Thermionic energy converter (TEC) is a device to generate electricity from heat in a silent, vibration-free operation. Non-idealities such as negative space-charge effect and electron reflection from collector surface adversely effect output current density and device efficiency. Using a range of thin film deposition techniques such as rf plasma magnetron sputtering, electrochemical deposition and electroless process, different surface structures were developed and tested for suppression of electron reflection using Cs/O vapor plasma TECs. Principles of both vacuum and solution based synthesis of thin films, and promising device configurations for thermionic energy converters are presented. This book overviews evolution of thermionics technology in a comprehensive manner, identifies key issues and challenges to be addressed, and suggests feasible solutions based on a sensible choice of materials and processes. The contents of this book are useful for teaching at both undergraduate and postgraduate levels as well as for researchers working on thin film synthesis and characterization for applications in energy, microelectronics, and surface engineering industries.