H. Nishikiori et al., Monomer-dimer equilibrium of rhodamine B encapsulated in Si-Al and Si-Ti binary-oxide thin films, J SOL-GEL S, 20(1), 2001, pp. 95-104
Si-Al and Si-Ti binary-oxide thin films including Rhodamine B (RB) have bee
n prepared. They were dip-coated as a function of time after mixing of each
sol-gel reaction system. The absorption and fluorescence spectra of the in
dividual films have been observed. These spectra were analyzed in order to
clarify the behavior of RB along with the change in the environment around
the RB molecules, caused by the progress of the sol-gel reaction, in the fl
uid sol and the prepared thin films. Some amount of the RB dimers (H- and J
-types) were formed in the Si-Al and Si-Ti binary-oxide films (Si : M = 75
: 25) prepared at the initial stage of the sol-gel reaction and aged under
relative humidity of 60%. In the case of Si-Al binary-oxide films, the amou
nt of the J-dimer decreased along with the reaction time at which the films
were prepared, indicating that growing polymer networks of metal alkoxides
around the RB molecules prevent the formation of the J-dimer. On the other
hand, larger amounts of the H- and J-dimers were formed in the Si-Ti binar
y-oxide films prepared at longer reaction time of the solution. RB interact
s more strongly with -TiOH compared with -AlOH. In the case of the Si-Ti bi
nary-oxide films, with the progress of the sol-gel reaction, RB molecules i
n the prepared films easily cohere around the -TiOH and form the dimers bec
ause of increase in the amount of the -TiOH and contraction in the volume o
f the spaces where RB molecules exist.