Lithium containing A(I)B(III)C(VI) semiconductors are being considered as alternative materials for room temperature neutron detection. Materials such as LiGaSe2 have been synthesized for non-linear optical applications; however, when the crystal is grown enriched in the Li-6 isotope, it is possible to imagine a radiation detector. A nuclear reaction occurs with Li-6, which can be detected within the semiconductor crystal. As such, high quality crystals are required, which have few defects which prohibit charge collection. One of the primary challenges in growing a high quality crystal is the reactivity of lithium metal. Vacuum purified lithium metal was therefore reacted with gallium to form LiGa as an intermediate to LiGaSe2 synthesis. Vertical and horizontal Bridgman growth was then conducted to determine the optimal growth conditions. Vertical Bridgman growth resulted in more pure crystals. Annealing in lithium metal vapor reduced crystal defects and improved optical and electrical properties of the subsequent LiGaSe2 crystal. Published by Elsevier B.V.