Butrymowicz-Kubiak A, Muzioł T M, Kaczmarek-Kędziera A, Jureddy C S, Maćkosz K, Utke I, Szymańska I B
Faculty of Chemistry, Nicolaus Copernicus University in Toruń, Gagarina 7, 87-100 Toruń, Poland.
Empa - Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Mechanics of Materials and Nanostructures, Feuerwerkerstrasse 39, CH - 3602 Thun, Switzerland.
Dalton Trans. 2024 Aug 13;53(32):13662-13677. doi: 10.1039/d4dt01287a.
We report the synthesis and characterization of new palladium(II) β-ketoesterate complexes [Pd(CHCOCHCOR)] with alkyl substituents R = Bu, Pr, Et. These compounds can have potential use in focused electron beam induced deposition (FEBID), which is a direct write method for the growth of structures at the nanoscale. However, it is still a major challenge to obtain deposits with a high metal content, and new precursor molecules are needed to overcome this. Single crystal X-ray diffraction, infrared spectroscopy, nuclear magnetic resonance spectroscopy, and density-functional theory calculations were used to confirm the compounds' composition and structure. Using thermal analysis and sublimation experiments, we investigate their thermal stability and volatility. These studies show that the palladium complexes sublimate over the range 348-353 K under 10 mbar pressure. The electron-induced decomposition of the complex molecules in the gas phase and their thin layers on silicon substrates were analysed using electron impact mass spectrometry (EI MS) and microscopy studies (SEM/EDX). They confirm that the precursor electron-induced fragmentation depends on the molecular structure. The obtained results reveal that [Pd(CHCOCHCOBu)] with -positioned -butyl groups may be a promising FEBID precursor, and we carried out preliminary deposition experiments using this compound.
我们报道了具有烷基取代基R = Bu、Pr、Et的新型钯（II）β-酮酸酯配合物[Pd(CHCOCHCOR)]的合成与表征。这些化合物在聚焦电子束诱导沉积（FEBID）中可能具有潜在应用，FEBID是一种用于在纳米尺度上生长结构的直接写入方法。然而，获得高金属含量的沉积物仍然是一个重大挑战，需要新的前驱体分子来克服这一问题。利用单晶X射线衍射、红外光谱、核磁共振光谱和密度泛函理论计算来确定化合物的组成和结构。通过热分析和升华实验，我们研究了它们的热稳定性和挥发性。这些研究表明，钯配合物在10毫巴压力下于348 - 353 K范围内升华。使用电子轰击质谱（EI MS）和显微镜研究（SEM/EDX）分析了气相中以及硅衬底上的配合物分子薄层的电子诱导分解。结果证实前驱体的电子诱导碎片化取决于分子结构。所得结果表明，具有对位丁基的[Pd(CHCOCHCOBu)]可能是一种有前景的FEBID前驱体，并且我们使用该化合物进行了初步沉积实验。
