Zilevu Daniel, Miller Kennedi M, Arrykova Naira, Locke Autumn B, Creutz Sidney E
Department of Chemistry, Mississippi State University, Mississippi State, MS 39759, USA.
Nanoscale. 2024 Sep 19;16(36):17126-17140. doi: 10.1039/d4nr02412e.
Chalcogenide perovskites, especially BaZrS and its related alloys, present a promising alternative to lead halide perovskites for optoelectronic applications due to their reduced toxicity and enhanced stability. However, the elevated temperature conditions necessary for preparing these materials create a barrier to their incorporation into thin-film devices. In this work, we report a solution-phase synthesis of colloidal nanoparticles of titanium-alloyed BaZrS, Ba(ZrTi)S. The titanium alloying was achieved using reactive amide precursors in oleylamine solvent, and ,'-diethylthiourea served as the sulfur source. Our methodology allowed for the synthesis of Ba(ZrTi)S nanomaterials at temperatures at or below 300 °C. The resulting nanocrystals exhibited a phase transition from an orthorhombic distorted perovskite structure to a hexagonal non-perovskite phase as the titanium content surpassed = 0.11, accompanied by a morphological evolution from nanoplatelets to nanohexagons and ultimately nanobars. The UV-Vis-NIR absorption spectra of Ba(ZrTi)S nanoparticles exhibit increasing low-energy absorption as the titanium content is increased. This work contributes to the development of low-temperature synthesis methods for Ba(ZrTi)S nanomaterials, offering new potential pathways for materials design of chalcogenide perovskites for advanced optoelectronic applications.
硫族钙钛矿，尤其是BaZrS及其相关合金，由于其毒性降低和稳定性增强，在光电子应用中是卤化铅钙钛矿的一个有前途的替代品。然而，制备这些材料所需的高温条件阻碍了它们被纳入薄膜器件。在这项工作中，我们报道了一种溶液相合成钛合金化的BaZrS（Ba(ZrTi)S）胶体纳米颗粒的方法。钛合金化是通过在油胺溶剂中使用反应性酰胺前体实现的，并且'-二乙硫脲用作硫源。我们的方法允许在300°C或更低的温度下合成Ba(ZrTi)S纳米材料。当钛含量超过=0.11时，所得纳米晶体表现出从正交畸变钙钛矿结构到六方非钙钛矿相的相变，伴随着从纳米片到纳米六边形并最终到纳米棒的形态演变。随着钛含量的增加，Ba(ZrTi)S纳米颗粒的紫外-可见-近红外吸收光谱显示出低能量吸收增加。这项工作有助于开发Ba(ZrTi)S纳米材料的低温合成方法，为用于先进光电子应用的硫族钙钛矿材料设计提供了新的潜在途径。
