Reduced Ensemble Plasmon Line Widths and Enhanced Two-Photon Luminescence in Anodically Formed High Surface Area Au–TiO2 3D Nanocomposites

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• 作者：Samira Farsinezhad ; Shyama Prasad Banerjee ; Bharath Bangalore Rajeeva ; Benjamin D. Wiltshire ; Himani Sharma ; Anton Sura ; Arash Mohammadpour ; Piyush Kar ; Robert Fedosejevs ; Karthik Shankar
• 刊名：ACS Applied Materials & Interfaces
• 出版年：2017
• 出版时间：January 11, 2017
• 年：2017
• 卷：9
• 期：1
• 页码：740-749
• 全文大小：720K
• ISSN：1944-8252

文摘

Localized surface plasmon resonances (LSPR) in TiO₂ nanorod and nanotube arrays decorated by gold nanoparticles can be exploited to improve photocatalytic activity, enhance nonlinear optical coefficients, and increase light harvesting in solar cells. However, the LSPR typically has a low quality factor, and the resonance is often obscured by the Urbach tail of the TiO₂ band gap absorption. Attempts to increase the LSPR extinction intensity by increasing the density of gold nanoparticles on the surface of the TiO₂ nanostructures invariably produce peak broadening due to the effects of either agglomeration or polydispersity. We present a new class of hybrid nanostructures containing gold nanoparticles (NPs) partially embedded in nanoporous/nanotubular TiO₂ by performing the anodization of cosputtered Ti–Au thin films containing a relatively high ratio of Au:Ti. Our method of anodizing thin film stacks containing alternate layers of Ti and TiAu results in very distinctive LSPR peaks with quality factors as high as 6.9 and ensemble line widths as small as 0.33 eV even in the presence of an Urbach tail. Unusual features in the anodization of such films are observed and explained, including oscillatory current transients and the observation of coherent heterointerfaces between the Au NPs and anatase TiO₂. We further show that such a plasmonic NP-embedded nanotube structure dramatically outperforms a plasmonic NP-decorated anodic nanotube structure in terms of the extinction coefficient, and achieves a strongly enhanced two-photon fluorescence due to the high density of gold nanoparticles in the composite film and the plasmonic local field enhancement.