Abstract
We observe the isothermal amorphous-to-crystalline transition of TiO2 thin films deposited by reactive RF magnetron sputtering with in-situ optical microscopy at several temperatures. The crystalline fraction of single-phase anatase, brookite, and rutile films as a function of time is analyzed within the Johnson–Mehl–Avrami–Kolmogorov framework to extract model parameters. Avrami exponents near 3 for anatase are consistent with 2-dimensional growth and a constant nucleation rate but are significantly higher for brookite and rutile, which we attribute to an increasing nucleation rate. The number of crystallization centers per unit area for rutile is higher than for brookite which in turn is higher than anatase. Total crystallization times for brookite and anatase decrease with increasing film thickness, consistent with a volume-induced nucleation model. Brookite grows anisotropically in contrast to the circular morphology observed for anatase and rutile.
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Acknowledgments
This work was supported as part of the Center for Next Generation Materials by Design: Incorporating Metastability, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award No. DE-AC3608GO28308. We thank Joseph Kreb for assistance with film thickness measurements. We acknowledge the use of the Oregon State University MASC cleanroom and the Raman microscope in the Rorrer Laboratory.
Funding
The research leading to these results received funding from the United States Department of Energy, Office of Science, Basic Energy Sciences under Award No. DE-AC3608GO28308 (EFRC: Center for Next Generation Materials by Design: Incorporating Metastability).
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OA performed materials preparation, data collection, and analysis and contributed to the study conception and design. PB contributed to the data collection and analysis. JT designed the study and contributed to analysis. OA wrote the first draft of the manuscript, and all authors reviewed and approved the final version.
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Ağırseven, O., Biswas, P. & Tate, J. Amorphous-to-crystalline transition of thin-film TiO2 precursor films to brookite, anatase, and rutile polymorphs. Journal of Materials Research 37, 1135–1143 (2022). https://doi.org/10.1557/s43578-021-00478-x
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DOI: https://doi.org/10.1557/s43578-021-00478-x