White light emitting phosphor RbVO3 films have been successfully fabricated by means of a vacuum ultraviolet (VUV) irradiation using an excimer lamp after spin coating of metal-organic solution onto substrates. The metal-organic carboxylates coated on substrates decomposed and reacted under the VUV irradiation. The metal-organic bonds were efficiently cleaved by the VUV illumination not only in air but also in vacuum, however, there was not a strong driving force for the reaction process to the formation of RbVO3 in the vacuum atmosphere. On the contrary, the reaction and crystallization simultaneously proceeded under photo-chemically produced active oxygen and/or ozone atmospheres due to the VUV illumination in air. The reaction between the photo-activated Rb-O and V-O species could be strongly enhanced by the oxidation atmospheres at the moment of the metal-organic bond cleavage under the VUV irradiation. (C) 2009 Elsevier B. V. All rights reserved.