Fe2O3 films on Si wafer and fused silica substrates have been prepared by spray pyrolysis. The influence of the Si dopant and the SnO2 interfacial layer on the crystal structure and orientation of the Fe2O3 films has been systematically studied. It is found that Si doping results in the formation of beta-Fe2O3, while the SnO2 interfacial layer directs the growth of alpha-Fe2O3 in the [1 1 0] direction. The Raman spectrum of beta-Fe2O3 is identified and the thermal stability of beta-Fe2O3 was investigated. It appears that beta-Fe2O3 is a metastable phase that is stabilized by the presence of the Si dopant. (C) 2009 Elsevier B. V. All rights reserved.