Zinc oxide (ZnO) is one of the most versatile semiconductor materials with multifarious potential applications. Easily accessible alkylzinc alkoxides have been widely exploited as single-source precursors of ZnO-based nanomaterials but their multi-step decomposition pathways have not been understood in detail. Herein, the formation mechanism of ZnO nanocrystals via solid-state thermal decomposition of a model pre-organised alkylzinc alkoxide precursor, i.e. [tBuZn(μ₃-OtBu)]₄, is elucidated using in situ valence-to-core X-ray emission (v2c-XES) and high energy resolution off-resonant spectroscopy (HEROS) in conjunction with theoretical calculations. Combination of in situ spectroscopic measurements and theoretical simulations indicates that the precursor structural evolution is initiated by the homolytic cleavage of the R–Zn bond, which leads to the formation of a transient radical ([˙Zn(μ₃-OR)][RZn(μ₃-OR)]₃) species, which is responsible for the initial decomposition process. The ensuing multistep transformations involve the formation of intermediate radical zinc oxo-alkoxide clusters with gapless electronic states. Hitherto, the formation of clusters of this type has not been considered either as intermediate structures en route to a semiconductor ZnO phase or as potential species accounting for various defect states of ZnO NCs, particularly the singly charged oxygen vacancy, V_o⁺.

中文翻译：

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预组织的烷氧基锌热转变为氧化锌纳米晶体过程中的隐藏无隙态†

氧化锌（ZnO）是用途最广泛的最通用的半导体材料之一。易获得的烷基锌醇盐已被广泛用作基于ZnO的纳米材料的单源前体，但尚未详细了解其多步分解途径。在此，氧化锌的纳米晶体的形成机理经由一个有组织的预模型烷基锌的醇盐前体的固态热分解，即[吨BuZn（μ ₃ -O吨丁基）] ₄，使用阐明原位化合价X射线发射（v2c-XES）和高能分辨率非共振光谱（HEROS），并结合理论计算。的组合原位光谱测量和理论模拟表明，该前体结构演变由RZN键的均裂，发起这导致瞬时自由基（[ZN（μ形成₃ -OR）] [RZN （μ ₃ - OR）] ₃）物种，它负责初始分解过程。随后的多步转化涉及形成具有无间隙电子态的中间自由基氧羰基-烷氧基锌簇。迄今为止，这种簇的形成既不被认为是通向半导体ZnO相的中间结构，也不被认为是解决ZnO NCs各种缺陷状态的潜在物种，特别是单电荷氧空位V _o ⁺。