Precursor Selection Strategies for Two-Dimensional Anisotropic Growth and Morphological Control of BaTiS3 Nanocrystals

V Mauritz and A Ziegler and L Klerner and J Englhard and KE Dehm and T Uhlein and K Gubanov and C Knüpfer and S Harder and RH Fink and B Meyer and RW Crisp, CHEMISTRY OF MATERIALS, 37, 6552-6561 (2025).

DOI: 10.1021/acs.chemmater.5c00956

Understanding and controlling crystal growth mechanisms are essential for advancing materials development for optoelectronic applications. By controlling the morphology of the material, ultrathin transistors, flexible devices, surface-sensitive sensors, and the charge density wave phenomenon become realizable. Here, we report a solution-based synthesis of BaTiS3 nanostructures using tetrakis(dimethylamido)titanium, N,N'-diethylthiourea, and either barium bis(trimethylsilyl)amide (BaN(SiMe3)22) or barium iodide (BaI2) in oleylamine. The choice of barium precursor critically influences the morphology and crystal phase of the target material: BaN(SiMe3)22 yields ellipsoids that evolve into nanorods, while BaI2 produces two-dimensional (2D) nanoribbons, both in a nonperovskite hexagonal phase. Density functional theory calculations reveal that iodide ions selectively block specific crystal facets during growth, driving the formation of anisotropic nanoribbons. In situ mass spectrometry was employed to analyze gaseous species during synthesis, providing insights into the distinct growth mechanisms driven by precursor chemistry. X-ray diffraction patterns of the nanoribbons display sharp, periodic low 2 theta reflections, indicative of superlattice formation, which can be tuned by varying ligand chain lengths, which enables formation of metamaterials and photonic crystals by precisely controlling the supercrystal periodicity. Establishing a robust synthetic method using widely available precursors and equipment is a key step forward in applying this material in advanced devices. This study highlights the role of precursor selection and surface chemistry in controlling the growth and assembly of BaTiS3 nanostructures, offering a pathway for designing advanced 2D materials for optoelectronic applications.

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