A pulsed ArF laser is used to photochemically deposit thin films of silicon dioxide on silicon substrates. As the substrate temperature was increased during film deposition, the etch rate, dielectric constant, flatband voltage shift, and hydrogen bonding of the SiO2film decreased while the refractive index, resistivity, and breakdown voltage increased. The etch rate and infrared absorbance of bonded hydrogen incorporated in the SiO2film also decreased when surface photons impinged on the growing films or when a post‐deposition anneal was performed.