Journal of the American Chemical Society, Vol.137, No.14, 4831-4839, 2015
Structure, Stability, and Properties of the Intergrowth Compounds ([SnSe](1+delta))(m)(NbSe2)(n), where m = n=1-20
Intergrowth compounds of ([SnSe](1+delta))(m)(NbSe2)(n), where 1 <= m = n <= 20, with the same atomic composition but different c-axis lattice parameters and number of interfaces per volume were synthesized using the modulated elemental reactant technique. A c-axis lattice parameter change of 1.217(6) nm as a function of one unit of m = n was observed. In-plane X-ray diffraction shows an increase in distortion of the rock salt layer as a function of m and a broadening of the NbSe2 reflections as n increases, indicating the presence of different coordination environments for Nb (trigonal prismatic and octahedral) and smaller crystallite size, which were confirmed via scanning transmission electron microscopy investigations. The electrical resistivities of all 12 compounds exhibit metallic temperature dependence and are similar in magnitude as would be expected for isocompositional compounds. Carrier concentration and mobility of the compounds vary within a narrow range of 2-6 x 10(21) cm(3) and 2-6 cm(-2) V-1 s(-1), respectively. Even at a thickness of 12 nm for the SnSe and NbSe2 blocks, the properties of the intergrowth compounds cannot be explained as composite behavior, due to significant charge transfer between them. Upon being annealed at 500 degrees C, the higher order m = n compounds were found to convert to the thermodynamically stable phase, the (1,1) compound. This suggests that the capacitive energy of the interfaces stabilizes these intergrowth compounds.