Semiconductor-to-metal transition in rutile TiO2 induced by tensile strain

Benson, Eric E.; Miller, Elisa M.; Nanayakkara, Sanjini U.; Svedruzic, Drazenka; Ferrere, Suzanne; Neale, Nathan R.; van de Lagemaat, Jao; Gregg, Brian A.

doi:10.1021/acs.chemmater.6b04881

Title: Semiconductor-to-metal transition in rutile TiO₂ induced by tensile strain

Journal Article · Fri Feb 10 04:00:00 UTC 2017 · Chemistry of Materials

DOI: https://doi.org/10.1021/acs.chemmater.6b04881 · OSTI ID:1347505

^[1]; Miller, Elisa M. ^[1]; Nanayakkara, Sanjini U. ^[1]; Svedruzic, Drazenka ^[1]; Ferrere, Suzanne ^[1]; Neale, Nathan R. ^[1]; van de Lagemaat, Jao ^[1]; Gregg, Brian A. ^[1]

National Renewable Energy Lab. (NREL), Golden, CO (United States)

Here, we report the first observation of a reversible, degenerate doping of titanium dioxide with strain, which is referred to as a semiconductor-to-metal transition. Application of tensile strain to a ~50 nm film of rutile TiO₂ thermally grown on a superelastic nitinol (NiTi intermetallic) substrate causes reversible degenerate doping as evidenced by electrochemistry, X-ray photoelectron spectroscopy (XPS), and conducting atomic force microscopy (CAFM). Cyclic voltammetry and impedance measurements show behavior characteristic of a highly doped n-type semiconductor for unstrained TiO₂ transitioning to metallic behavior under tensile strain. The transition reverses when strain is removed. Valence band XPS spectra show that samples strained to 5% exhibit metallic-like intensity near the Fermi level. Strain also induces a distinct transition in CAFM current-voltage curves from rectifying (typical of an n-type semiconductor) to ohmic (metal-like) behavior. We propose that strain raises the energy distribution of oxygen vacancies (n-type dopants) near the conduction band and causes an increase in carrier concentration. As the carrier concentration is increased, the width of the depletion region is reduced, which then permits electron tunneling through the space charge barrier resulting in the observed metallic behavior.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

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

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1347505

Report Number(s):: NREL/JA--5900-68053

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 5 Vol. 29; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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71 CLASSICAL AND QUANTUM MECHANICS
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semiconductor-to-metal
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Title: Semiconductor-to-metal transition in rutile TiO2 induced by tensile strain

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Title: Semiconductor-to-metal transition in rutile TiO₂ induced by tensile strain