Po. Jackson et al., An investigation of the role of cross-linking and photodegradation of side-chain coumarin polymers in the photoalignment of liquid crystals, CHEM MATER, 13(2), 2001, pp. 694-703
A surface anisotropy has been shown previously to be induced in thin films
of photoreactive coumarin side-chain polymers by polarized UV illumination.
Consequently, the resultant cross-linked polymer layers can be used as pho
toalignment layers for liquid crystal displays. Homogeneous alignment of a
nematic liquid crystal in contact with a layer of a model coumarin side cha
in polymer is obtained with the director parallel or perpendicular to the U
V polarization axis depending on the incident fluence. Spectroscopic analys
is of the alignment layer now confirms that both photodegradation and cross
-linking occur with different dependencies on fluence. Low UV fluences give
parallel photoalignment and high cross-linking reactivity. However, the re
sidual, unreacted polymer side chains show negligible anisotropy because of
their freedom to move in an isotropic fashion. Hence, parallel liquid crys
tal alignment is attributed to a steric interaction between the liquid crys
tal and syndimerized side chains of the cross-linked polymer. A switch of t
he photoalignment direction accompanies the subsequent development of aniso
tropy of the intact, unreacted polymer side chains. The side-chain anisotro
py and hence perpendicular liquid crystal alignment is ascribed to photodeg
radation rather than cross-linking.