We have investigated the electronic structure of nanosized iron oxide by scanning tunneling microscopy and spectroscopy as well as by photoelectron spectroscopy. The nanoparticles were produced by the thermal treatment of ferritin molecules containing a self-assembled core of iron oxide. Depending on the thermal treatment we were able to prepare different phases of iron oxide nanoparticles resembling $\gamma \text{−}{\mathrm{Fe}}_2{\mathrm{O}}_3$, $\alpha \text{−}{\mathrm{Fe}}_2{\mathrm{O}}_3$, and a phase which apparently contains both $\gamma \text{−}{\mathrm{Fe}}_2{\mathrm{O}}_3$ and $\alpha \text{−}{\mathrm{Fe}}_2{\mathrm{O}}_3$. The changes to the electronic structure of these materials were studied under reducing conditions. We show that the surface band gap of the electronic excitation spectrum can differ from that of bulk material and is dominated by surface effects.

• Received 6 December 2004

DOI:https://doi.org/10.1103/PhysRevB.71.165409