Periodically ordered nanoscale islands and mesoporous films composed of nanocrystalline multimetallic oxides


Innovative strategies to produce well-defined nanoparticles and other nanostructures such as nanofibres, quantum wells and mesoporous materials have revitalized materials science1,2 for the potential benefit to society. Here, we report a controlled process, involving soft-chemistry-based deposition, template-assisted mesostructured growth, and tuned annealing conditions that allows the preparation of ordered mesoporous crystalline networks and mesostructured nano-island single layers, composed of multicationic metal oxides having perovskite, tetragonal or ilmenite structures. This strategy to obtain meso-organized multi-metal-oxide nanocrystalline films (M3NF) bridges the gap between conventional mesoporous materials and the remarkable properties of crystalline ternary or quaternary metallic oxides. Nanocrystalline mesoporous films with controlled wall thickness (10–20 nm) of dielectric SrTiO3, photoactive MgTa2O6 or ferromagnetic semi-conducting CoxTi1−xO2−x were prepared by evaporation-induced self-assembly (EISA) using a specially designed non-ionic block-copolymer template. A tuned thermal treatment of the mesoporous films permits the transfer of the wall structure into nanocrystallites, with all tectonic units being tightly incorporated into mechanically stable ordered tri- or bidimensional nanocrystalline networks. This methodology should allow multifunctionalization, miniaturization and integration during development of devices such as smart sensors and actuators, better-performing photocatalysts, and fast electrochromic devices. On the other hand, organized arrays of dispersed ferromagnetic or ferroelectric nanoparticles are promising materials for spintronics and for cheap, non-volatile 'flash' memories.

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Figure 1: Scheme of the mesocrystallization process where the three critical steps are detailed.
Figure 2: HRTEM images showing the typical morphology of a SrTiO3 mesoporous ordered network before and after crystallization into M3NF.
Figure 3: In situ time-resolved simultaneous SAXS and WAXS investigations.
Figure 4: The deposition and crystallization processes used to prepare single layers of crystalline nano-islands with controlled dimension and dispersity.


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The authors would like to thank C. Sinturel (Université d'Orléans, France), A. Brunet-Brunneau (Université Pierre et Marie Curie, France), and D. Jalabert (Centre de Microscopie d'Orléans, France) for AFM, RBS and HRTEM analyses respectively. The European community is greatly acknowledged for funding experiments at the Elettra Synchrotron facility.

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Correspondence to Clément Sanchez.

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