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Studies using in-situ Auger electron spectroscopy and reflection high energy electron diffraction, and ex-situ high resolution X-ray diffraction and electron backscatter diffraction reveal that a MgS thin film grown directly on a GaAs (100) substrate by molecular beam epitaxy adopts its most stable phase, the rocksalt structure, with a lattice constant of 5.20 Å. A Au/MgS/n+-GaAs (100) Schottky-barrier photodiode was fabricated and its room temperature photoresponse was measured to have a sharp fall-off edge at 235 nm with rejection of more than three orders at 400 nm and higher than five orders at 500 nm, promising for various solar-blind UV detection applications.