Abstract

We report direct measurement of the modulus change that accompanies the crosslinking of a single molecular monolayer. We measured a change in elastic modulus of 5×1010 dyn cm-2 as a result of UV-induced photocrosslinking of a single surface-confined monolayer of the conjugated diacetylenic thiol HS(CH2)10Câ–·CCâ–·C(CH2)10CO2H (DAT). The modulus measurement was made on a monolayer of DAT chemisorbed upon a gold film on the surface of a 97-MHz ST-quartz surface acoustic wave (SAW) delay line. The ratio of the changes recorded in SAW velocity and attenuation, ca. 4:1, suggests that the measured effect is mainly a change in the elastic (real) component of the complex shear modulus, viscous changes playing a lesser role. In relation to typical polymer modulus values, the change of 5×1010 dyn cm-2 is consistent with a change from a rubbery material (G′≈107–108 dyn cm-2) to a fairly rigid, glassy material (G′≈1010 dyn cm-2), reasonable for comparison of the monolayer in its as-adsorbed and crosslinked forms. This report of the direct measurement of the modulus change that accompanies the crosslinking of a single molecular monolayer is consistent with previous insitu measurements of this process using thickness-shear mode resonators

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