Colloidal Synthesis of Bipolar Off-Stoichiometric Gallium Iron Oxide Spinel-Type Nanocrystals with Near-IR Plasmon Resonance.

Title Colloidal Synthesis of Bipolar Off-Stoichiometric Gallium Iron Oxide Spinel-Type Nanocrystals with Near-IR Plasmon Resonance.
Authors C. Urso; M. Barawi; R. Gaspari; G. Sirigu; I. Kriegel; M. Zavelani-Rossi; F. Scotognella; M. Manca; M. Prato; L. De Trizio; L. Manna
Journal J Am Chem Soc
DOI 10.1021/jacs.6b11063
Abstract

We report the colloidal synthesis of ~5.5nm inverse spinel-type oxide Ga2FeO4 (GFO) nanocrystals (NCs) with control over the gallium and iron content. As recently theoretically predicted, some classes of spinel-type oxide materials can be intrinsically doped by means of structural disorder and/or change in stoichiometry. Here we show that, indeed, while stoichiometric Ga2FeO4 NCs are intrinsic small bandgap semiconductors, off-stoichiometric GFO NCs, produced under either Fe-rich or Ga-rich conditions, behave as degenerately doped semiconductors. As a consequence of the generation of free carriers, both Fe-rich and Ga-rich GFO NCs exhibit a localized surface plasmon resonance in the near-infrared at ~1000nm, as confirmed by our pump-probe absorption measurements. Our fitting of experimental LSPR curves revealed that off-stoichiometric GFO NCs have a concentration of free carriers in the order of 1022cm-3, in line with common/typical extrinsically doped metal oxide materials. Noteworthy, the photo-electrochemical characterization of our GFO NCs reveal that the majority carriers are holes in Fe-rich samples, and electrons in Ga-rich ones, highlighting the bipolar nature of this material. The behavior of such off-stoichiometric NCs was explained by our density functional theory calculations as follow: the substitution of Ga3+ by Fe2+ ions, occurring in Fe-rich conditions, can generate free holes (p-type doping), while the replacement of Fe2+ by Ga3+ cations, taking place in Ga-rich samples, produces free electrons (n-type doping). These findings underscore the potential relevance of spinel-type oxides as p-type transparent conducive oxides and as plasmonic semiconductors.

Citation C. Urso; M. Barawi; R. Gaspari; G. Sirigu; I. Kriegel; M. Zavelani-Rossi; F. Scotognella; M. Manca; M. Prato; L. De Trizio; L. Manna.Colloidal Synthesis of Bipolar Off-Stoichiometric Gallium Iron Oxide Spinel-Type Nanocrystals with Near-IR Plasmon Resonance.. J Am Chem Soc. 2016. doi:10.1021/jacs.6b11063

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Iron

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