title: Onset potential behavior in α-Fe2O3 photoanodes: the influence of surface and diffusion Sn doping on the surface states.
abstract: The onset potential is an important parameter that affects the water oxidation performance of photoanodes. Herein, we investigated the behavior of the photocurrent onset potential of hematite (α-Fe2O3) photoanodes by incorporating Sn(4+) cations via external (surface overlayer) or self (underlying FTO substrate) doping. The α-Fe2O3/FTO photoanodes fabricated at both low (550 °C) and high (800 °C) temperatures were chosen for surface Sn(4+) doping (0-10 mM SnCl4). At the lower temperature, Sn(4+) doping enriched the conductivity of α-Fe2O3/FTO, thereby improving the photocurrent response at higher applied potentials. In addition, the surface incorporation of Sn(4+) shifted the onset of the water oxidation reaction in the positive direction. In the case of high temperature-annealed photoanodes, Sn leaching (resulting from FTO deformation) also affected the water oxidation performance of the photoanodes. This was caused by the loss of FTO conductivity as well as by the unfavourable surface properties due to the excessive incorporation of Sn ions (SnOx) into the hematite matrix. The anodic shift of the onset potential in both cases was due to the decreased surface state capacitance, as revealed by electrochemical impedance spectroscopy (EIS). The different annealing conditions, where lattice distortion and deformation-directed Sn diffusion-doping occur, were also found to affect the surface states associated with hematite and its water oxidation onset potential. Crystallographic analyses made by synchrotron XRD further support the results obtained from the EIS study. Sn doping was found to be concurrent with the respective changes in the (104) and (110) planes of hematite, which are associated with the onset potential-driving surface states and the photocurrent-boosting electron mobility, respectively.
authors.affiliation: Division of Biotechnology, Advanced Institute of Environmental and Bioscience, College of Environmental and Bioresource Sciences, Chonbuk National University, Iksan 570-752, Republic of Korea. jangjs75@jbnu.ac.kr.
authors.forename: Pravin S
authors.initials: PS
authors.lastname: Shinde
authors.affiliation: Pohang Accelerator Laboratory (PAL), Pohang University of Science and Technology (POSTECH), Pohang 790-784, Republic of Korea.
authors.forename: Sun Hee
authors.initials: SH
authors.lastname: Choi
authors.affiliation: Pohang Accelerator Laboratory (PAL), Pohang University of Science and Technology (POSTECH), Pohang 790-784, Republic of Korea.
authors.forename: Yongsam
authors.initials: Y
authors.lastname: Kim
authors.affiliation: Mineral Resources Research Division, Korea Institute of Geoscience and Mineral Resources (KIGAM), Daejeon 305-350, Republic of Korea. jryu@kigam.re.kr.
authors.forename: Jungho
authors.initials: J
authors.lastname: Ryu
authors.affiliation: Division of Biotechnology, Advanced Institute of Environmental and Bioscience, College of Environmental and Bioresource Sciences, Chonbuk National University, Iksan 570-752, Republic of Korea. jangjs75@jbnu.ac.kr.
authors.forename: Jum Suk
authors.initials: JS
authors.lastname: Jang