.

Tunable Intervalence Charge Transfer in Ruthenium Prussian Blue Analog Enables Stable and Efficient Biocompatible Artificial Synapses.

Emerging concepts for neuromorphic computing, bioelectronics, and brain-computer interfacing inspire new research avenues aimed at understanding the relationship between oxidation state and conductivity in unexplored materials. This report expands the materials playground for neuromorphic devices to include a mixed valence inorganic 3D coordination framework, a ruthenium Prussian blue analog (RuPBA), for flexible and biocompatible artificial synapses that reversibly switch conductance by more than four orders of magnitude based on electrochemically tunable oxidation state. The electrochemically tunable degree of mixed valency and electronic coupling between N-coordinated Ru sites controls the carrier concentration and mobility, as supported by density functional theory computations and application of electron transfer theory to in situ spectroscopy of intervalence charge transfer.

Electronic Structure and Stacking Arrangement of Tungsten Disulfide at the Gold Contact.

There is an intensive effort to control the nature of attractive interactions between ultrathin semiconductors and metals and to understand its impact on the electronic properties at the junction. Here, we present a photoelectron spectroscopy study on the interface between WS films and gold, with a focus on the occupied electronic states near the Brillouin zone center (i.e.

Charge Transfer Screening and Energy Level Alignment at Complex Organic-Inorganic Interfaces: A Tractable GW Approach.

Complex organic-inorganic interfaces are important for device and sensing applications. Charge transfer doping is prevalent in such applications and can affect the interfacial energy level alignments (ELA), which are determined by many-body interactions. We develop an approximate many-body GW approach that can capture many-body interactions due to interfacial charge transfer.

Defying Thermodynamics: Stabilization of Alane Within Covalent Triazine Frameworks for Reversible Hydrogen Storage.

The highly unfavorable thermodynamics of direct aluminum hydrogenation can be overcome by stabilizing alane within a nanoporous bipyridine-functionalized covalent triazine framework (AlH @CTF-bipyridine). This material and the counterpart AlH @CTF-biphenyl rapidly desorb H between 95 and 154 °C, with desorption complete at 250 °C. Sieverts measurements, Al MAS NMR and Al{ H} REDOR experiments, and computational spectroscopy reveal that AlH @CTF-bipyridine dehydrogenation is reversible at 60 °C under 700 bar hydrogen, >10 times lower pressure than that required to hydrogenate bulk aluminum.

Nanoconfinement of Molecular Magnesium Borohydride Captured in a Bipyridine-Functionalized Metal-Organic Framework.

The lower limit of metal hydride nanoconfinement is demonstrated through the coordination of a molecular hydride species to binding sites inside the pores of a metal-organic framework (MOF). Magnesium borohydride, which has a high hydrogen capacity, is incorporated into the pores of UiO-67bpy (ZrO(OH)(bpydc) with bpydc = 2,2'-bipyridine-5,5'-dicarboxylate) by solvent impregnation. The MOF retained its long-range order, and transmission electron microscopy and elemental mapping confirmed the retention of the crystal morphology and revealed a homogeneous distribution of the hydride within the MOF host.

Prospects for Bioinspired Single-Photon Detection Using Nanotube-Chromophore Hybrids.

The human eye is an exquisite photodetection system with the ability to detect single photons. The process of vision is initiated by single-photon absorption in the molecule retinal, triggering a cascade of complex chemical processes that eventually lead to the generation of an electrical impulse. Here, we analyze the single-photon detection prospects for an architecture inspired by the human eye: field-effect transistors employing carbon nanotubes functionalized with chromophores.

Bulk-free topological insulator BiSe nanoribbons with magnetotransport signatures of Dirac surface states.

Many applications of topological insulators (TIs) as well as new phenomena require devices with reduced dimensions. While much progress has been made to realize thin films of TIs with low bulk carrier densities, nanostructures have not yet been reported with similar properties, despite the fact that reduced dimensions should help diminish the contributions from bulk carriers. Here we demonstrate that BiSe nanoribbons, grown by a simple catalyst-free physical-vapour deposition, have inherently low bulk carrier densities, and can be further made bulk-free by thickness reduction, thus revealing the high mobility topological surface states.

Interlayer Coupling and Gate-Tunable Excitons in Transition Metal Dichalcogenide Heterostructures.

Bilayer van der Waals (vdW) heterostructures such as MoS/WS and MoSe/WSe have attracted much attention recently, particularly because of their type II band alignments and the formation of interlayer exciton as the lowest-energy excitonic state. In this work, we calculate the electronic and optical properties of such heterostructures with the first-principles GW+Bethe-Salpeter Equation (BSE) method and reveal the important role of interlayer coupling in deciding the excited-state properties, including the band alignment and excitonic properties. Our calculation shows that due to the interlayer coupling, the low energy excitons can be widely tuned by a vertical gate field.

Two-dimensional metal-organic frameworks with high thermoelectric efficiency through metal ion selection.

Two-dimensional (2D) materials have attracted much attention due to their novel properties. An exciting new class of 2D materials based on metal-organic frameworks (MOFs) has recently emerged, displaying high electrical conductivity, a rarity among organic nanoporous materials. The emergence of these materials raises intriguing questions about their fundamental electronic, optical, and thermal properties, but few studies exist in this regard.

Dynamic Wavelength-Tunable Photodetector Using Subwavelength Graphene Field-Effect Transistors.

Dynamic wavelength tunability has long been the holy grail of photodetector technology. Because of its atomic thickness and unique properties, graphene opens up new paradigms to realize this concept, but so far this has been elusive experimentally. Here we employ detailed quantum transport modeling of photocurrent in graphene field-effect transistors (including realistic electromagnetic fields) to show that wavelength tunability is possible by dynamically changing the gate voltage.

Dynamical Excitonic Effects in Doped Two-Dimensional Semiconductors.

It is well-known that excitonic effects can dominate the optical properties of two-dimensional materials. These effects, however, can be substantially modified by doping free carriers. We investigate these doping effects by solving the first-principles Bethe-Salpeter equation.

Tunable band gaps and excitons in doped semiconducting carbon nanotubes made possible by acoustic plasmons.

Doping of semiconductors is essential in modern electronic and photonic devices. While doping is well understood in bulk semiconductors, the advent of carbon nanotubes and nanowires for nanoelectronic and nanophotonic applications raises some key questions about the role and impact of doping at low dimensionality. Here we show that for semiconducting carbon nanotubes, band gaps and exciton binding energies can be dramatically reduced upon experimentally relevant doping, and can be tuned gradually over a broad range of energies in contrast with higher dimensional systems.

Angle-resolved photoemission spectra of graphene from first-principles calculations.

Angle-resolved photoemission spectroscopy (ARPES) is a powerful experimental technique for directly probing electron dynamics in solids. The energy versus momentum dispersion relations and the associated spectral broadenings measured by ARPES provide a wealth of information on quantum many-body interaction effects. In particular, ARPES allows studies of the Coulomb interaction among electrons (electron-electron interactions) and the interaction between electrons and lattice vibrations (electron-phonon interactions).

First-principles study of electron linewidths in graphene.

We present first-principles calculations of the linewidths of low-energy quasiparticles in n-doped graphene arising from both the electron-electron and the electron-phonon interactions. The contribution to the electron linewidth arising from the electron-electron interactions varies significantly with wave vector at fixed energy; in contrast, the electron-phonon contribution is virtually wave vector independent. These two contributions are comparable in magnitude at a binding energy of approximately 0.

Bound excitons in metallic single-walled carbon nanotubes.

We extend previous ab initio calculations on excitonic effects in metallic single-walled carbon nanotubes to more experimentally realizable larger diameter tubes. Our calculations predict bound exciton states in both the (10,10) and (12,0) tubes with binding energies of approximately 50 meV providing experimentally verifiable changes to the absorption line shape in each case. The second and third van Hove singularities in the joint density of states also give rise to a single optically active bound or resonant excitonic state.

Excitons and many-electron effects in the optical response of single-walled boron nitride nanotubes.

We report first-principles calculations of the effects of quasiparticle self-energy and electron-hole interaction on the optical properties of single-walled boron nitride nanotubes. Excitonic effects are shown to be even more important in BN nanotubes than in carbon nanotubes. Electron-hole interactions give rise to complexes of bright (and dark) excitons, which qualitatively alter the optical response.

Theory and ab initio calculation of radiative lifetime of excitons in semiconducting carbon nanotubes.

We present a theoretical analysis and first-principles calculation of the radiative lifetime of excitons in semiconducting carbon nanotubes. An intrinsic lifetime of the order of 10 ps is computed for the lowest optically active bright excitons. The intrinsic lifetime is, however, a rapid increasing function of the exciton momentum.

Structural transformations of carbon nanotubes under hydrostatic pressure.

We used simulations with a classical force field to study the transformation under hydrostatic pressure of isolated single-walled nanotubes (SWNT) from a circular to a collapsed cross section. Small-diameter SWNTs deform continuously under pressure, whereas larger-diameter SWNTs display hysteresis and undergo a first-order-like transformation. The different behavior is due to the changing proportions in the total energy of the wall-curvature energy and the van der Waals attraction between opposite walls of the tube.