were chosen to meet the requirements of a given instrumental analysis. Substrate surfaces were cleaned by immersion into a H 2 SO 4 :H 2 O 2 = 7:3 (v/v) solution for a few minutes followed by washing thoroughly by Milli-Q water and methanol.
Preparation of gel and oxide films: The spreading solutions were prepared by dissolving TBT and C 18 AA in chloroform or TBZ and C 18 AA in hexane with the alkoxide/C 18 AA molar ratio of 3 (TBT and TBZ, 3 mmol L Β±1 ; C 18 AA 1 mmol L Β±1 ), and were kept for more than 2 h at room temperature to allow complexation [10]. A 100 mL portion of the solution was spread at 288 K on the surface of pure water in an LB trough (ca. 600 cm 2 ) using a syringe. After evaporating the spreading solvents for 15 min, two-dimensional compression was performed on the LB trough using a computer-controlled film balance (USI system Co. Ltd., FSD 110) and was monitored by measurement of the surface pressure-area (p-A) isotherm. The LB deposition of gel films were performed at a surface pressure of 20 mN m Β±1 by a vertical dipping of a substrate at 10 mm min Β±1 with the film balance and a lifter (USI system Co. Ltd., FSD 23). The progress of the LB deposition was monitored by measurement of the time course of area (A-t curve). The precursor gel film for (ZrO 2 /TiO 2 ) n heterolayered film was prepared by n times alternate deposition of the TBT-C 18 AA gel film (29-layers) and TBZ-C 18 AA gel film (29-layer) on Si-substrate. The conversion of gel films into oxide films was carried out by heat treatment at 773 K for 30 min in air as previously reported [10].
Instrumental analysis: UV-vis absorption spectra of quartz-supported films were recorded on a Shimadzu UV-3100 spectrometer in the transmission mode. IR spectra of CaF 2 -supported films were measured using a Perkin-Elmer 1650 spectrometer in transmission mode. The high resolution transmission electron microscope (HRTEM) used was a JEOL JEM-2010HT (200 kV) equipped with an energy-dispersive X-ray spectrometer (EDX) system (Oxford Link ISIS spectrometer). Si-supported films were sliced perpendicular to the film surface and ion-thinned by an Ar + beam accelerated at 5 eV (Gatan PIPS 691 ion polisher), allowing a cross-sectional view of the film. Atomic force microscopic (AFM) images were taken on Sisupported films using a Topometrix Explorer 2000 scanning probe microscope with a 2 mm scanner and silicon nitride tips (spring constant = 34Β± 44 N m Β±1 , F 0 = 176 KHz). AFM images were taken in air in the non-contact mode and were examined in at least three different sites for a given sample. X-Ray photoelectron spectra (XPS) of quartz-supported films were recorded on a Shimadzu ESCA-850 instrument with a Mg Ka source (1253.6 eV). The binding energies were calibrated in reference to the C 1s line of carbon (285.0 eV) or the Si 2p line of SiO 2 (103.5 eV). The depth-profiling XPS analysis was performed by alternate repeats of the spectra acquisition and the Ar + sputtering (2.0 eV, 25 mA). X-Ray diffraction (XRD) patterns of films deposited on borosilicate glass were taken with a Rigaku LINT-2200 instrument using Cu Ka radiation.