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.

X-ray diffraction and STM study of reactive surfaces under electrochemical control: Cl and I on Cu(100).

The surface structure of Cu(100) modified by chloride and iodide has been studied in an electrochemical environment by means of in-situ scanning tunneling microscopy in combination with in-situ surface X-ray diffraction with a particular focus on adsorbate and potential dependent surface relaxation phenomena. For positive potentials close to the on-set of the copper dissolution reaction, the X-ray data disclose an extraordinarily large Cu-Cl bond length of 2.61 A for the c(2 x 2)-Cl phase. This finding points to a largely ionic character of the Cu-Cl interaction at the Cu(100) surface, with chloride particles likely to retain their full charge upon adsorption. Together with the positive surface charging at these high potentials, this ionic Cu-Cl bond drives the observed 2.2% outward relaxation between the first two copper layers. These results indicate that the bond between the first and the second copper layer is significantly weakened which appears as the crucial prerequisite for the high surface mobility of copper-chloride species under electrochemical annealing conditions at these high potentials. With 2.51 A the Cu-I bond is 4% shorter than the Cu-Cl bond implying that the nature of the Cu-I bond is mainly covalent. Accordingly, we observe a significant inward relaxation of the top Cu layers upon substituting chloride by iodide at the same electrode potential, which suggests that the iodide adsorption involves charge transfer from the halide to the copper substrate.