  In the last years, important non-linear optical results on sol-gel and
polymeric materials have been reported, with values comparable to those found
in crystals. These new materials contain push-pull chromophores either
incorporated as guest in a high Tg polymeric matrix (doped polymers) or grafted
onto the polymeric matrix. These systems present several advantages; however
they require significant improvement at the molecular level - by designing
optimized chromophores with very large molecular figure of merit, specific to
each application targeted. Besides, it was recently stated in polymers that the
chromophore-chromophore electrostatic interactions, which are dependent of
chromophore concentration, have a strong effect into their non-linear optical
properties. This has not been explored at all in sol-gel systems. In this work,
the sol-gel route was used to prepare hybrid organic-inorganic thin films with
different NLO chromophores grafted into the skeleton matrix. Combining a
molecular engineering strategy for getting a larger molecular figure of merit
and by controlling the intermolecular dipole-dipole interactions through both:
the tuning of the push-pull chromophore concentration and the control of TEOS
(Tetraethoxysilane) concentration, we have obtained a r33 coefficient around 15
pm/V at 633 nm for the classical DR1 azo-chromophore and a r33 around 50 pm/V
at 831 nm for a new optimized chromophore structure.
