Visible-light photoconductivity of Zn1-xCoxO and its dependence on Co2+ concentration
Many metal oxides investigated for solar photocatalysis or photoelectrochemistry have band gaps that are too wide to absorb a sufficient portion of the solar spectrum. Doping with impurity ions has been extensively explored as a strategy to sensitize such oxides to visible light, but the electronic structures of the resulting materials are frequently complex and poorly understood. Here, we report a detailed photoconductivity investigation of the wide-gap II-VI semiconductor ZnO doped with Co2+ (Zn1-xCoxO), which responds to visible light in photoelectrochemical and photoconductivity experiments and thus represents a well-defined model system for understanding dopant-sensitized oxides. Variable-temperature scanning photoconductivity measurements have been performed on high-structural-quality Zn1-xCoxO epitaxial films to examine the relationship between dopant concentration (x) and visible-light photoconductivity, with particular focus on mid-gap d-d photoactivity. Excitation into the intense 4T1(P) d-d band at ~2.0 eV (620 nm) leads to Co2+/3+ ionization with a quantum efficiency that increases with decreasing cobalt concentration and increasing sample temperature. Both spontaneous and thermally assisted ionization from the Co2+ d-d excited state are found to become less effective as x is increased, attributed to an increasing conduction-band-edge potential. These trends counter the increasing light absorption with increasing x, explaining the experimental maximum in external photon-to-current conversion efficiencies at values well below the solid solubility of Co2+ in ZnO.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1025658
- Report Number(s):
- PNNL-SA-79985; 19394; KP1704020; TRN: US201120%%669
- Journal Information:
- Physical Review. B. Condensed Matter and Materials Physics, Vol. 84, Issue 12; ISSN 1098-0121
- Country of Publication:
- United States
- Language:
- English
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