Using a combination of rigorous coupled-wave analysis and simulated annealing, parallel-face slanted surface-relief gratings (PFSSRGs) are optimized. For substrate-mode optical interconnects, profiles are presented for both polymer and silicon PFSSRGs for both TE and TM polarizations at normal incidence with grating periods designed to give a 45 degrees output angle in the negative-first forward-diffracted order. The resulting diffraction efficiencies range from 70% to 99%, with a majority of the optimized profiles yielding over 90%. Optimized polymer profiles for TE and TM polarizations exhibit similar high diffraction efficiencies, but the TM profiles generally require greater groove depths. Silicon profiles optimized for TM polarization have greater diffraction efficiencies than those for TE polarization. Profiles that can feasibly be fabricated are identified, and sensitivities to groove depth, filling factor, slant angle, and incident angle are shown to be modest.