Centre for Materials Science and Nanotechnology (SMN), Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, Oslo N-0315, Norway.
Nat Commun. 2016 Nov 23;7:13578. doi: 10.1038/ncomms13578.
Thin films of stable metal-organic frameworks (MOFs) such as UiO-66 have enormous application potential, for instance in microelectronics. However, all-gas-phase deposition techniques are currently not available for such MOFs. We here report on thin-film deposition of the thermally and chemically stable UiO-66 in an all-gas-phase process by the aid of atomic layer deposition (ALD). Sequential reactions of ZrCl and 1,4-benzenedicarboxylic acid produce amorphous organic-inorganic hybrid films that are subsequently crystallized to the UiO-66 structure by treatment in acetic acid vapour. We also introduce a new approach to control the stoichiometry between metal clusters and organic linkers by modulation of the ALD growth with additional acetic acid pulses. An all-gas-phase synthesis technique for UiO-66 could enable implementations in microelectronics that are not compatible with solvothermal synthesis. Since this technique is ALD-based, it could also give enhanced thickness control and the possibility to coat irregular substrates with high aspect ratios.
热稳定和化学稳定的 UiO-66 金属有机骨架（MOFs）薄膜在微电子学等领域具有巨大的应用潜力。然而，目前还没有适用于此类 MOFs 的全气相沉积技术。本研究通过原子层沉积（ALD）报道了在全气相工艺中沉积热稳定和化学稳定的 UiO-66 薄膜。ZrCl 和 1,4-苯二甲酸的顺序反应生成无定形的有机-无机杂化薄膜，然后通过在醋酸蒸气中处理将其晶化为 UiO-66 结构。我们还引入了一种新方法，通过用额外的醋酸脉冲调制 ALD 生长来控制金属簇和有机配体之间的化学计量比。UiO-66 的全气相合成技术可以在与溶剂热合成不兼容的微电子学中实现。由于该技术基于 ALD，因此它还可以提供更好的厚度控制，并有可能在具有高纵横比的不规则衬底上进行涂覆。
