Direct characterization of intrinsic defects in monolayer ReSe2 on graphene.

Understanding the characteristics of intrinsic defects in crystals is of great interest in many fields, from fundamental physics to applied materials science. Combined investigations of scanning tunneling microscopy/spectroscopy (STM/S) and density functional theory (DFT) are conducted to understand the nature of Se vacancy defects in monolayer (ML) ReSe2 grown on a graphene substrate. Among four possible Se vacancy sites, we identify the Se4 vacancy close to the Re layer by registry between STM topography and DFT simulated images. The Se4 vacancy is also thermodynamically favored in formation energy calculations, supporting its common observation via STM. dI/dV spectroscopy shows that the Se4 vacancy has a defect state at around -1.0 V, near the valence band maximum (EVBM). DOS calculations done for all four Se vacancies indicate that only the Se4 vacancy presents such a defect state near EVBM, confirming experimental observations. Our work provides valuable insights into the behavior of ML ReSe2/graphene heterojunctions containing naturally occurring Se vacancies, which may have strong implications in electronic device applications.

Controlling Spin-Orbit Coupling to Tailor Type-II Dirac Bands.

NiTe2, a type-II Dirac semimetal with a strongly tilted Dirac band, has been explored extensively to understand its intriguing topological properties. Here, using density functional theory calculations, we report that the strength of the spin-orbit coupling (SOC) in NiTe2 can be tuned by Se substitution. This results in negative shifts of the bulk Dirac point (BDP) while preserving the type-II Dirac band. Indeed, combined studies using scanning tunneling spectroscopy and angle-resolved photoemission spectroscopy confirm that the BDP in the NiTe2-xSex alloy moves from +0.1 eV (NiTe2) to -0.3 eV (NiTeSe) depending on the Se concentrations, indicating the effective tunability of type-II Dirac Fermions. Our results demonstrate an approach to tailor the type-II Dirac band in NiTe2 by controlling the SOC strength via chalcogen substitution. This approach can be applicable to different types of topological materials.

Novel polymorphic phase of two-dimensional VSe2: the 1T' structure and its lattice dynamics.

Polymorphisms allowing multiple structural phases are among the most fascinating properties of transition metal dichalcogenides (TMDs). Herein, the polymorphic 1T' phase and its lattice dynamics for bilayer VSe2 grown on epitaxial bilayer graphene are investigated via low temperature scanning tunneling microscopy (STM). The 1T' structure, mostly observed in group-6 TMDs, is unexpected in VSe2, which is a group-5 TMD. Emergence of the 1T' structure in bilayer VSe2 suggests the important roles of interface and layer configurations, providing new possibilities regarding the polymorphism of TMDs. Detailed topographical analysis elucidates the microscopic nature of the 1T' structure, confirming that Se-like and V-like surfaces can be resolved depending on the polarity of the sample bias. In addition, bilayer VSe2 can transit from a static state of the 1T' phase to a dynamic state consisting of lattice vibrations, triggered by tunneling current from the STM tip. Topography also shows hysteretic behavior during the static-dynamic transition, which is attributed to latent energy existing between the two states. The observed lattice dynamics involve vibrational motion of the Se atoms and the middle V atoms. Our observations will provide important information to establish in-depth understanding of the microscopic nature of 1T' structures and the polymorphism of two-dimensional TMDs.

Atomistic study of the alloying behavior of crystalline SnSe1-xSx.

Recently, layered chalcogenide alloys (LCAs) have been extensively investigated for use in various practical applications by selectively controlling the amount of foreign components. However, the alloying behavior of layered chalcogenides has been rarely explored at the atomistic level. Here, we study the microstructural evolution of SnSe1-xSx alloys on the atomic scale by combining scanning tunneling microscopy (STM) measurements with first-principles density functional theory (DFT) calculations. STM topographic images suggest that S atoms substituted in SnSe1-xSx are not randomly distributed, but tend to form local SnS clusters. The degree of S atom alloying was quantitatively estimated to be about 60% from STM images, indicating that homo-atoms (S-S) are a preferred arrangement over hetero-atoms (S-Se). Our DFT calculations further confirmed that the mixing energy of random SnSe1-xSx alloys showed positive behavior over the whole S composition range considered. This result suggests that SnSe1-xSx has a tendency toward local phase segregation into SnSe and SnS rather than random alloys. We expect our atomistic study on the alloying behavior to provide important insight for fabricating optimal SnSe1-xSx alloys with high thermoelectric properties.