Volatile and Thermally Stable Polymeric Tin Trifluoroacetates
journal contributionposted on 08.01.2020, 21:13 by Goran Bačić, Conor D. Rankine, Jason D. Masuda, Derek A. Wann, Seán T. Barry
Tin trifluoroacetates are effective vapor phase single-source precursors for F-doped SnO2, but their structures have been poorly understood for decades. Here we undertook a comprehensive structural analysis of these compounds in both the solid and gas phases through a combined single-crystal X-ray crystallography, gas phase electron diffraction, and density functional theory investigation. Tin(II) bis(trifluoroacetate) (1) thermally decomposes into a 1:1 mixture of 1 and ditin(II) μ-oxybis(μ-trifluoroacetate) (2) during sublimation, which then polymerize into hexatin(II)-di-μ3-oxyoctakis(μ-trifluoroacetate) (3) upon solidification. Reversible depolymerization occurred readily upon heating, making 3 a useful vapor phase precursor itself. Tin(IV) tetrakis(trifluoroacetate) (5) was also found to be polymeric in the solid state, but it evaporated as a monomer over 130 °C lower than 3. This counterintuitive improvement in volatility by polymerization was possibly due to the large entropy change during sublimation, which offers a strategic new design feature for vapor phase deposition precursors.
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design featuregas phase electron diffractionReversible depolymerizationcounterintuitive improvementsublimationgas phasesThermally Stable Polymeric Tin Trifluoroacetates Tin trifluoroacetatessingle-crystal X-ray crystallographyentropy changevapor phase precursortheory investigationF-doped SnO 2vapor phase deposition precursorsvapor phase single-source precursors