Implementations described herein generally relate to processes for the fabrication of semiconductor devices in which a self-assembled monolayer (“SAM”) is used to achieve selective epitaxial deposition. In one implementation, a method of processing a substrate is provided. The method comprises exposing a substrate to a self-assembled monolayer (“SAM”) forming molecule to selectively deposit a SAM film on an exposed dielectric material, wherein the substrate comprises the exposed dielectric material and an exposed silicon material. The SAM forming molecule is a chlorosilane molecule. The method further comprises epitaxially and selectively depositing a silicon-containing material layer on the exposed silicon material at a temperature of 400 degrees Celsius or lower. The method further comprises removing the SAM film from the exposed dielectric material.