Materials Science Institute and Chemistry Department, University of Oregon , Eugene, Oregon 97403, United States.
Los Alamos National Laboratory , Los Alamos, New Mexico 87544, United States.
ACS Nano. 2015 Aug 25;9(8):8440-8. doi: 10.1021/acsnano.5b03361. Epub 2015 Jul 21.
A series of ferecrystalline compounds ([SnSe]1+δ)1(VSe2)1 with varying Sn/V ratios were synthesized using the modulated elemental reactant technique. Temperature-dependent specific heat data reveal a phase transition at 102 K, where the heat capacity changes abruptly. An abrupt increase in electrical resistivity occurs at the same temperature, correlated with an abrupt increase in the Hall coefficient. Combined with the magnitude and nature of the specific heat discontinuity, this suggests that the transition is similar to the charge density wave transitions in transition metal dichalcogenides. An ordered intergrowth was formed over a surprisingly wide compositional range of Sn/V ratios of 0.89 ≤ 1 + δ ≤ 1.37. X-ray diffraction and transmission electron microscopy reveal the formation of various volume defects in the compounds in response to the nonstoichiometry. The electrical resistivity and Hall coefficient data of samples with different Sn/V ratios show systematic variation in the carrier concentration with the Sn/V ratio. There is no significant change in the onset temperature of the charge density wave transition, only a variation in the carrier densities before and after the transition. Given the sensitivity of the charge density wave transitions of transition metal dichalcogenides to variations in composition, it is very surprising that the charge density wave transition observed at 102 K for ([SnSe]1.15)1(VSe2)1 is barely influenced by the nonstoichiometry and structural defects. This might be a consequence of the two-dimensional nature of the structurally independent VSe2 layers.
采用调制元素反应物技术合成了一系列具有不同 Sn/V 比的费结晶化合物([SnSe]1+δ)1(VSe2)1。温度依赖的比热数据显示在 102 K 处发生相变,热容在此处突然变化。在相同温度下,电阻率突然增加,霍尔系数也随之突然增加。这与比热不连续的幅度和性质相结合,表明该转变类似于过渡金属二卤化物中的电荷密度波转变。在 Sn/V 比为 0.89≤1+δ≤1.37 的相当宽的组成范围内形成了有序的共生长。X 射线衍射和透射电子显微镜揭示了化合物中形成了各种体积缺陷,以应对非化学计量比。不同 Sn/V 比的样品的电阻率和霍尔系数数据表明,载流子浓度随 Sn/V 比的系统变化。电荷密度波转变的起始温度没有明显变化,只是在转变前后载流子密度发生了变化。考虑到过渡金属二卤化物中电荷密度波转变对组成变化的敏感性,非常令人惊讶的是,在 102 K 下观察到的([SnSe]1.15)1(VSe2)1 的电荷密度波转变几乎不受非化学计量比和结构缺陷的影响。这可能是结构独立的 VSe2 层的二维性质的结果。