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In situ micro-Raman studies of laser-induced bismuth oxidation reveals metastability of beta-Bi2O3 microislands

Journal Article


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Abstract


  • We report the laser irradiation-induced oxidation of bismuth metal investigated in situ by micro-Raman spectroscopy as a function of irradiation power and time. The purely optical synthesis and characterization of beta-Bi2O3 oxide microislands on metallic Bi surfaces is shown to be stable over time, even at room-temperature. By closely examining possible reactions on simple Bi morphologies it is revealed for the first time that the ensuing oxide phase is critically dependent on the final oxide volume and follows a fixed kinetic transformation sequence: 3/2 O2(g)+2Bi(l) -> beta-Bi2O3(s) -> alpha-Bi2O3(s). These findings are unusual within the framework of traditional Bi2O3 thermal transformation relations. An electrostatic mechanism involving a changing Bi2O3 surface-to-volume ratio is proposed to explain the room-temperature metastability of small beta-Bi2O3 volumes and the subsequent transformation sequence, as well as unifying the results of previous studies.

Authors


Publication Date


  • 2014

Citation


  • Steele, J. A. & Lewis, R. A. (2014). In situ micro-Raman studies of laser-induced bismuth oxidation reveals metastability of beta-Bi2O3 microislands. Optical Materials Express, 4 (10), 2133-2144.

Scopus Eid


  • 2-s2.0-84907462196

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=5051&context=eispapers

Ro Metadata Url


  • http://ro.uow.edu.au/eispapers/4032

Number Of Pages


  • 11

Start Page


  • 2133

End Page


  • 2144

Volume


  • 4

Issue


  • 10

Place Of Publication


  • http://www.opticsinfobase.org/ome/abstract.cfm?uri=ome-4-10-2133

Abstract


  • We report the laser irradiation-induced oxidation of bismuth metal investigated in situ by micro-Raman spectroscopy as a function of irradiation power and time. The purely optical synthesis and characterization of beta-Bi2O3 oxide microislands on metallic Bi surfaces is shown to be stable over time, even at room-temperature. By closely examining possible reactions on simple Bi morphologies it is revealed for the first time that the ensuing oxide phase is critically dependent on the final oxide volume and follows a fixed kinetic transformation sequence: 3/2 O2(g)+2Bi(l) -> beta-Bi2O3(s) -> alpha-Bi2O3(s). These findings are unusual within the framework of traditional Bi2O3 thermal transformation relations. An electrostatic mechanism involving a changing Bi2O3 surface-to-volume ratio is proposed to explain the room-temperature metastability of small beta-Bi2O3 volumes and the subsequent transformation sequence, as well as unifying the results of previous studies.

Authors


Publication Date


  • 2014

Citation


  • Steele, J. A. & Lewis, R. A. (2014). In situ micro-Raman studies of laser-induced bismuth oxidation reveals metastability of beta-Bi2O3 microislands. Optical Materials Express, 4 (10), 2133-2144.

Scopus Eid


  • 2-s2.0-84907462196

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=5051&context=eispapers

Ro Metadata Url


  • http://ro.uow.edu.au/eispapers/4032

Number Of Pages


  • 11

Start Page


  • 2133

End Page


  • 2144

Volume


  • 4

Issue


  • 10

Place Of Publication


  • http://www.opticsinfobase.org/ome/abstract.cfm?uri=ome-4-10-2133