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Dynamic chemical expansion of thin-film non-stoichiometric oxides at extreme temperatures

Nature Materials volume 16, pages 749–754 (2017)Cite this article

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Abstract

Actuator operation in increasingly extreme and remote conditions requires materials that reliably sense and actuate at elevated temperatures, and over a range of gas environments. Design of such materials will rely on high-temperature, high-resolution approaches for characterizing material actuation in situ. Here, we demonstrate a novel type of high-temperature, low-voltage electromechanical oxide actuator based on the model material PrxCe1−xO2−δ (PCO). Chemical strain and interfacial stress resulted from electrochemically pumping oxygen into or out of PCO films, leading to measurable film volume changes due to chemical expansion. At 650 °C, nanometre-scale displacement and strain of >0.1% were achieved with electrical bias values <0.1 V, low compared to piezoelectrically driven actuators, with strain amplified fivefold by stress-induced structural deflection. This operando measurement of films ‘breathing’ at second-scale temporal resolution also enabled detailed identification of the controlling kinetics of this response, and can be extended to other electrochemomechanically coupled oxide films at extreme temperatures.

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Figure 1: Dynamic chemical expansion upon oscillating electrical bias.
Figure 2: Sample frequency response to expanding Pr0.1Ce0.9O2−δ film.
Figure 3: Factors controlling oxide film breathing.
Figure 4: Schematic of processes occurring during direct chemical-expansion measurement.

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Acknowledgements

This work was supported by the US Department of Energy, Basic Energy Sciences, Division of Materials Science and Engineering under award number DE-SC0002633. J.G.S. acknowledges support from the DOE-SCGF Fellowship Program administered by ORISE-ORAU under contract no. DE-AC05-06OR23100. J.J.K. thanks the Kwanjeong Educational Foundation for fellowship support. The authors acknowledge C. S. Kim for additional sample preparation and F. Frankel for assistance with figure preparation. This work made use of the Shared Experimental Facilities supported in part by the MRSEC Program of the National Science Foundation under award number DMR-1419807.

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Authors and Affiliations

  1. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA

    Jessica G. Swallow, Jae Jin Kim, John M. Maloney, Di Chen, Sean R. Bishop, Harry L. Tuller & Krystyn J. Van Vliet

  2. Materials Processing Center, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA

    Jessica G. Swallow, Jae Jin Kim, Di Chen, Sean R. Bishop, Harry L. Tuller & Krystyn J. Van Vliet

  3. Micro Materials Ltd., Wrexham LL13 7YL, UK

    James F. Smith

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Contributions

J.G.S., J.J.K., H.L.T. and K.J.V.V. designed the study. J.G.S. developed the dynamic expansion measurement technique and conducted displacement measurements and data analysis. J.J.K. deposited films and conducted impedance measurements, structural characterization and imaging. S.R.B. developed analysis methods and relationships between impedance and mechanical results. J.M.M. designed LabView signal analysis code for detecting expansion phase lag and amplitude. D.C. contributed to sample design and application of the defect model. J.F.S. contributed to frequency-based measurement experimental design. J.G.S., J.J.K., S.R.B., H.L.T. and K.J.V.V. wrote the manuscript.

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Correspondence to Krystyn J. Van Vliet.

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Swallow, J., Kim, J., Maloney, J. et al. Dynamic chemical expansion of thin-film non-stoichiometric oxides at extreme temperatures. Nature Mater 16, 749–754 (2017). https://doi.org/10.1038/nmat4898

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