A careful engineering of the central metal coordination spheres provides adducts with excellent properties for application as precursors in vapor phase and solution processes. The family of precursors under study concerns the fluorinated metal-organic β-diketonates of alkaline, alkaline-earth and rare-earth metals adducted with a polyether, with general formula M(hfa)n·L (M = Ca, Na, Y, Yb, Er, Tm; Hhfa = 1,1,1,5,5,5 hexafluoroacetylacetone, L = diglyme or tetraglyme). Mass transport properties, such as volatility and thermal stability, of these adducts have been deeply analyzed through thermogravimetric analysis and differential scanning calorimetric measurements. These properties are rationalized in relation to the metal coordination sphere in the precursors and their applications. In particular, the precursors under focus have been applied to metal organic chemical vapor deposition and a combined sol–gel/spin-coating approach. Both methods allow us to obtain selectively and reproducibly CaF2 and NaYF4 phases with several combinations of lanthanide doping ions, using a proper mixture of fluorinated precursors. A careful optimization of both synthetic strategies is the key point for the production of different lanthanide-doped binary and multicomponent fluoride films, i.e., CaF2:Yb3+,Er3+; CaF2:Yb3+,Tm3+; CaF2:Yb3+,Er3+,Tm3+ and NaYF4:Yb3+,Er3+; NaYF4:Yb3+,Tm3+, with suitable morphologies, compositions and crystalline structures. The films show very promising upconversion properties, thus pointing to their appealing applications in photovoltaic systems and white light emission devices.

中文翻译：

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能量转换系统：金属前体的分子结构工程及其在气相和溶液路线中的应用

中心金属配位球的精心设计为加合物提供了优异的性能，可用作气相和溶液过程中的前体。正在研究的前体家族涉及碱金属、碱土金属和稀土金属与聚醚加成的氟化金属-有机 β-二酮酸盐，通式为 M(hfa)n·L (M = Ca, Na, Y, Yb、Er、Tm；Hhfa = 1,1,1,5,5,5 六氟乙酰丙酮，L = 二甘醇二甲醚或四甘醇二甲醚）。已经通过热重分析和差示扫描量热测量深入分析了这些加合物的传质特性，例如挥发性和热稳定性。这些性质与前体中的金属配位球及其应用有关。特别是，重点关注的前体已应用于金属有机化学气相沉积和溶胶-凝胶/旋涂组合方法。这两种方法都使我们能够使用氟化前体的适当混合物，通过几种镧系元素掺杂离子的组合，选择性和可重复地获得 CaF2 和 NaYF4 相。两种合成策略的仔细优化是生产不同镧系元素掺杂的二元和多组分氟化物薄膜的关键点，即 CaF2:Yb3+、Er3+；CaF2:Yb3+,Tm3+; CaF2:Yb3+,Er3+,Tm3+ 和 NaYF4:Yb3+,Er3+；NaYF4:Yb3+,Tm3+，具有合适的形态、成分和晶体结构。这些薄膜显示出非常有前途的上转换特性，因此表明它们在光伏系统和白光发射装置中具有吸引力的应用。