Abstract: Methods and articles of manufacture for free-standing lithium phosphorus oxynitride (LiPON) thin films are disclosed. The methods facilitate synthesizing the LiPON thin films in a free-standing form with controllable film thicknesses and areas. The free-standing LiPON thin films, absent a solid substrate contacting the LiPON thin films, enable studying fundamental properties of LiPON thin films including mechanical properties and glassy transition behavior. In some embodiments, the method includes modifying a surface of a substrate, forming a layer of LiPON on the modified surface of the substrate, and separating the layer of LiPON from the substrate. The free-standing LiPON thin films, no longer requiring solid substrates, may be used in applications requiring an ionically conductive or electronically insulating coating, film, or barrier layer.