Journal of Physical Chemistry, Vol.100, No.1, 368-373, 1996
Dependences of Thermal Behaviors on the Number of Layers in Langmuir-Blodgett-Films of 2-Octadecyl-7,7,8,8-Tetracyanoquinodimethane .1. Order-Disorder Transitions in the Films Investigated by Ultraviolet-Visible and Infrared Spectroscopies
Dependences of thermal behaviors on the number of layers in Langmuir-Blodgett (LB) films of 2-octadecyl-7,7,8,8-tetracyanoquinodimethane (octadecyl-TCNQ) have been investigated for both morphological and molecular structural aspects by using ultraviolet-visible (UV-vis) and infrared (IR) spectroscopies. The temperature-dependent morphological changes have been monitored by the base-line shift in the UV-vis spectra of the LB films. The changes in the base-line in the 450-600 nm region suggest that the domains in the one-layer film decompose progressively with temperature even just above room temperature. In contrast, the domains in the seven- and 11-layer films are stable until 80 degrees C and undergo rather abrupt collapse between 80 and 90 degrees C. These differences in the thermal behaviors of the domain structure between the one-layer film and the seven- and 11-layer films may be attributed to the differences in the film thickness, the effect of the interaction between the first layer and a CaF2 substrate, and the longitudinal interaction between the domains. The IR spectral measurements for the LB films at elevated temperatures reveal that the order-disorder transition temperature of the one-layer LB film is lower by about 5 degrees C than that of the 11-layer film, which is close to the chain melting point of the bulk material. Of particular interest is that the domain structure of the one-layer film shows the gradual temperature change but that the molecular orientation and structure in the domains experience the clear order-disorder transition.
Keywords:INTEGRATED OPTICAL TECHNIQUES;LB FILMS;CONDUCTING FILMS;PHASE-BEHAVIOR;RAMAN;2-DODECYL-7;7;8;8-TETRACYANOQUINODIMETHANE;MONOLAYERS;ABSORPTION