Shape-Controlled Synthesis of Colloidal Nanorods and Nanoparticles of Barium Titanium Sulfide
Shape-Controlled Synthesis of Colloidal Nanorods and Nanoparticles of Barium Titanium Sulfide
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DOI：
10.1021/acs.chemmater.1c01193
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发表时间：
2021-07
影响因子：
8.6
通讯作者：
Daniel Zilevu;Sidney E. Creutz
中科院分区：
文献类型：
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作者：
Daniel Zilevu;Sidney E. Creutz
三元过渡金属硫化物的通式为(AE)MIVS3(AE=Ca，Sr，Ba；M=Zr，Ti，Hf)，由于它们的光学、电学和热学性质，最近引起了越来越多的关注，可能的应用包括光伏吸收和近红外探测器。然而，获得这些材料的合成路线，特别是作为纳米材料，仍然有限。在这里，我们报道了通过使用活性金属酰胺前驱体，在低至280°C的温度下，采用基于溶液的湿化学方法合成了胶体纳米材料BaTiS3。我们证明，通过选择一种合成方法(加热或热注射)以及通过调节反应温度和浓度，可以制备出典型的长宽比约为8：1(50 nm长，6 nm宽)的纳米颗粒或纳米棒，并对纳米晶的尺寸和形状进行综合控制。结构数据(粉末X射线衍射)显示复合晶体的特征与偏离理想化学计量比有关。BaTiS3纳米棒表现出强烈的可调近红外吸收(∼0。8 eV)，其能量与纳米棒结构和化学计量比有关。这些结果为利用溶液路线合成这类材料的纳米晶提供了原理证明。
Ternary transition-metal sulfides with the general formula (AE)MIVS3(AE = Ca, Sr, Ba;M= Zr, Ti, Hf) have recently drawn increasing attention because of their optical, electronic, and thermal properties, with possible applications including photovoltaic absorbers and NIR detectors. However, synthetic routes to these materials, especially as nanomaterials, remain limited. Here, we report the synthesis of BaTiS3as colloidal nanomaterials using a solution-based, wet-chemical approach at temperatures as low as 280 °C through the use of reactive metal amide precursors. We demonstrate that nanoparticles or nanorods with typical aspect ratios of approximately 8:1 (50 nm length, 6 nm width) can be prepared, with synthetic control over the nanocrystal size and shape afforded through the choice of a synthetic method (heat-up or hot injection) and through the modulation of the reaction temperature and concentration. Structural data (powder X-ray diffraction) show the hallmarks of a composite crystal correlated with deviations from the ideal stoichiometry. The BaTiS3nanorods show a strong and tunable NIR absorbance (∼0. 8 eV), whose energy is correlated to the nanorod structure and stoichiometry. These results provide a proof-of-principle for the synthesis of nanocrystals of this class of materials using solution routes.