Hematite (α-Fe₂O₃)-based photoanodes are promising materials for photoelectrochemical hydrogen generation. We report on fundamental studies of surface structure and reaction chemistry associated with the heterogeneous oxidation of water on such materials by applying a classical surface science approach. We have characterized the structure and properties of Ni-doped and mixed-oxide hematite surfaces formed by vapor deposition under controlled conditions utilizing a range of techniques for surface analysis. The structure of Ni-modified thin films of α-Fe₂O₃ model catalysts with different morphology and geometry was characterized by LEED and STM. Then, water adsorption and reaction were studied by TPD, XPS, UPS, and vibrational spectroscopy by HREELS, characterizing the influence of Ni-modification on thermal and photochemical reaction mechanisms. Ni doping is found to be associated with a new termination for the α-Fe₂O₃(0001) film. Water TPD shows that Ni doping induces new surface chemistry, as revealed by a new, higher temperature OH recombination desorption peak, which is due to more stable surface-bound OH groups as identified by UPS. These surface-science type experiments were combined with photoelectrochemical water oxidation measurements on photoanodes prepared by thin-film and nano-materials synthesis to elucidate new information on the surface phases of hematite-based photoanodes and about their specific stability and reactivity toward photoelectrochemical water splitting.

This work was supported by the Addy/ISN North American Low Carbon Emission Energy Self-Sufficiency Fund of the Andlinger Center for Energy and the Environment (ACEE) and by the Grand Challenges Program at Princeton University.

¹ A. Mattsson, S-L. Hu, K, Hermansson, L. Österlund, Journal of Chemical Physics 140 (2014) 034705

² L. Österlund, Solid State Phenomena 162 (2010) 203-219

We have grown GaN layers alloyed with GaAs, GaSb and GaBi compounds using plasma-assisted molecular beam epitaxy (PA-MBE) and extensively characterized their structural, optical and electrical properties.

Electronic band structures of these so-called highly mismatched alloys (HMAs) are described by the band anticrossing (BAC) model which predicts that the alloys should exhibit a wide range of direct energy gaps. We have shown previously that the energy gap of GaN_1-xAs_x alloys varies from 0.7eV to 3.4eV. An even larger modification of the band structures is anticipated for more extremely mismatched GaN_1-xSb_x and GaN_1-xBi_x alloys. The large band gap range and controllable conduction and valence band edge positions makes the HMAs promising materials for efficient solar energy conversion devices. For example, these HMAs may be suitable for solar water splitting applications for hydrogen production. As efficient photoelectrodes, the bandgap of the semiconductor must be >2 eV to induce electrochemical decomposition of water but still small enough to absorb a significant portion of the solar spectrum. In addition the band edges must also straddle the H₂O redox potentials.

At dilute doping levels, substitutions of As, Sb and Bi into the N sublattice results in formation of localized energy levels above the valence band in GaN. Our measurements on GaN doped with As and Sb have demonstrated that the As and the Sb impurity levels lie at about 0.7eV and 1.2eV above the valence band edge of GaN, respectively.

The BAC model predicts that at a higher concentration of the group V elements the interaction of the impurity levels with the extended states of the valence band leads to formation of an impurity-derived, fully occupied narrow band that plays a role of the new valence band edge. This results in an abrupt upward shift of the valence band edge and a reduction of the optical gap of the HMAs. We have achieved the enhanced incorporation of As, Sb and Bi by growing the layers at extremely low temperatures (down to about 100^oC). Although the layers become amorphous for high As, Sb and Bi content, the measured composition dependence of the optical absorption edge are consistent with the predictions of the BAC model, indicating that the amorphous HMAs samples have a short-range order resembling random crystalline alloys. The large band gap range and controllable positions of the conduction and valence bands make these HMAs promising materials for efficient solar energy conversion devices.

TiO₂ is an important photocatalyst with many practical applications. However, fundamental understanding of thermal and non-thermal reactions on TiO₂ surfaces is still lacking. We have investigated the ultraviolet (UV) photon-stimulated reactions acetone and oxygen adsorbed on reduced rutile TiO₂(110). Previous research suggests that a thermal reaction between acetone and chemisorbed oxygen forms acetone diolate – a photochemically active product.¹ During UV irradiation, a methyl radical is ejected leaving acetate on the surface. Using infrared reflection absorption spectroscopy, we have identified the acetone diolate, which degrades during UV irradiation forming a new product. We have also measured the angular distribution of the photodesorbing methyl radicals, which is consistent with their ejection from the acetone diolate. Specifically, a peak in the distribution near ~60° to the surface normal is detected in the plane perpendicular to the BBO rows. However, we have also observed a second channel for photo-ejection of methyl radical for larger acetone:O₂ ratios. It manifests itself with a photodesorption peak normal to the surface and slower signal decay kinetics. These studies provide new insights into mechanisms responsible for the photochemistry of small molecules on TiO₂ and other oxide surfaces. This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. The work was performed using EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL) . PNNL is a multiprogram national laboratory operated for DOE by Battelle under Contract DE-AC05-76RL01830 .

(1) Henderson, M. A. Relationship of O₂ Photodesorption in Photooxidation of Acetone on TiO₂ . J. Phys. Chem. C, 2008 ,112, 11433-11440.

III-V photoelectrochemical (PEC) devices have achieved high solar-to-hydrogen water splitting efficiencies but corrosion greatly limits their operating lifetime. A dynamic three-phase semiconductor-electrolyte-hydrogen (oxygen) system exists at a photocathode (photoanode) surface during operation. Understanding the interaction of water, hydrogen, and oxygen with III-V surfaces is critical to optimizing device performance and applying corrosion-resistant surface modifications. In this work, we use photoluminescence (PL) to probe the surface response of p-type GaInP₂ to several gas and solution ambients in-situ. X-ray photoelectron spectroscopy and photoelectrochemical techniques are used to characterize surface changes ex-situ. Pretreating p-GaInP₂ with sulfuric acid removes surface oxide and doubles p-GaInP₂ band-to-band PL yield when measured in air. Measurements in vacuum show that PL of pretreated samples increases reversibly with adsorption isotherm dependence on water vapor at partial pressures below 2 Torr while samples without the pretreatment show no PL response to water vapor. A comparison of water to other vapor phase ambients suggests that PL response increases with the dipole strength and involves dissociative adsorption. In oxygen ambient, the PL decays irreversibly which we attribute to photo-oxidation of the p-GaInP₂ surface. We will also present results from measurements in hydrogen ambient and PL measurements and monitoring in electrolyte solutions with a discussion of their relevance to PEC device performance and usefulness in characterizing corrosion resistant surface modifications.