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   Kamp, Kendall R; Wang, Yiran; Poeppelmeier, Kenneth R (December 2023, Solid State Sciences)

   The design of both molecular and non-molecular solid materials with specific properties fundamentally relies on the controlled synthesis of crystals with desired functional groups, bonding motifs, polarity, chirality, and more. To this end, fluoride and oxide-fluoride anions have been utilized as basic building units (BBUs) in the synthesis of noncentrosymmetric racemic materials for their ability to create polar axes that facilitate the breaking of an inversion center as demonstrated in a series of compounds with [MF6]2- anions (M = Ti, Zr, Hf). Targeting an analog with a [TaOF5]2- anion, the phase space of (CuO, Ta2O5)/bpy/HF(aq)/H2O (bpy = 2,2′- bipyridine) was investigated and three new compounds with Cu-bpy cations and Ta-fluoride or Ta-oxyfluoride anions were synthesized: [Cu(bpy)2][TaF6], [Cu (bpy)2][Ta2OF10], and [Cu(bpy)F(H2O)2]2[TaF7]•H2O with the anions [TaF6]-, [Ta2OF10]2-, and [TaF7]2-, respectively. The formation of these anions was found to be a product of both the concentration of hydrofluoric acid in solution and the ratio of metal-oxide starting materials to ligand. This work contributes to the understanding of mixed anion formation in the solid state. 

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4. Spontaneous Ordering of Oxide-Oxide Epitaxial Vertically Aligned Nanocomposite Thin Films

   https://doi.org/10.1146/annurev-matsci-091719-112806  

   Sun, Xing; MacManus-Driscoll, Judith L.; Wang, Haiyan (July 2020, Annual Review of Materials Research)

   null (Ed.)

   The emerging field of self-assembled vertically aligned nanocomposite (VAN) thin films effectively enables strain, interface, and microstructure engineering as well as (multi)functional improvements in electric, magnetic, optical, and energy-related properties. Well-ordered or patterned microstructures not only empower VAN thin films with many new functionalities but also enable VAN thin films to be used in nanoscale devices. Comparative ordered devices formed via templating methods suffer from critical drawbacks of processing complexity and potential contamination. Therefore, VAN thin films with spontaneous ordering stand out and display many appealing features for next-generation technological devices, such as electronics, optoelectronics, ultrahigh-density memory systems, photonics, and 3D microbatteries. The spontaneous ordering described in this review contains ordered/patterned structures in both in-plane and out-of-plane directions. In particular, approaches to obtaining spontaneously ordered/patterned structures in-plane are systematically reviewedfrom both thermodynamic and kinetic perspectives. Out-of-plane ordering is also discussed in detail. In addition to reviewing the progress of VAN films with spontaneous ordering, this article also highlights some recent developments in spontaneous ordering approaches and proposes future directions. 

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