No abstract

A modification of the modulated elemental reactants synthetic technique was developed and used to synthesize eleven members of the [(SnSe) 1.15 ] m (TaSe 2 ) n family of compounds, with m and n equal to integer values between 1 and 6. Each of the intergrowth compounds contained highly oriented intergrowths of SnSe bilayers and TaSe 2 monolayers with abrupt interfaces perpendicular to the c-axis. The c-lattice parameter increased 0.579(1) nm per SnSe bilayer and 0.649(1) nm per Se−Ta−Se trilayer (TaSe 2 ) as m and n were varied. ab-plane X-ray diffraction patterns and transmission electron microscope images revealed a square in-plane structure of the SnSe constituent, a hexagonal in-plane structure for the TaSe 2 constituent, and rotational disorder between the constituent layers. Temperature dependent electrical resistivity, measured on several specimens, revealed metallic behavior, and a simple model is presented to explain the differences in resistivity as a function of m and n.

The compounds, ([SnSe]1.15)1(VSe2)n with n = 1, 2, 3, and 4, were prepared using designed precursors in order to investigate the influence of the thickness of the VSe2 constituent on the charge density wave transition. The structure of each of the compounds was determined using X-ray diffraction and scanning transmission electron microscopy. The charge density wave transition observed in the resistivity of ([SnSe]1.15)1(VSe2)1 was confirmed. The electrical properties of the n = 2 and 3 compounds are distinctly different. The magnitude of the resistivity change at the transition temperature is dramatically lowered and the temperature of the resistivity minimum systematically increases from 118 K (n = 1) to 172 K (n = 3). For n = 1, this temperature correlates with the onset of the charge density wave transition. The Hall-coefficient changes sign when n is greater than 1, and the temperature dependence of the Hall coefficient of the n = 2 and 3 compounds is very similar to the bulk, slowly decreasing as the temperature is decreased, while for the n = 1 compound the Hall coefficient increases dramatically starting at the onset of the charge density wave. The transport properties suggest an abrupt change in electronic properties on increasing the thickness of the VSe2 layer beyond a single layer.

The synthesis and characterization of a new layered compound with the composition (PbSe)1·16TiSe2 in thin-film form is reported in this study. The structure of the new compound was characterized by specular and in-plane synchrotron x-ray diffraction studies, which indicate that the compound can be described as a layered intergrowth of PbSe and TiSe2 in which the individual constituents are precisely layered yet rotationally (turbostratically) disordered with an average in-plane domain size in the order of 10 nm. In contrast to crystalline (PbSe)1·16(TiSe2)2 prepared by solid-state reaction at high temperature, the electrical resistivity in the range 20–300 K is nearly temperature independent. The Seebeck coefficient at room temperature was measured to be S = −66(1) μV/K at the carrier concentration of n = 2·1(5) × 1021 cm−3, indicating behavior characteristic of a heavily doped semiconductor. The electrical transport properties for the (PbSe)1·16TiSe2 compound are compared and contrasted to those of other misfi t-layered and turbostratically disordered (MX)1+δ(TX2)n compounds.

Four compounds [(SnSe)1.15] m (VSe2)1, where m = 1–4, were synthesized to explore the effect of increasing the distance between Se–V–Se dichalcogenide layers on electrical transport properties. These kinetically stable compounds were prepared using designed precursors that contained a repeating pattern of elemental layers with the nanoarchitecture of the desired product. XRD and STEM data revealed that the precursors self-assembled into the desired compounds containing a Se–V–Se dichalcogenide layer precisely separated by a SnSe layer. The 00l diffraction data are used to determine the position of the Sn, Se, and V planes along the c-axis, confirming that the average structure is similar to that observed in the STEM images, and the resulting data agrees well with results obtained from calculations based on density functional theory and a semiempirical description of van der Waals interactions. The in-plane diffraction data contains reflections that can be indexed as hk0 reflections coming from the two independent constituents. The SnSe layers diffract independently from one another and are distorted from the bulk structure to lower the surface free energy. All of the samples showed metallic-like behavior in temperature-dependent resistivity between room temperature and about 150 K. The electrical resistivity systematically increases as m increases. Below 150 K the transport data strongly indicates a charge density wave transition whose onset temperature systematically increases as m increases. This suggests increasing quasi-two-dimensional behavior as increasingly thick layers of SnSe separate the Se–V–Se layers. This is supported by electronic structure calculations.