Emergent layer stacking arrangements in c-axis confined MoTe2.

The layer stacking order in 2D materials strongly affects functional properties and holds promise for next-generation electronic devices. In bulk, octahedral MoTe2 possesses two stacking arrangements, the ferroelectric Weyl semimetal Td phase and the higher-order topological insulator 1T' phase. However, in thin flakes of MoTe2, it is unclear if the layer stacking follows the Td, 1T', or an alternative stacking sequence. Here, we use atomic-resolution scanning transmission electron microscopy to directly visualize the MoTe2 layer stacking. In thin flakes, we observe highly disordered stacking, with nanoscale 1T' and Td domains, as well as alternative stacking arrangements not found in the bulk. We attribute these findings to intrinsic confinement effects on the MoTe2 stacking-dependent free energy. Our results are important for the understanding of exotic physics displayed in MoTe2 flakes. More broadly, this work suggests c-axis confinement as a method to influence layer stacking in other 2D materials.

Atomic-Resolution Cryogenic Scanning Transmission Electron Microscopy for Quantum Materials.

ConspectusThe rich physics permeating the phase diagrams of quantum materials have commanded the attention of the solid-state chemistry, materials science, and condensed-matter physics communities, sparking immense research into quantum phase transitions including superconducting, ferroic, and charge-order transitions. Many of these transitions occur at low temperatures and involve electronic, magnetic, or lattice order, which emerges on the atomic to mesoscopic scales. The complex interplay of these states and the heterogeneity that arises due to competition and intertwining of phases, however, is not fully understood and requires probes that capture ordering over multiple length scales down to the local atomic symmetries. Advances in scanning transmission electron microscopy (STEM) have enabled atomic-resolution imaging as well as mapping of functional picometer-scale atomic displacements inside materials. In this Account, we discuss our group's work to expand the reach of atomic-resolution STEM to cryogenic temperatures (cryo-STEM) to study quantum materials with focus on charge-ordered systems.Charge-ordered phases, in which electrons as well as the atomic lattice form periodic patterns that lift the translational symmetries of the crystal, are not only intertwined with superconductivity but also underlie other exotic electronic phenomena such as colossal magnetoresistance and metal-insulator transitions. The periodic lattice distortions (PLDs) modulate the positions of the crystal's nuclei, which can be readily probed by electron microscopy. In a set of examples, we demonstrate cryo-STEM as a powerful technique for probing local order, nanometer-scale heterogeneities, and topological defects in charge-ordered manganites and in transition metal dichalcogenide charge density wave (CDW) systems.With the nearly commensurate-to-commensurate CDW transition upon cooling in 1T-TaS2, we show that nanoscale lattice textures in CDW phases can be revealed through direct imaging. These early atomic-resolution results, however, also highlighted the need for improvements in cryo-STEM imaging, which led to a push to advance data collection and analysis for direct spatial mapping and quantification of PLDs. By introducing an image registration algorithm developed specifically to accommodate fast, low signal-to-noise image acquisitions of crystalline lattices, we address previous limitations due to sample drift in cryo-STEM experiments. This has enabled subangstrom cryo-STEM imaging with sufficient signal-to-noise to reveal the low temperature structure of 1T'-TaTe2. Furthermore, it allows mapping and quantification of PLD atomic displacements in the charge-ordered manganites Bi0.35Sr0.18Ca0.47MnO3 and Nd0.5Sr0.5MnO3 with picometer precision at ∼95 K to resolve not only distinct ordered phases (i.e., site- and bond-centered charge order) but also their nanoscale coexistence within the same sample.Atomic-resolution cryo-STEM opens new opportunities for understanding the microscopic underpinnings of quantum phases. In this Account, we focus on spatial mapping of lattice degrees of freedom in phases that are present at temperatures down to liquid nitrogen. Further advances in instrumentation are needed to expand the temperature range and to also enable atomic-resolution measurements that rely on weaker signals such as electron energy loss spectroscopy (EELS) for probing of electronic structure or 4D-STEM approaches to map electric and magnetic fields.

Large-area ultrathin Te films with substrate-tunable orientation.

Anisotropy in a crystal structure can lead to large orientation-dependent variations of mechanical, optical, and electronic properties. Material orientation control can thus provide a handle to manipulate properties. Here, a novel sputtering approach for 2D materials enables growth of ultrathin (2.5-10 nm) tellurium films with rational control of the crystalline orientation templated by the substrate. The anisotropic Te 〈0001〉 helical chains align in the plane of the substrate on highly oriented pyrolytic graphite (HOPG) and orthogonally to MgO(100) substrates, as shown by polarized Raman spectroscopy and high-resolution electron microscopy. Furthermore, the films are shown to grow in a textured fashion on HOPG, in contrast with previous reports. These ultrathin Te films cover exceptionally large areas (>1 cm2) and are grown at low temperature (25 °C) affording the ability to accommodate a variety of substrates including flexible electronics. They are robust toward oxidation over a period of days and exhibit the non-centrosymmetric P3121 Te structure. Raman signals are acutely dependent on film thickness, suggesting that optical anisotropy persists and is even enhanced at the ultrathin limit. Hall effect measurements indicate orientation-dependent carrier mobility up to 19 cm2 V-1 s-1. These large-area, ultrathin Te films grown by a truly scalable, physical vapor deposition technique with rational control of orientation/thickness open avenues for controlled orientation-dependent properties in semiconducting thin films for applications in electronic and optoelectronic devices.

Atomic-Resolution Cryo-STEM Across Continuously Variable Temperatures.

Atomic-resolution cryogenic scanning transmission electron microscopy (cryo-STEM) has provided a path to probing the microscopic nature of select low-temperature phases in quantum materials. Expanding cryo-STEM techniques to broadly tunable temperatures will give access to the rich temperature-dependent phase diagrams of these materials. With existing cryo-holders, however, variations in sample temperature significantly disrupt the thermal equilibrium of the system, resulting in large-scale sample drift. The ability to tune the temperature without negative impact on the overall instrument stability is crucial, particularly for high-resolution experiments. Here, we test a new side-entry continuously variable temperature dual-tilt cryo-holder which integrates liquid nitrogen cooling with a 6-pin micro-electromechanical system (MEMS) sample heater to overcome some of these experimental challenges. We measure consistently low drift rates of 0.3-0.4 Å/s and demonstrate atomic-resolution cryo-STEM imaging across a continuously variable temperature range from ~100 K to well above room temperature. We conduct additional drift stability measurements across several commercial sample stages and discuss implications for further developments of ultra-stable, flexible cryo-stages.

Emerging Applications of Elemental 2D Materials.

As elemental main group materials (i.e., silicon and germanium) have dominated the field of modern electronics, their monolayer 2D analogues have shown great promise for next-generation electronic materials as well as potential game-changing properties for optoelectronics, energy, and beyond. These atomically thin materials composed of single atomic variants of group III through group VI elements on the periodic table have already demonstrated exciting properties such as near-room-temperature topological insulation in bismuthene, extremely high electron mobilities in phosphorene and silicone, and substantial Li-ion storage capability in borophene. Isolation of these materials within the postgraphene era began with silicene in 2010 and quickly progressed to the experimental identification or theoretical prediction of 15 of the 18 main group elements existing as solids at standard pressure and temperatures. This review first focuses on the significance of defects/functionalization, discussion of different allotropes, and overarching structure-property relationships of 2D main group elemental materials. Then, a complete review of emerging applications in electronics, sensing, spintronics, plasmonics, photodetectors, ultrafast lasers, batteries, supercapacitors, and thermoelectrics is presented by application type, including detailed descriptions of how the material properties may be tailored toward each specific application.

Tunable Magnetic Transition to a Singlet Ground State in a 2D van der Waals Layered Trimerized Kagomé Magnet.

Incorporating magnetism into two-dimensional (2D) van der Waals (vdW) heterostructures is crucial for the development of functional electronic and magnetic devices. Here, we show that Nb3X8 (X = Cl, Br) is a family of 2D layered trimerized kagomé magnets that are paramagnetic at high temperatures and undergo a first-order phase transition on cooling to a singlet magnetic state. X-ray diffraction shows that a rearrangement of the vdW stacking accompanies the magnetic transition, with high- and low-temperature phases consistent with scanning transmission electron microscopy images of the end members α-Nb3Cl8 and ß-Nb3Br8. The temperature of this transition is systematically varied across the solid solution Nb3Cl8-xBrx (x = 0-8), with x = 6 having transitions near room temperature. The solid solution also varies the optical properties, which are further modulated by the phase transition. As such, they provide a platform on which to understand and exploit the interplay between dimensionality, magnetism, and optoelectronic behavior in vdW materials.

A Computational and Experimental Investigation of the Phonon and Optical Properties of Au2P3.

In a combined experimental and theoretical study of gold phosphide (Au2P3), we investigate its vibrational properties, band structure, and dielectric properties, providing new insight into the properties of this underexplored material. Using a simple synthesis route, Au2P3 thin films were produced, enabling the first reported Raman analysis of this material. Coupled with first-principles calculations of these Raman modes, this analysis reveals that low-frequency vibrations are due to Au or mixed Au to P, and at higher frequencies, they are due to P vibrations. Further band structure and dielectric calculations reveal Au2P3 to be a narrow band (0.16 eV) indirect semiconductor. This work helps to fill major gaps in our understanding of key properties in this material that will benefit future research in this field.

Solid-Vapor Reaction Growth of Transition-Metal Dichalcogenide Monolayers.

Two-dimensional (2D) layered semiconducting transition-metal dichalcogenides (TMDCs) are promising candidates for next-generation ultrathin, flexible, and transparent electronics. Chemical vapor deposition (CVD) is a promising method for their controllable, scalable synthesis but the growth mechanism is poorly understood. Herein, we present systematic studies to understand the CVD growth mechanism of monolayer MoSe2 , showing reaction pathways for growth from solid and vapor precursors. Examination of metastable nanoparticles deposited on the substrate during growth shows intermediate growth stages and conversion of non-stoichiometric nanoparticles into stoichiometric 2D MoSe2 monolayers. The growth steps involve the evaporation and reduction of MoO3 solid precursors to sub-oxides and stepwise reactions with Se vapor to finally form MoSe2 . The experimental results and proposed model were corroborated by ab initio Car-Parrinello molecular dynamics studies.

Strain-Induced Electronic Structure Changes in Stacked van der Waals Heterostructures.

Vertically stacked van der Waals heterostructures composed of compositionally different two-dimensional atomic layers give rise to interesting properties due to substantial interactions between the layers. However, these interactions can be easily obscured by the twisting of atomic layers or cross-contamination introduced by transfer processes, rendering their experimental demonstration challenging. Here, we explore the electronic structure and its strain dependence of stacked MoSe2/WSe2 heterostructures directly synthesized by chemical vapor deposition, which unambiguously reveal strong electronic coupling between the atomic layers. The direct and indirect band gaps (1.48 and 1.28 eV) of the heterostructures are measured to be lower than the band gaps of individual MoSe2 (1.50 eV) and WSe2 (1.60 eV) layers. Photoluminescence measurements further show that both the direct and indirect band gaps undergo redshifts with applied tensile strain to the heterostructures, with the change of the indirect gap being particularly more sensitive to strain. This demonstration of strain engineering in van der Waals heterostructures opens a new route toward fabricating flexible electronics.

Improving the stability and optical properties of germanane via one-step covalent methyl-termination.

Two-dimensional van der Waals materials have shown great promise for a variety of electronic, optoelectronic, sensing and energy conversion applications. Since almost every atom in these two-dimensional crystals is exposed to the surface, covalent surface termination could provide a powerful method for the controlled tuning of material properties. Here we demonstrate a facile, one-step metathesis approach that directly converts CaGe2 crystals into mm-sized crystals of methyl-terminated germanane (GeCH3). Replacing --H termination in GeH with --CH3 increases the band gap by ~0.1 eV to 1.7 eV, and produces band edge fluorescence with a quantum yield of ~0.2%, with little dependence on layer thickness. Furthermore, the thermal stability of GeCH3 has been increased to 250 °C compared with 75 °C for GeH. This one-step metathesis approach should be applicable for accessing new families of two-dimensional van der Waals lattices that feature precise organic terminations and with enhanced optoelectronic properties.

Stability and exfoliation of germanane: a germanium graphane analogue.

Graphene's success has shown not only that it is possible to create stable, single-atom-thick sheets from a crystalline solid but that these materials have fundamentally different properties than the parent material. We have synthesized for the first time, millimeter-scale crystals of a hydrogen-terminated germanium multilayered graphane analogue (germanane, GeH) from the topochemical deintercalation of CaGe2. This layered van der Waals solid is analogous to multilayered graphane (CH). The surface layer of GeH only slowly oxidizes in air over the span of 5 months, while the underlying layers are resilient to oxidation based on X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy measurements. The GeH is thermally stable up to 75 °C; however, above this temperature amorphization and dehydrogenation begin to occur. These sheets can be mechanically exfoliated as single and few layers onto SiO2/Si surfaces. This material represents a new class of covalently terminated graphane analogues and has great potential for a wide range of optoelectronic and sensing applications, especially since theory predicts a direct band gap of 1.53 eV and an electron mobility ca. five times higher than that of bulk Ge.