Atamtürk Ufuk, Brune Veronika, Mishra Shashank, Mathur Sanjay
Institute of Inorganic Chemistry, University of Cologne, Greinstraße 6, 50939 Cologne, Germany.
Institut de Recherches sur la Catalyse et l'Environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1, CNRS, UMR 5256, 2 Avenue Albert Einstein, 69626 Villeurbanne, France.
Molecules. 2021 Sep 3;26(17):5367. doi: 10.3390/molecules26175367.
Extraordinary low-temperature vapor-phase synthesis of SnS thin films from single molecular precursors is attractive over conventional high-temperature solid-state methods. Molecular-level processing of functional materials is accompanied by several intrinsic advantages such as precise control over stoichiometry, phase selective synthesis, and uniform substrate coverage. We report here on the synthesis of a new heteroleptic molecular precursor containing (i) a thiolate ligand forming a direct Sn-S bond, and (ii) a chelating O^N^N-donor ligand introducing a "launch vehicle"-effect into the synthesized compound, thus remarkably increasing its volatility. The newly synthesized tin compound [Sn(SBu)()] was characterized by single-crystal X-ray diffraction analysis that verified the desired Sn:S ratio in the molecule, which was demonstrated in the direct conversion of the molecular complex into SnS thin films. The multi-nuclei (H, C, F, and Sn) and variable-temperature 1D and 2D NMR studies indicate retention of the overall solid-state structure of in the solution and suggest the presence of a dynamic conformational equilibrium. The fragmentation behavior of was analyzed by mass spectrometry and compared with those of homoleptic tin tertiary butyl thiolates [Sn(SBu)] and [Sn(SBu)]. The precursor was then used to deposit SnS thin films on different substrates (FTO, Mo-coated soda-lime glass) by CVD and film growth rates at different temperatures (300-450 °C) and times (15-60 min), film thickness, crystalline quality, and surface morphology were investigated.
通过单分子前驱体进行的超低温气相合成硫化锡薄膜，相较于传统的高温固态方法具有吸引力。功能材料的分子级加工具有若干内在优势，例如对化学计量比的精确控制、相选择性合成以及均匀的基底覆盖。我们在此报告一种新型杂配分子前驱体的合成，该前驱体包含：（i）形成直接锡 - 硫键的硫醇盐配体，以及（ii）向合成化合物引入“运载效应”从而显著提高其挥发性的螯合O^N^N供体配体。新合成的锡化合物[Sn(SBu)()]通过单晶X射线衍射分析进行表征，该分析验证了分子中所需的锡与硫的比例，这在分子络合物直接转化为硫化锡薄膜中得到了证明。多核（氢、碳、氟和锡）以及变温一维和二维核磁共振研究表明，在溶液中保留了的整体固态结构，并表明存在动态构象平衡。通过质谱分析了的碎片化行为，并与均配叔丁基硫醇锡[Sn(SBu)]和[Sn(SBu)]的碎片化行为进行了比较。然后使用该前驱体通过化学气相沉积在不同基底（FTO、涂钼钠钙玻璃）上沉积硫化锡薄膜，并研究了不同温度（300 - 450°C）和时间（15 - 60分钟）下的薄膜生长速率、薄膜厚度、晶体质量和表面形态。
