Amorphous Li3PS4 films were synthesized by pulsed laser deposition (PLD) at room temperature using Li3PS4 targets with excess lithium and sulfur. Raman and X‐ray photoemission spectroscopies indicated that the Li3PS4 film synthesized with a stoichiometric amount of Li3PS4 target contained lithium‐deficient phases such as Li4P2S6, Li2−xS and sulfur due to composition deviation caused during the ablation process. The film synthesized with a 14% Li2S‐excess target (Li3.42PS4.21) contained fewer impurities, and exhibited a higher ionic conductivity of 5.3 × 10−4 S/cm at 298 K than the lithium‐deficient film (3.1 × 10−4 S/cm). The target composition is an important factor for the fabrication of highly conductive Li3PS4 films for electrolytes in thin‐film batteries.
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