Au
nanoparticle (NP)-decorated titanium dioxide (TiO2) thin
films (Au-TO), prepared by a unique surfactant-assisted 2D
self-assembling technique of Au NP layering onto a titanium dioxide
matrix (TO) with molecular-level control, in conjunction with a classic
sol–gel route, showed a significant decrease in the optical
band gap (ΔE
g = ∼0.6 eV)
of Au-TO films compared to the conventional sol–gel-prepared
pristine counterpart. Strong dependence on surfactant type and deposition
temperature of the 2D Au NP layer was observed upon a band gap decrease
of the films. Unlike spin-coated Au NP overlayers on TiO2, which resulted in Au NP agglomeration, in this modified inverted
Langmuir–Schaefer (MILS) technique, the organic surfactant
induced 2D patterned confinement of Au NP layers on TiO2, causing an increase in the active surface area of the Au NP–TiO2 interface. Results of X-ray diffraction and near-edge X-ray
absorption fine structure spectroscopy indicated changes in crystal
structure as well as in electronic states at the O k absorption edge
for Au NP–surfactant patterned films, changes being maximum
for films showing a maximum band gap decrease. A temperature evolution
of morphology of Au-TO films and their Au NP–surfactant monolayer
counterpart at the air–water interface, by ellipsometric imaging
and Brewster angle microscopy, respectively, revealed that Au NP patterning
was induced by surfactant and varied with the temperature of the Au
NP–surfactant monolayer, the band gap decrease being closely
associated with a change in the active Au NP–TiO2 surface area. The maximum band gap decrease was observed for Au-TO
films having tree- or finger-like 2D Au NP patterns, clearly indicating
that an increase in active Au–TiO2 surface area
causes enhancement in structural changes and hence a greater band
gap decrease of the system. Results demonstrate the potential of the
MILS technique of surfactant-aided Au NP-patterned confinement in
semiconducting oxides, in band gap engineering of the latter.