Zirconium butoxide

Zirconium butoxide (Zr(OBu)₄, 80% wt. in n-butanol), and methacrylic acid were employed for the synthesis of the oxocluster and were purchased from Sigma-Aldrich, while methyl methacrylate (MMA, 99% wt.), 2,2,2-trifluoroethylmethacrylate (TFMA, 99% wt.), 3-methacryloxypropyltrimethoxysilane (MAPTMS), benzoyl peroxide (≥97% wt.) and toluene, purchased from Sigma-Aldrich, were used for the synthesis of the hybrid materials. The monomers were previously filtered on neutral alumina to remove the inhibitors. Hydrogen peroxide (35% wt. in H₂O), acetonitrile (≥99.8%), methyl p-tolyl sulphide (99% wt.), purchased from Sigma-Aldrich, were used for the oxidation reaction. Dichloromethane (≥99.9%), undecane (≥99%), triphenylphosphine, were used as solvents, a reference compound and an H₂O₂ quencher for the GC analysis, respectively.

Polycrystalline PbZrO₃ films were prepared by chemical solution deposition using an inverted mixing order chemistry⁴¹ . The solution comprised zirconium butoxide (80 wt.% in butanol, Sigma Aldrich), lead (IV) acetate (Sigma Aldrich), methanol, and acetic acid. A 0.35 M solution was used with 35 mol% excess Pb to account for loss to the substrate and atmosphere during high-temperature annealing. The PZO film was coated on a 100 nm Pt/40 nm ZnO/300 nm SiO₂/(001) Si substrate by spin casting at 4000 RPM for 30 s followed by a pyrolysis step at 350 °C for 1 min⁴² . After four coating and pyrolysis steps, an additional layer of a 0.1 M PbO solution was coated onto the surface to provide a PbO overpressure and the film was annealed at 700 °C for 10 min in a preheated box furnace⁴³ . The final PbZrO₃ film thickness was 300 nm. X-ray diffraction was performed using a PanAlytical Empyrean diffractometer in a Bragg–Brentano geometry with a GaliPIX detector and Cu Kα radiation, and scanning electron microscopy was performed using a FEI Quanta 650 with a concentric backscatter detector and an acceleration voltage of 15 kV⁴⁴ .