On the Origin of Metallicity and Stability of the Metastable Phase in Chemically Exfoliated MoS2_2

Chemical exfoliation of MoS$_2$ via Li-intercalation route has led to many desirable properties and spectacular applications due to the presence of a metastable state in addition to the stable H phase. However, the nature of the specific metastable phase formed, and its basic charge conduction properties have remained controversial. Using spatially resolved Raman spectroscopy (~1 micrometer resolution) and photoelectron spectroscopy (~120 nm resolution), we probe such chemically exfoliated MoS$_2$ samples in comparison to a mechanically exfoliated H phase sample and confirm that the dominant metastable state formed by this approach is a distorted T' state with a small semiconducting gap. Investigating two such samples with different extents of Li residues present, we establish that Li+ ions, not only help to exfoliate MoS$_2$ into few layer samples, but also contribute to enhancing the relative stability of the metastable state as well as dope the system with electrons, giving rise to a lightly doped small bandgap system with the T' structure, responsible for its spectacular properties.Comment: 34 pages, Main manuscript + Supplementary Materia

Understanding the Chemical Nature of the Buried Nanostructures in Low Thermal Conductive Sb-Doped SnTe by Variable-Energy Photoelectron Spectroscopy

Nanoprecipitates embedded in a matrix of thermoelectric materials decrease the lattice thermal conductivity significantly by extensive heat carrying phonon scattering. Recently, two-dimensional layered intergrowth nanostructures of Sn$_m$Sb$_{2n}$Te$_{3n+m}$ embedded in SnTe matrix have provided record low lattice thermal conductivity in SnTe, but an understanding of the chemical nature of these layered nanostructures is still not clear. Herein, we studied the chemical nature of the intergrowth nanostructures of a series Sb-doped SnTe by variable-energy X-ray photoelectron spectroscopy at synchrotron, which is well known to probe buried interfaces and embedded nanostructures. The primary oxidation states of Sb, Sn, and Te in these intergrowth structures are found to be in +3, +2, and −2, respectively, which is expected from the composition. However, both the Sn and Sb are found to be slightly oxidized in the surface. From the intensity variation with photon energy, we have found a thin layer of SnO$_2$ (∼4.5 nm) on the sample surfaces and the thickness decreases with Sb doping. Te is also found in 0 oxidation states, which corroborates with the variation of Sn vacancies with Sb doping. The valence band features near the edge do not change significantly with Sb doping. This understanding of the chemical nature of low lattice thermal conductive Sb-doped SnTe will help further to design the thermoelectric materials with their surface phenomenon

Conducting LaVO3/SrTiO3 Interface: Is Cationic Stoichiometry Mandatory?

The origin of the conductivity at the interface of two insulating perovskite oxides is a matter of intensive studies. The conductivity generated at the interface of insulating LaVO3 (LVO) and SrTiO3 (STO) is explained in terms of polar catastrophe. Here, the authors grown LVO films on (001) TiO2-terminated STO substrate employing pulsed laser deposition technique and demonstrate a transition from conducting to insulating interface by changing the La-stoichiometry by only 1%, whereby such transition takes place for La-deficient films. The effect of cation (non)stoichiometry of LVO film on both carrier density and mobility is studied and compared with previously reported LaAlO3-STO interface. This observation suggests a revisit to the explanation of possible origin of such conductivity beyond the polar catastrophe scenario and can be instrumental in search for novel conducting interfaces

Local structural evolution in the anionic solid solution ZnSex_xS1−x_{1−x}

The century-old Vegard‘s law has been remarkably accurate in describing the evolution of the lattice parameters of almost all solid solutions. Contractions or expansions of lattice parameters of such systems depend on the size of the guest atom being smaller or larger than the host atom it replaces to form the solid solution. This has given rise to the concept of “chemical pressure” in analogy to the physical pressure. We have investigated using EXAFS the evolution of the local structure in terms of atom-pair distances extending up to the third-nearest neighbors in the family of compounds, ZnSe$_x$S$_{1−x}$ as an example of an anionic solid solution, in contrast to all previous studies focusing on cationic solid solutions. Our results establish several common features between these two types of solid solutions, while strongly suggesting that the concept of a chemical pressure is inaccurate and misleading. Most interestingly, we also find a qualitative difference between the cationic solid solutions, reported earlier, and the anionic solid solution