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Nanostructured arrays of semiconducting octahedral molecular sieves by pulsed-laser deposition

Nature Materials volume 9, pages 54–59 (2010)Cite this article

Abstract

Cryptomelane-type manganese oxide (OMS-2) has been widely used to explore the semiconducting and catalytic properties of molecular sieves with mixed-valent frameworks. Selective synthesis of patterned thin films of OMS-2 with hierarchical nanostructures and oriented crystals is challenging owing to difficulties in preserving the mixed valence, porosity and crystalline phase. Here, we report that pulsed-laser ablation of OMS-2 in an oxygen-rich medium produces a three-dimensional nanostructured array of parallel and inclined OMS-2 fibres on bare substrates of (001) single-crystal strontium titanate. Both parallel and inclined OMS-2 fibres elongate along the [001]OMS-2 direction. The parallel fibres interact strongly with the substrate and grow epitaxially along 〈110〉STO with lattice misfits of less than 4%, whereas the inclined fibres are oriented with (301) parallel to the substrate surface. The spontaneous orientation of the crystalline OMS-2 domains over the STO surface opens up a new avenue in lattice-engineered synthesis of multilayer materials.

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Figure 1: Morphology and evolution of the OMS-2 nanostructured array.
Figure 2: Crystal structure and preferred orientation.
Figure 3: Microstructure of the OMS-2 nanostructured array.
Figure 4: Heteroepitaxial growth.

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Acknowledgements

We thank the US Department of Energy (DOE), Geosciences and Biosciences Division, Office of Basic Energy Sciences, Office of Science and NSF award number DMR-0907197, for financial support. We would like to thank R. Ristau for preparing cross-section samples on the FIB-TEM and J. Romanow for helping acquiring secondary-electron SEM images. X. Shen and F. Galasso were very helpful with suggestions and encouragement.

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Authors and Affiliations

  1. Institute of Materials Science, University of Connecticut, Storrs, Connecticut 06269-3136, USA

    Anais E. Espinal, Laura Espinal, Mark Aindow & Steven L. Suib

  2. Chemical, Materials & Biomolecular Engineering, University of Connecticut, Storrs, Connecticut 06269-3222, USA

    Lichun Zhang, Mark Aindow & Steven L. Suib

  3. Chemistry Department, University of Connecticut, Storrs, Connecticut 06269-3060, USA

    Chun-Hu Chen, Aimee Morey, Raymond Joesten & Steven L. Suib

  4. Department of Physics, University of Connecticut, Storrs, Connecticut 06269-3046, USA

    Yuefeng Nie & Barrett O. Wells

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  1. Anais E. Espinal
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Contributions

A.E.E., C.-H.C. and S.L.S conceived and designed the experiments. A.E.E., Y.N. and B.O.W. carried out PLD experiments. A.E.E collected crystal structure data and SEM images and analysed them along with L.E., R.J. and S.L.S. L.Z. and M.A. collected the TEM data and analysed the orientation relationships. A.M. prepared the OMS-2 target material. A.E.E., L.E, L.Z., M.A. and S.L.S. co-wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Steven L. Suib.

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Espinal, A., Zhang, L., Chen, CH. et al. Nanostructured arrays of semiconducting octahedral molecular sieves by pulsed-laser deposition. Nature Mater 9, 54–59 (2010). https://doi.org/10.1038/nmat2567

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