Solid-state batteries (SSBs) are safer, cheaper, and higher energy density alternatives to conventional Li-ion batteries, of which the global production capacity has reached 150 GWh/year. However, development of new materials and their optimization to predicted ideal structure-property characteristics can typically take >10 years of capital-intensive research to find the best solidification and dopant strategies. Typical solid-state manufacture considers high temperature synthesis based on powder sintering for Co-free cathode material integration, which is time and labor intensive, produces a large CO₂ footprint, and incurs high costs. In contrast, wet-chemical fabrication methods like sequential deposition synthesis (SDS) can realize faster achievements in direct liquid precursor to solidified electrolyte translation. Li₇La₃Zr₂O₁₂ (LLZO) is a promising solid electrolyte that has seen much interest in the battery field and has been demonstrated to be manufacturable with thickness between 1-15 µm via SDS. In this work, we demonstrate for the first time a high throughput, computer-controlled SDS deposition system to rapidly fabricate LLZO and alter its structure-property characteristics with precursor and deposition modulations. Dopant amounts are adjusted in real-time to easily control film composition and test a wide parameter field. In-situ annealing is achieved via an advanced heating element implemented directly into the chamber. Raman spectroscopy exhibits sufficient sensitivity to the phases under study, is a contactless and nondestructive technique, and has a low data acquisition time allowing for high-volume analysis coupled to high throughput synthesis. A quantification of Raman spectra is presented and a surrogate model is used in a Bayesian optimization framework for greater experimental efficiency by selecting interesting regions by phase and other 2nd order characteristics of the experimental space to selectively sample for desired phases. The capabilities of the new experimental framework are discussed for further work in accelerated solid-state ceramic materials discovery and we employ here careful considerations on the synthesis methods and computational approaches chosen towards the plethora of ceramic process options. This framework is capable of rapidly synthesizing solid-state electrolytes with a variety of composition and deposition conditions to optimize their properties so they can rapidly be deployed in next-generation batteries in significantly shorter times than traditional methods allow.