AbstractHigh quality AgGaSe2single crystals with 20 mm in diameter and 55 mm in length have been grown by the modified Bridgman technique and the growth habits of AgGaSe2single crystals have been investigated in detail. It is found that the shape of the growth ampoule affects greatly the nucleation and the growth of AgGaSe2single crystal. A new cleavage face (101) and the natural faces are observed in the as‐grown crystals. For some cases, the growing direction is normal to the (316) fac