Growth kinetics and thermodynamic stability of octadecyltrichlorosilane self-assembled monolayer on Si (100) substrate

We have studied the growth kinetics and thermodynamic stability of octadecyltrichlorosilane (OTS) self-assembled monolayers on Si (100) substrate in order to understand its role in controlling the adhesion and surface hydrophobicity. Time-dependent contact angle measurements, using water as a function of OTS concentration, show rapid monolayer formation in the initial stage followed by a slow attainment of full coverage and the overall kinetics approximately follows the Langmuir adsorption isotherm. The adsorption rate constant (ka = 150 M− 1 s− 1) is found to be significantly greater than the desorption rate constant (kd = 0.156 s− 1) while the Gibbs free energy (ΔGads) change amounts to − 4.2 kcal/mol suggesting thermodynamic stability of OTS monolayer on a silicon surface. Partial monolayer formation by a ‘uniform’ growth mechanism, even at low coverage, is revealed by atomic force microscopy (AFM) in conjunction with grazing angle FTIR spectroscopy. Analysis of the interfacial adhesion properties using Zisman plot suggests a critical surface tension (γc) of 20.7 dyn/cm for OTS monolayer on Si (100) surface.