Methods and systems for coating articles are described herein. The methods and systems described herein include, but are not limited to, steps for actively or passively controlling the temperature during the coating process, steps for providing intimate contact between the substrate and the support holding the substrate in order to maximize energy transfer, and/or steps for preparing gradient coatings. Methods for depositing high molecular weight polymeric coatings, end-capped polymer coatings, coatings covalently bonded to the substrate or one another, metallic coatings, and/or multilayer coatings are also disclosed. Deposition of coatings can be accelerated and/or improved by applying an electrical potential and/or through the use of inert gases.