Selective Brookite Polymorph Formation Related to the Amorphous Precursor State in TiO2 Thin Films

Mangum, John S.; Agirseven, Okan; Haggerty, James E. S.; Perkins, John D.; Schelhas, Laura T.; Kitchaev, Daniil A.; Garten, Lauren M.; Ginley, David S.; Toney, Michael F.; Tate, Janet; Gorman, Brian P.

doi:10.1016/j.jnoncrysol.2018.10.049

Selective Brookite Polymorph Formation Related to the Amorphous Precursor State in TiO₂ Thin Films

Journal Article · Thu Nov 08 00:00:00 EST 2018 · Journal of Non-Crystalline Solids

DOI:https://doi.org/10.1016/j.jnoncrysol.2018.10.049· OSTI ID:1485571

Mangum, John S. ^[1]; Agirseven, Okan ^[2]; Haggerty, James E. S. ^[2]; Perkins, John D. ^[3]; Schelhas, Laura T. ^[4]; Kitchaev, Daniil A. ^[5]; Garten, Lauren M. ^[3]; Ginley, David S. ^[3]; Toney, Michael F. ^[4]; Tate, Janet ^[2]; Gorman, Brian P. ^[1]

Colorado School of Mines, Golden, CO (United States)
Oregon State Univ., Corvallis, OR (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

A wide variety of brookite TiO₂ synthesis methods have been published over the past several decades, but few studies discuss the underlying mechanism that stabilizes brookite over its stable counterparts, rutile and anatase. Here in this study, we investigate of the effect of pulsed laser deposition parameters on the as-deposited amorphous precursor titania thin films, which subsequently crystallize into stable and metastable TiO₂ polymorphs upon annealing. We find that oxygen pressure in the deposition chamber strongly influences the non-equilibrium state of the amorphous precursor, which ultimately allows for selective polymorph formation. Rutile forms as the dominant phase at low pO₂ < 0.1 mTorr, while anatase is favored at high pO₂ > 5 mTorr. Brookite forms primarily at intermediate pO₂ (0.5-1.0 mTorr). Controlling the amorphous structure (i.e. Ti - O bonding and polyhedral arrangement) of the precursors via oxygen deficiency is therefore likely for the selective formation of crystalline TiO₂ polymorphs from sub-stoichiometric amorphous precursors. Lastly, directing phase selectivity by manipulating the structure and internal energy of the precursor amorphous state may have tremendous potential for synthesis of metastable crystalline phases that exhibit more desirable properties in comparison to their stable counterparts.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Next Generation of Materials by Design: Incorporating Metastability (CNGMD); National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1485571

Alternate ID(s):: OSTI ID: 1635947

Report Number(s):: NREL/JA--5K00-72918

Journal Information:: Journal of Non-Crystalline Solids, Journal Name: Journal of Non-Crystalline Solids Journal Issue: C Vol. 505; ISSN 0022-3093

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited By (2)

Crystallization of TiO ₂ polymorphs from RF-sputtered, amorphous thin-film precursors Agirseven, O.; Rivella, D. T.; Haggerty, J. E. S. AIP Advances, Vol. 10, Issue 2 https://doi.org/10.1063/1.5140368	journal	February 2020
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Related Subjects

36 MATERIALS SCIENCE
TiO2
amorphous precursors
oxygen deficiency
polymorphs
selective crystallization
thin films