Films of alternately layered zirconium and hafnium phosphonates have been prepared on a silicon substrate by immersing a silicon wafer, modified with an anchoring agent [OHSiMe2-(CH2)3PO3H2 1], into aqueous solutions in the following order: ZrOCl2, H2O3P(CH2)10PO3H2 (DBPA), HfOCl2, DBPA, ZrOCl2.