Optical Properties of Au Nanoparticles Included in Mesoporous TiO2 Thin Films: A Dual Experimental and Modeling Study

Gold nanoparticles (NP) were synthesized inside ordered mesoporous TiO2 thin films (MTTF) by stepwise reduction of AuCl4 − with NaBH4. This leads to an optical material (Au@TiO2) of interest for plasmonic applications. The films (pure titania or gold-titania nanocomposites) were thoroughly characterized by UV−visible and ellipsometry spectroscopies. The dielectric function of the MTTF, considered as the dielectric environment in which the NP are embedded, was acquired by ellipsometry and rationalized by the asymmetric Bruggeman model as an effective medium formed by the mixture of dense TiO2 and air. Nanocomposite Au@TiO2 systems present an isotropic dispersion of Au NP in the 5−8 nm range. The UV−visible spectra obtained with a low nanoparticle filling fraction of the pore volume (f NP < 2%) are accurately reproduced by both Maxwell−Garnett (MG) and Mie theories. Accurate and coincident values of f NP and NP size are obtained by this method. The dielectric function of Au NP used in this work was studied in detail; in particular, the interface damping parameter related to the NP/MTTF interface was determined by comparison with TEM microscopy. The potential of the ellipsometry technique to determine the material plasmonic response, and its correspondence with the UV−visible spectra, are discussed. This spectroscopy technique opens the possibility to study the plasmon response of the material to changes in the environment due to the presence of vapors, and other in situ experiments, as well as to provide nanostructural information of metallic nanoparticles (NP size, interparticle distance, number of NP) with well-defined spatial localization in a multilayered system. Fil: Sanchez, Veronica Muriel. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Martínez, Eduardo David. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Martinez Ricci, Maria Luz. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina Fil: Troiani, Horacio Esteban. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Instituto Balseiro; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Soler Illia, Galo Juan de Avila Arturo. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina