A method is disclosed for forming multi-layered structures on polymeric or other materials that provide optical functions or protect underlying layers from exposure to oxygen and water vapor. Novel devices are also disclosed that may include both multi-layered protective structures and AMOLED display, OLED lighting or photovoltaic devices. The protective multi-layer structure itself may be made by depositing successively on a substrate at least three very thin layers of material with different density or composition. In some methods for deposition of such film, the layers are deposited by varying the energy of ion bombardment per unit thickness of the film. Any layer of the structure may include one or more of the materials: silicon nitride, silicon oxide, silicon oxynitride, or metallic nitride or oxide. Specific commercial applications that benefit from this include manufacturing of photovoltaic devices or organic light emitting diode devices (OLED) including lighting and displays.