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In millimeter-wave channels, most of the received energy is carried by a few paths. Traditional precoders sweep the angle-of-departure (AoD) and angle-of-arrival (AoA) space with directional precoders to identify directions with largest power. Such precoders are heuristic and lead to suboptimal AoD/AoA estimation. We derive optimal precoders, minimizing the Cramér-Rao bound (CRB) of the AoD/AoA under a given uncertainty range, assuming a fully digital architecture at the transmitter and spatial filtering of a single path. The precoders are found by solving a suitable convex optimization problem. We demonstrate that the accuracy can be improved by at least a factor of two over traditional precoders, and show that there is an optimal number of distinct precoders beyond which the CRB does not improve.