Targeting One- and Two-Dimensional Ta-Te Structures via Nanotube Encapsulation.

Fine control over material synthesis on the nanoscale can facilitate the stabilization of competing crystalline structures. Here, we demonstrate how carbon nanotube reaction vessels can be used to selectively create one-dimensional TaTe3 chains or two-dimensional TaTe2 nanoribbons with exquisite control of the chain number or nanoribbon thickness and width. Transmission electron microscopy and scanning transmission electron microscopy reveal the detailed atomic structure of the encapsulated materials. Complex superstructures such as multichain spiraling and apparent multilayer moirés are observed. The rare 2H phase of TaTe2 (1H in monolayer) is found to be abundant as an encapsulated nanoribbon inside carbon nanotubes. The experimental results are complemented by density functional theory calculations for the atomic and electronic structure, which uncovers the prevalence of 2H-TaTe2 due to nanotube-to-nanoribbon charge transfer and size confinement. Calculations also reveal new 1T' type charge density wave phases in TaTe2 that could be observed in experimental studies.

Resonantly Enhanced Electromigration Forces for Adsorbates on Graphene.

We investigate the electromigration forces for weakly bonded adsorbates on graphene by using density-functional based calculations. We find that the nature of electromigration forces on an adsorbate critically depends on the energy level alignment between the adsorbate state and the Fermi level of the graphene. For a resonant adsorbate, whose frontier orbitals lie close to the Fermi level, the electromigration force is dominated by the electron wind force that is strongly enhanced along the electron flow direction, irrespective of the sign of the adsorbate charge. For a nonresonant adsorbate, the electromigration force is essentially the direct force that depends on the adsorbate charge. We also show that the magnitude of electromigration forces can be continuously tunable through electrostatic gating for resonant adsorbates. Our results provide new insight for understanding and controlling how nanoscale objects behave in or on host materials.

Nonstoichiometric Salt Intercalation as a Means to Stabilize Alkali Doping of 2D Materials.

Although doping with alkali atoms is a powerful technique for introducing charge carriers into physical systems, the resulting charge-transfer systems are generally not air stable. Here we describe computationally a strategy towards increasing the stability of alkali-doped materials that employs stoichiometrically unbalanced salt crystals with excess cations (which could be deposited during, e.g., in situ gating) to achieve doping levels similar to those attained by pure alkali metal doping. The crystalline interior of the salt crystal acts as a template to stabilize the excess dopant atoms against oxidation and deintercalation, which otherwise would be highly favorable. We characterize this doping method for graphene, NbSe_{2}, and Bi_{2}Se_{3} and its effect on direct-to-indirect band gap transitions, 2D superconductivity, and thermoelectric performance. Salt intercalation should be generally applicable to systems which can accommodate this "ionic crystal" doping (and particularly favorable when geometrical packing constraints favor nonstoichiometry).

Magnetism and interlayer bonding in pores of Bernal-stacked hexagonal boron nitride.

When single-layer h-BN is subjected to a high-energy electron beam, triangular pores with nitrogen edges are formed. Because of the broken sp2 bonds, these pores are known to possess magnetic states. We report on the magnetism and electronic structure of triangular pores as a function of their size. Moreover, in the Bernal-stacked h-BN (AB-h-BN), multilayer pores with parallel edges can be created, which is not possible in the commonly fabricated multilayer AA'-h-BN. Given that these pores can be manufactured in a well-controlled fashion using an electron beam, it is important to understand the interactions of pores in neighboring layers. We find that in certain configurations, the edges of the neighboring pores remain open and retain their magnetism, and in others, they form interlayer bonds. We present a comprehensive report on these configurations for small nanopores. We find that at low temperatures, these pores have near degenerate magnetic configurations, and may be utilized in magnetoresistance and spintronics applications. In the process of forming larger multilayer nanopores, interlayer bonds can form, reducing the magnetization. Yet, unbonded parallel multilayer edges remain available at all sizes. Understanding these pores is also helpful in a multitude of applications such as DNA sequencing and quantum emission.

Ultranarrow TaS2 Nanoribbons.

Imposing additional confinement in two-dimensional (2D) materials yields further control over their electronic, optical, and topological properties. However, synthesis of ultranarrow nanoribbons (NRs) remains challenging, particularly for transition metal dichalcogenides (TMDs), and synthesizing TMD NRs narrower than 50 nm has remained elusive. Here, we report the vapor-phase synthesis of ultranarrow TaS2 NRs. The NRs are grown within carbon nanotubes, limiting their width and layer number, while stabilizing them against the environment. The NRs reach monolayer thickness and exhibit widths down to 2.5 nm. Atomic-resolution scanning transmission electron microscopy reveals the detailed atomic structure of the ultranarrow NRs and we observe a hitherto unseen atomic structure supermodulation of ordered defect arrays within the NRs. Density functional theory calculations show the presence of flat bands and boundary-localized states, and help identify the atomic configuration of the supermodulation. Nanotube-templated synthesis represents a unique, transferable, and broadly deployable route toward ultranarrow TMD NR growth.

Stabilization of NbTe3, VTe3, and TiTe3 via Nanotube Encapsulation.

The structure of MX3 transition metal trichalcogenides (TMTs, with M a transition metal and X a chalcogen) is typified by one-dimensional (1D) chains weakly bound together via van der Waals interactions. This structural motif is common across a range of M and X atoms (e.g., NbSe3, HfTe3,TaS3), but not all M and X combinations are stable. We report here that three new members of the MX3 family which are not stable in bulk, specifically NbTe3, VTe3, and TiTe3, can be synthesized in the few- (2-4) to single-chain limit via nanoconfined growth within the stabilizing cavity of multiwalled carbon nanotubes. Transmission electron microscopy (TEM) and atomic-resolution scanning transmission electron microscopy (STEM) reveal the chain-like nature and the detailed atomic structure. The synthesized materials exhibit behavior unique to few-chain quasi-1D structures, such as few-chain spiraling and a trigonal antiprismatic rocking distortion in the single-chain limit. Density functional theory (DFT) calculations provide insight into the crystal structure and stability of the materials, as well as their electronic structure.

High-Performance Atomically-Thin Room-Temperature NO2 Sensor.

The development of room-temperature sensing devices for detecting small concentrations of molecular species is imperative for a wide range of low-power sensor applications. We demonstrate a room-temperature, highly sensitive, selective, stable, and reversible chemical sensor based on a monolayer of the transition-metal dichalcogenide Re0.5Nb0.5S2. The sensing device exhibits a thickness-dependent carrier type, and upon exposure to NO2 molecules, its electrical resistance considerably increases or decreases depending on the layer number. The sensor is selective to NO2 with only minimal response to other gases such as NH3, CH2O, and CO2. In the presence of humidity, not only are the sensing properties not deteriorated but also the monolayer sensor shows complete reversibility with fast recovery at room temperature. We present a theoretical analysis of the sensing platform and identify the atomically sensitive transduction mechanism.

Frustration and Atomic Ordering in a Monolayer Semiconductor Alloy.

Frustrated interactions can lead to short-range ordering arising from incompatible interactions of fundamental physical quantities with the underlying lattice. The simplest example is the triangular lattice of spins with antiferromagnetic interactions, where the nearest-neighbor spin-spin interactions cannot simultaneously be energy minimized. Here we show that engineering frustrated interactions is a possible route for controlling structural and electronic phenomena in semiconductor alloys. Using aberration-corrected scanning transmission electron microscopy in conjunction with density functional theory calculations, we demonstrate atomic ordering in a two-dimensional semiconductor alloy as a result of the competition between geometrical constraints and nearest-neighbor interactions. Statistical analyses uncover the presence of short-range ordering in the lattice. In addition, we show how the induced ordering can be used as another degree of freedom to considerably modify the band gap of monolayer semiconductor alloys.

Emergence of Topologically Nontrivial Spin-Polarized States in a Segmented Linear Chain.

The synthesis of new materials with novel or useful properties is one of the most important drivers in the fields of condensed matter physics and materials science. Discoveries of this kind are especially significant when they point to promising future basic research and applications. van der Waals bonded materials comprised of lower-dimensional building blocks have been shown to exhibit emergent properties when isolated in an atomically thin form [1-8]. Here, we report the discovery of a transition metal chalcogenide in a heretofore unknown segmented linear chain form, where basic building blocks each consisting of two hafnium atoms and nine tellurium atoms (Hf_{2}Te_{9}) are van der Waals bonded end to end. First-principle calculations based on density functional theory reveal striking crystal-symmetry-related features in the electronic structure of the segmented chain, including giant spin splitting and nontrivial topological phases of selected energy band states. Atomic-resolution scanning transmission electron microscopy reveals single segmented Hf_{2}Te_{9} chains isolated within the hollow cores of carbon nanotubes, with a structure consistent with theoretical predictions. van der Waals bonded segmented linear chain transition metal chalcogenide materials could open up new opportunities in low-dimensional, gate-tunable, magnetic, and topological crystalline systems.

Electrostatically Driven Nanoballoon Actuator.

We demonstrate an inflatable nanoballoon actuator based on geometrical transitions between the inflated (cylindrical) and collapsed (flattened) forms of a carbon nanotube. In situ transmission electron microscopy experiments employing a nanoelectromechanical manipulator show that a collapsed carbon nanotube can be reinflated by electrically charging the nanotube, thus realizing an electrostatically driven nanoballoon actuator. We find that the tube actuator can be reliably cycled with only modest control voltages (few volts) with no apparent wear or fatigue. A complementary theoretical analysis identifies critical parameters for nanotube nanoballoon actuation.

Inhibiting Klein Tunneling in a Graphene p-n Junction without an External Magnetic Field.

We study by first-principles calculations a densely packed island of organic molecules (F_{4}TCNQ) adsorbed on graphene. We find that with electron doping the island naturally forms a p-n junction in the graphene sheet. For example, a doping level of ∼3×10^{13} electrons per cm^{2} results in a p-n junction with an 800 meV electrostatic potential barrier. Unlike in a conventional p-n junction in graphene, in the case of the junction formed by an adsorbed organic molecular island we expect that the Klein tunneling is inhibited, even without an applied external magnetic field. Here Klein tunneling is inhibited by the ferromagnetic order that spontaneously occurs in the molecular island upon doping. We estimate that the magnetic barrier in the graphene sheet is around 10 mT.

Nanostructured Carbon Allotropes with Weyl-like Loops and Points.

Carbon allotropes are subject of intense investigations for their superb structural, electronic, and chemical properties, but not for topological band properties because of the lack of strong spin-orbit coupling (SOC). Here, we show that conjugated p-orbital interactions, common to most carbon allotropes, can in principle produce a new type of topological band structure, forming the so-called Weyl-like semimetal in the absence of SOC. Taking a structurally stable interpenetrated graphene network (IGN) as example, we show, by first-principles calculations and tight-binding modeling, that its Fermi surface is made of two symmetry-protected Weyl-like loops with linear dispersion along perpendicular directions. These loops are reduced to Weyl-like points upon breaking of the inversion symmetry. Because of the topological properties of these band-structure anomalies, remarkably, at a surface terminated by vacuum there emerges a flat band in the loop case and two Fermi arcs in the point case. These topological carbon materials may also find applications in the fields of catalysts.

Carbon kagome lattice and orbital-frustration-induced metal-insulator transition for optoelectronics.

A three-dimensional elemental carbon kagome lattice, made of only fourfold-coordinated carbon atoms, is proposed based on first-principles calculations. Despite the existence of 60° bond angles in the triangle rings, widely perceived to be energetically unfavorable, the carbon kagome lattice is found to display exceptional stability comparable to that of C(60). The system allows us to study the effects of triangular frustration on the electronic properties of realistic solids, and it demonstrates a metal-insulator transition from that of graphene to a direct gap semiconductor in the visible blue region. By minimizing s-p orbital hybridization, which is an intrinsic property of carbon, not only the band edge states become nearly purely frustrated p states, but also the band structure is qualitatively different from any known bulk elemental semiconductors. For example, the optical properties are similar to those of direct-gap semiconductors GaN and ZnO, whereas the effective masses are comparable to or smaller than those of Si.

Small phonon contribution to the photoemission kink in the copper oxide superconductors.

Despite over two decades of intense research efforts, the origin of high-temperature superconductivity in the copper oxides remains elusive. Angle-resolved photoemission spectroscopy experiments have revealed a kink in the dispersion relations (energy versus wavevector) of electronic states in the copper oxides at binding energies of 50-80 meV, raising the hope that this anomaly could be a key to understanding high-temperature superconductivity. The kink is often interpreted in terms of interactions between the electrons and a bosonic field. Although there is no consensus on the nature of the bosons (or even whether a boson model is appropriate), both phonons and spin fluctuations have been proposed as possible candidates. Here we report first-principles calculations of the role of phonons and the electron-phonon interaction in the photoemission spectra of La(2 - x)Sr(x)CuO4. Our calculations within the standard formalism demonstrate that the phonon-induced renormalization of the electron energies and the Fermi velocity is almost one order of magnitude smaller than the effect observed in photoemission experiments. Therefore, our result rules out electron-phonon interaction in bulk La(2 - x)Sr(x)CuO4 as the exclusive origin of the measured kink. Our conclusions are consistent with those reached independently in a recent study of the related compound YBa2Cu3O7.

SiX2 (X = S, Se) Single Chains and (Si-Ge)X2 Quaternary Alloys.

Layered or chain materials have received significant research attention owing to their interesting physical properties, which can dramatically change when the material is thinned from bulk (three-dimensional) to thin two-dimensional sheet or one-dimensional (1D) chain form. Materials with the stoichiometry AX2 with A = Si or Ge and X = S or Se form an especially intriguing semiconducting class. For example, bulk silicon dichalcogenides (SiX2) consist of 1D chains held together by van der Waals forces. Although this structural configuration has the potential to reveal interesting physical phenomena within the 1D limit, obtaining SiX2 single chains has been challenging. We here examine experimentally and theoretically SiX2 materials in the low chain number limit. Carbon nanotubes serve as growth templates and stabilize and protect the structures, and atomic-resolution scanning transmission electron microscopy directly identifies the atomic structure. Two distinct chain structures are observed for SiX2. SixGe1-xS2(1-y)Se2y quaternary alloy chains are also synthesized and characterized, demonstrating tunable semiconducting properties at the atomic-chain level. Density functional theory calculations reveal that the band gap of these alloy chains can be widely tuned through composition engineering. This work offers the possibilities for synthesizing and controlling semiconductor compositions at the single-chain limit to tailor material properties.

Surface atom motion to move iron nanocrystals through constrictions in carbon nanotubes under the action of an electric current.

Under the application of electrical currents, metal nanocrystals inside carbon nanotubes can be bodily transported. We examine experimentally and theoretically how an iron nanocrystal can pass through a constriction in the carbon nanotube with a smaller cross-sectional area than the nanocrystal itself. Remarkably, through in situ transmission electron imaging and diffraction, we find that, while passing through a constriction, the nanocrystal remains largely solid and crystalline and the carbon nanotube is unaffected. We account for this behavior by a pattern of iron atom motion and rearrangement on the surface of the nanocrystal. The nanocrystal motion can be described with a model whose parameters are nearly independent of the nanocrystal length, area, temperature, and electromigration force magnitude. We predict that metal nanocrystals can move through complex geometries and constrictions, with implications for both nanomechanics and tunable synthesis of metal nanoparticles.

Evidence for the R8 phase of germanium.

The formation of R8 germanium is reported. The ß-Sn phase is first induced by the indentation of amorphous germanium (a-Ge) and the resultant phases on pressure release are characterized by Raman scattering. The expected Raman line frequencies for the various phases of Ge are determined from first-principles calculations using density functional perturbation theory of the zone-center phonons in the diamond, ST12, BC8, and R8 Ge phases. In addition to the R8 phase, traces of BC8 may also be present following pressure release.

Anisotropy and isotope effect in superconducting solid hydrogen.

Elucidating the phase diagram of solid hydrogen is a key objective in condensed matter physics. Several decades ago, it was proposed that at low temperatures and high pressures, solid hydrogen would be a metal with a high superconducting transition temperature. This transition to a metallic state can happen through the closing of the energy gap in the molecular solid or through a transition to an atomic solid. Recent experiments have managed to reach pressures in the range of 400-500 GPa, providing valuable insights. There is strong evidence suggesting that metallization via either of these mechanisms occurs within this pressure range. Computational and experimental studies have identified multiple promising crystal phases, but the limited accuracy of calculations and the limited capabilities of experiments prevent us from determining unequivocally the observed phase or phases. Therefore, it is crucial to investigate the superconducting properties of all the candidate phases. Recently, we reported the superconducting properties of theC2/c-24,Cmca-12,Cmca-4 andI41/amd-2 phases, including anharmonic effects. Here, we report the effects of anisotropy on superconducting properties using Eliashberg theory. Then, we investigate the superconducting properties of deuterium and estimate the size of the isotope effect for each phase. We find that the isotope effect on superconductivity is diminished by anharmonicity in theC2/c-24 andCmca-12 phases and enlarged in theCmca-4 andI41/amd-2 phases. Our anharmonic calculations of theC2/c-24 phase of deuterium agree closely with the most recent experiment by Loubeyreet al(2022Phys. Rev. Lett.29035501), indicating that theC2/c-24 phase remains the leading candidate in this pressure range, and has a strong anharmonic character. These characteristics can serve to distinguish among crystal phases in experiment. Furthermore, expanding our understanding of superconductivity in pure hydrogen holds significance in the study of high-Tchydrides.

Tuning the Sharing Modes and Composition in a Tetrahedral GeX2 (X = S, Se) System via One-Dimensional Confinement.

The packing and connectivity of tetrahedral units are central themes in the structural and electronic properties of a host of solids. Here, we report one-dimensional (1D) chains of GeX2 (X = S or Se) with modification of the tetrahedral connectivity at the single-chain limit. Precise tuning of the edge- and corner-sharing modes between GeX2 blocks is achieved by diameter-dependent 1D confinement inside a carbon nanotube. Atomic-resolution scanning transmission electron microscopy directly confirms the existence of two distinct types of GeX2 chains. Density functional theory calculations corroborate the diameter-dependent stability of the system and reveal an intriguing electronic structure that sensitively depends on tetrahedral connectivity and composition. GeS2(1-x)Se2x compound chains are also realized, which demonstrate the tunability of the system's semiconducting properties through composition engineering.

1D Magnetic MX3 Single-Chains (M = Cr, V and X = Cl, Br, I).

Magnetic materials in reduced dimensions are not only excellent platforms for fundamental studies of magnetism, but they play crucial roles in technological advances. The discovery of intrinsic magnetism in monolayer 2D van der Waals systems has sparked enormous interest, but the single-chain limit of 1D magnetic van der Waals materials has been largely unexplored. This paper reports on a family of 1D magnetic van der Waals materials with composition MX3 (M = Cr, V, and X = Cl, Br, I), prepared in fully-isolated fashion within the protective cores of carbon nanotubes. Atomic-resolution scanning transmission electron microscopy identifies unique structures that differ from the well-known 2D honeycomb lattice MX3 structure. Density functional theory calculations reveal charge-driven reversible magnetic phase transitions.