Molecular engineering of pyroelectric polysiloxane Langmuir-Blodgett superlattices: synthesis, film preparation and pyroelectric properties

A wide range of linear and cyclic polysiloxanes substituted with side chains containing carboxylic acid groups have been synthesized and characterized in terms of their Langmuir/Langmuir-Blodgett (LB) film properties and their pyroelectric activity. The effects on these properties of varying the degree of side-group substitution, the length of aliphatic side groups, the incorporation of polar aromatic side groups and the deposition conditions utilized during the preparation of multilayer assemblies have been investigated. These materials form stable Langmuir layers at the air-water interface which can be transferred onto substrates such as glass and aluminium-coated glass. The alternate layer LB deposition technique, in which each polysiloxane layer is co-deposited in an alternating stacking sequence with monolayers of a monomeric aliphatic amine compound, has been used to fabricate macroscopically polar films which display a temperature-dependent electric polarization, the ‘pyroelectric effect’. Data are presented here for both linear and cyclic substituted polymer backbones showing that both systems provide useful insight into the pyroelectric behaviour of organic materials. Trends in the relationships between the pyroelectric activity and (1) the chemical structure of the materials and (2) the structure of the acid/amine superlattice have been identified and indicate that the optimum pyroelectric coefficient is observed for a linear copolysiloxane compound substituted with a polar aromatic pendant side group. Indeed, the pyroelectric coefficient measured for this material is ?10?Cm?2 K?1 which is currently the highest value reported for an LB assembly to our knowledge.