Neutron detectors fabricated from 10B enriched hexagonal boron nitride (h-10BN or h-BN) epilayers have demonstrated the highest thermal neutron detection efficiency among solid-state neutron detectors to date at about 53%. In this work, photoconductive-like vertical detectors with a detection area of 1 × 1 mm2 were fabricated from 50 μm thick free-standing h-BN epilayers using Ni/Au and Ti/Al bilayers as ohmic contacts. Leakage currents, mobility-lifetime (μτ) products under UV photoexcitation, and neutron detection efficiencies have been measured for a total of 16 different device configurations. The results have unambiguously identified that detectors incorporating the Ni/Au bilayer on both surfaces as ohmic contacts and using the negatively biased top surface for neutron irradiation are the most desired device configurations. It was noted that high growth temperatures of h-10BN epilayers on sapphire substrates tend to yield a higher concentration of oxygen impurities near the bottom surface, leading to a better device performance by the chosen top surface for irradiation than by the bottom. Preferential scattering of oxygen donors tends to reduce the mobility of holes more than that of electrons, making the biasing scheme with the ability of rapidly extracting holes at the irradiated surface while leaving the electrons to travel a large average distance inside the detector at a preferred choice. When measured against a calibrated 6LiF filled micro-structured semiconductor neutron detector, it was shown that the optimized configuration has pushed the detection efficiency of h-BN neutron detectors to 58%. These detailed studies also provided a better understanding of growth-mediated impurities in h-BN epilayers and their effects on the charge collection and neutron detection efficiencies.