| This dissertation explores a new vapor deposition route for synthesizing lithium phosphorus oxynitride (Lipon) thin-film electrolytes for rechargeable thin-film Li/Li-ion batteries. These batteries operate at a high voltage (around 4.0 V) and exhibit a long cyclic life (over 10,000 charge/discharge cycles). These features stem from the extremely low leakage current of the Lipon film electrolyte when in contact with a lithium anode, and its good Li-ion conductivity (in the 10-6-10-7 S/cm range). Lipon films have usually been synthesized by reactive RF-magnetron sputtering, which suffers from a very low deposition rate (∼2 nm/min). It therefore takes many hours to make the 1-2 mum thick films needed for battery applications. Other deposition approaches, such as Pulsed Laser Deposition, Ion Beam Assisted Deposition, and E-beam evaporation, have been investigated but resulted in unsatisfactory Lipon film performance.;Here, a plasma-assisted directed vapor deposition (PA-DVD) approach has been explored to synthesize dense, amorphous Lipon films. Unlike conventional e-beam evaporation, the e-beam based DVD approach employs an annular nozzle to generate a rarefied supersonic inert gas jet around the periphery of an electron beam evaporated source material. The vapor is entrained in the jet and rapidly transferred to a substrate. Because the supersonic gas jet focuses the vapor (it impedes lateral spreading of the vapor flux), most of the evaporant reaches the substrate. As a result, the deposition rate of Lipon films can be potentially much higher than most other processes. The PA-DVD approach used here employs a hollow cathode to create low-energy plasma through which the vapor is propagated. This plasma ionized some of the evaporant and reactive gases (nitrogen) that were added to the jet. This increased their reactivity and atomic mobility on a substrate enabling the reactive synthesis of lithium phosphorus oxynitride from a lithium phosphate source. This dissertation explores how varying the deposition conditions (that is, plasma current, nitrogen gas flux, and substrate bias) affected the properties of the Lipon films, and then identifies an optimized process for Lipon film synthesis at rates up to 100 times those reported for sputtering approaches. |
