This work investigates the deposition of polystyrene particles onto cross-linked polydimethylsiloxane (PDMS) substrates by using an impinging jet flow cell for different concentrations of sodium chloride in solution. Particle tracking reveals that particles near the substrate can be immobilized to different degrees. An attempt is made to classify the mobility of the particles close to the surface by distinguishing between weakly immobilized and strongly immobilized particles where only the latter ones are considered as deposited. Subsequently, the measured initial deposition rates for different concentrations of sodium chloride in solution are compared to the commonly applied theory based on the convective diffusion equation in which different surface interaction potentials were considered. With currently available data on the surface properties of PDMS, the extended Derjaguin-Landau-Verwey-Overbeek (extended DLVO) theory gave abetter description of the observed deposition rates as compared to the DLVO theory; however, in either case, the presence of significant surface charge heterogeneity had to be assumed in order to capture the observed trend of the deposition rates with respect to the electrolyte concentration. Careful analysis of the more weakly immobilized particles through particle displacement step analysis reveals that there is a buildup of a particle accumulation layer near the substrate in which particle motion parallel to the substrate is hindered by nonhydrodynamic effects. Possible reasons for the reduced particle motion in the accumulation layer are discussed. As a result, the presence of lateral surface interaction forces resulting from charge heterogeneity and surface roughness of the PDMS substrate is found to be the most plausible explanation for the hindered particle motion in the accumulation layer. This suggests that particles associated with the secondary minimum of the surface interaction potential may not always be freely mobile in any direction parallel to the substrate.