Hefei National Laboratory for Physical Sciences at Microscale, University of Science & Technology of China, Hefei, 230026, P.R. China.
Nanoscale. 2011 Jun;3(6):2609-14. doi: 10.1039/c1nr10179j. Epub 2011 May 9.
Monodisperse 10-nm V(2)O(3) pseudocubes enclosed by {012} facets were successfully synthesized for the first time via a novel and facile solvothermal method, offering the first opportunity to elucidate the effect of finite-size and facet on the temperature-induced reversible metal-insulator transition (MIT) behavior of V(2)O(3). Very excitingly, the transition temperature of these V(2)O(3) pseudocubes drastically depressed from 133 K to 36 K and their corresponding hysteresis width highly narrowed from 17 K to 5 K, compared to the MIT behaviors of other irregular V(2)O(3) particles with average sizes of 10 nm, 20 nm, 40 nm, 170 nm and 2 μm. Notably, the size-related surface energy, grain boundary connectivity and volume expansion could be used to account for their strong size-dependent transition temperature and hysteresis width. Moreover, the improved grain boundary connectivity associated with well-defined {012} facets enabled these 10-nm V(2)O(3) pseudocubes to display a 10 times higher resistivity jump (at the order of 10(5)) and by nearly one-half smaller hysteresis width of 5 K than the irregular 10-nm V(2)O(3) particles with randomly exposed facets, directly evidencing the pronounced influence of facets on the MIT behavior. Briefly, the present work not only develops an effective strategy for synthesizing high-quality nanocrystals but also provides an excellent platform to investigate the size- and facet-dependent temperature-induced MIT behavior, enabling to design smart electrical switching nano-devices in the rapidly developing ultra-low temperature field.
首次通过一种新颖且简便的溶剂热法成功合成了具有 {012} 面的单分散 10nm V(2)O(3) 伪立方,这为阐明有限尺寸和晶面对 V(2)O(3) 的温度诱导可逆金属-绝缘体转变 (MIT) 行为的影响提供了首次机会。令人非常兴奋的是,与具有平均尺寸为 10nm、20nm、40nm、170nm 和 2μm 的其他不规则 V(2)O(3) 颗粒的 MIT 行为相比,这些 V(2)O(3) 伪立方的转变温度从 133K 急剧降低到 36K,其相应的滞后宽度从 17K 显著减小到 5K。值得注意的是,尺寸相关的表面能、晶界连通性和体积膨胀可以用来解释其强烈的尺寸依赖的转变温度和滞后宽度。此外,与定义明确的 {012} 面相关的改善的晶界连通性使这些 10nm V(2)O(3) 伪立方具有 10 倍更高的电阻率跃变(约为 10(5))和近一半更小的滞后宽度 5K,比具有随机暴露面的不规则 10nm V(2)O(3) 颗粒小近一半,直接证明了晶面对 MIT 行为的显著影响。简而言之,本工作不仅开发了一种合成高质量纳米晶体的有效策略,而且为研究尺寸和晶面对温度诱导 MIT 行为的影响提供了一个极好的平台,能够在快速发展的超低温度领域设计智能电开关纳米器件。