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Metal-insulator-semiconductor structures were fabricated using 40-layers-thick Langmuir-Blodgett (LB) films of stearic acid (SA) on hydrophobic n-type silicon (n-Si) substrates. Cadmium sulphide (CdS) nanoparticles were introduced by exposure to H2S gas for a period of 12 h. Samples containing CdS nanoparticles exhibit lower dc leakage current but higher effective dielectric constant. The effective dielectric constant of the CdS embedded SA matrix is found to be 5.1. The Poole-Frenkel effect is prevalent for charge transport in the LB films containing CdS nanoparticles at the field higher than 107· Vm-1. The effect becomes saturated at higher fields.