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Group-IV monochalcogenides have recently shown great potential for their thermoelectric, ferroelectric, and other intriguing properties. The electrical properties of group-IV monochalcogenides exhibit a strong dependence on the chalcogen type. For example, GeTe exhibits high doping concentration, whereas S/Se-based chalcogenides are semiconductors with sizable bandgaps. Here, we investigate the electrical and thermoelectric properties of gamma-GeSe, a recently identified polymorph of GeSe. gamma-GeSe exhibits high electrical conductivity (~106 S/m) and a relatively low Seebeck coefficient (9.4 uV/K at room temperature) owing to its high p-doping level (5x1021 cm-3), which is in stark contrast to other known GeSe polymorphs. Elemental analysis and first-principles calculations confirm that the abundant formation of Ge vacancies leads to the high p-doping concentration. The magnetoresistance measurements also reveal weak-antilocalization because of spin-orbit coupling in the crystal. Our results demonstrate that gamma-GeSe is a unique polymorph in which the modified local bonding configuration leads to substantially different physical properties.

Understanding the nature of molecular excitons in low-dimensional molecular solids is of paramount importance in fundamental photophysics and various applications such as energy harvesting, switching electronics and display devices. Despite this, the spatial evolution of molecular excitons and their transition dipoles have not been captured in the precision of molecular length scales. Here we show in-plane and out-of-plane excitonic evolution in quasilayered two-dimensional (2D) perylene-3, 4, 9, 10-tetracarboxylic dianhydride (PTCDA) crystals assembly-grown on hexagonal boron nitride (BN) crystals. Complete lattice constants with orientations of two herringbone-configured basis molecules are determined with polarization-resolved spectroscopy and electron diffraction methods. In the truly 2D limit of single layers, two Frenkel emissions Davydov-split by Kasha-type intralayer coupling exhibit energy inversion with decreasing temperature, which enhances excitonic coherence. As the thickness increases, the transition dipole moments of newly emerging charge transfer excitons are reoriented because of mixing with the Frenkel states. The current spatial anatomy of 2D molecular excitons will inspire a deeper understanding and groundbreaking applications of low-dimensional molecular systems., Comment: 27 pages, 5 figures

Two-dimensional (2D) crystals' edge structures not only influence their overall properties but also dictate their formation due to edge-mediated synthesis and etching processes. Edges must be carefully examined because they often display complex, unexpected features at the atomic scale, such as reconstruction, functionalization, and uncontrolled contamination. Here, we examine atomic-scale edge structures and uncover reconstruction behavior in bilayer phosphorene. We use in situ transmission electron microscopy (TEM) of phosphorene/graphene specimens at elevated temperatures to minimize surface contamination and reduce e-beam damage, allowing us to observe intrinsic edge configurations. Bilayer zigzag (ZZ) edge was found the most stable edge configuration under e-beam irradiation. Through first-principles calculations and TEM image analysis under various tilting and defocus conditions, we find that bilayer ZZ edges undergo edge reconstruction and so acquire closed, self-passivated edge configurations. The extremely low formation energy of the closed bilayer ZZ edge and its high stability against e-beam irradiation are confirmed by first-principles calculations. Moreover, we fabricate bilayer phosphorene nanoribbons with atomically-sharp closed ZZ edges. The identified bilayer ZZ edges will aid in the fundamental understanding of the synthesis, degradation, reconstruction, and applications of phosphorene and related structures., Comment: 22 pages, 5 figures

Scanning transmission electron microscopy (STEM) is an indispensable tool for atomic-resolution structural analysis for a wide range of materials. The conventional analysis of STEM images is an extensive hands-on process, which limits efficient handling of high-throughput data. Here we apply a fully convolutional network (FCN) for identification of important structural features of two-dimensional crystals. ResUNet, a type of FCN, is utilized in identifying sulfur vacancies and polymorph types of ${MoS_2}$ from atomic resolution STEM images. Efficient models are achieved based on training with simulated images in the presence of different levels of noise, aberrations, and carbon contamination. The accuracy of the FCN models toward extensive experimental STEM images is comparable to that of careful hands-on analysis. Our work provides a guideline on best practices to train a deep learning model for STEM image analysis and demonstrates FCN's application for efficient processing of a large volume of STEM data., Comment: 24 pages, 5 figures

The family of group IV-VI monochalcogenides has an atomically puckered layered structure, and their atomic bond configuration suggests the possibility for the realization of various polymorphs. Here, we report the synthesis of the first hexagonal polymorph from the family of group IV-VI monochalcogenides, which is conventionally orthorhombic. Recently predicted four-atomic-thick hexagonal GeSe, so-called {\gamma}-GeSe, is synthesized and clearly identified by complementary structural characterizations, including elemental analysis, electron diffraction, high-resolution transmission electron microscopy imaging, and polarized Raman spectroscopy. The electrical and optical measurements indicate that synthesized {\gamma}-GeSe exhibits high electrical conductivity of 3x10^5 S/m, which is comparable to those of other two-dimensional layered semimetallic crystals. Moreover, {\gamma}-GeSe can be directly grown on h-BN substrates, demonstrating a bottom-up approach for constructing vertical van der Waals heterostructures incorporating {\gamma}-GeSe. The newly identified crystal symmetry of {\gamma}-GeSe warrants further studies on various physical properties of {\gamma}-GeSe., Comment: 24 pages, 5 figures

The properties of metal-semiconductor junctions are often unpredictable because of non-ideal interfacial structures, such as interfacial defects or chemical reactions introduced at junctions. Black phosphorus (BP), an elemental two-dimensional (2D) semiconducting crystal, possesses the puckered atomic structure with high chemical reactivity, and the establishment of a realistic atomic-scale picture of BP's interface toward metallic contact has remained elusive. Here we examine the interfacial structures and properties of physically-deposited metals of various kinds on BP. We find that Au, Ag, and Bi form single-crystalline films with (110) orientation through guided van der Waals epitaxy. Transmission electron microscopy and X-ray photoelectron spectroscopy confirm that atomically sharp van der Waals metal-BP interfaces forms with exceptional rotational alignment. Under a weak metal-BP interaction regime, the BP's puckered structure play an essential role in the adatom assembly process and can lead to the formation of a single crystal, which is supported by our theoretical analysis and calculations. The experimental survey also demonstrates that the BP-metal junctions can exhibit various types of interfacial structures depending on metals, such as the formation of polycrystalline microstructure or metal phosphides. This study provides a guideline for obtaining a realistic view on metal-2D semiconductor interfacial structures, especially for atomically puckered 2D crystals., Comment: 27 pages, 5 figures

Phosphorene, a monolayer of black phosphorus (BP), is an elemental two-dimensional material with interesting physical properties, such as high charge carrier mobility and exotic anisotropic in-plane properties. To fundamentally understand these various physical properties, it is critically important to conduct an atomic-scale structural investigation of phosphorene, particularly regarding various defects and preferred edge configurations. However, it has been challenging to investigate mono- and few-layer phosphorene because of technical difficulties arising in the preparation of a high-quality sample and damages induced during the characterization process. Here, we successfully fabricate high-quality monolayer phosphorene using a controlled thinning process with transmission electron microscopy, and subsequently perform atomic-resolution imaging. Graphene protection suppresses the e-beam-induced damage to multi-layer BP and one-side graphene protection facilitates the layer-by-layer thinning of the samples, rendering high-quality monolayer and bilayer regions. We also observe the formation of atomic-scale crystalline edges predominantly aligned along the zigzag and (101) terminations, which is originated from edge kinetics under e-beam-induced sputtering process. Our study demonstrates a new method to image and precisely manipulate the thickness and edge configurations of air-sensitive two-dimensional materials., Comment: 21 pages, 5 figures