Comparison of molecular orientation and phase transition behaviors in the two kinds of ordered ultrathin films of reversed duckweed polymer ES-3 studied by infrared grazing reflection–absorption spectroscopy

Abstract

A multilayer LB film and a casting film of reversed duckweed polymer ES-3 on Au-evaporated glass slides were investigated by Fourier Transform infrared grazing reflection–absorption spectroscopy. It is found that the two kinds of ordered ultrathin films have different orientation of alkyl chains, nearly perpendicular to the substrate surface for the LB film while rather tilted for the casting film. The studies on their thermal transition behaviors indicate that both of the films have three phase transition processes, respectively, occurring near 65, 105 and 140 °C for the former while near 80, 105 and 140 °C for the latter, but show different transition behavior in the each corresponding transition process. It is referred that at room temperature there are island-like domain structures formed in the LB film, but no ones in the casting film; however, the latter can form the domain structures between the first two transition points due to the desorption of solvents. The formation of domain structure seems to play two important roles, one of which is to make alkyl chains more perpendicular to the substrate surface, and the other to make alkyl chains more packed closely. Thermal cyclic experiments reveal that neither of the films could return to its original state after thermal cyclic treatment up to the temperature, which is above the third transition point, although its alkyl chain becomes highly ordered again.