A photocathode is formed on a monocrystalline silicon substrate having opposing illuminated (top) and output (bottom) surfaces. To prevent oxidation of the silicon, a thin (e.g., 1-5 nm) boron layer is disposed directly on the output surface using a process that minimizes oxidation and defects. An optional second boron layer is formed on the illuminated (top) surface, and an optional anti-reflective material layer is formed on the second boron layer to enhance entry of photons into the silicon substrate. An optional external potential is generated between the opposing illuminated (top) and output (bottom) surfaces. The photocathode forms part of novel electron-bombarded charge-coupled device (EBCCD) sensors and inspection systems.