© 2021 Author(s).Heterogeneous integration of β-(SnxGa1-x)2O3 (TGO) UV-C photodetectors on silicon substrates by molecular beam epitaxy is demonstrated. Multimodal electron microscopy and spectroscopy techniques reveal a direct correlation between structural, compositional, and optical properties of TGO and the functional properties of the photodetectors. Wavelength dispersive x-ray spectroscopy results accurately determine Sn concentrations (x) in the region of 0.020, and room temperature cathodoluminescence (CL) hyperspectral imaging shows changes in the CL emission intensity in TGO compared with a Ga2O3 sample with no Sn. Alloying Ga2O3 with Sn is shown to quench the red emission and enhance the blue emission. The increase in blue emission corresponds to the rise in VGa-related deep acceptors responsible for the high gain observed in the TGO detectors. A Ga2O3 nucleation layer is shown to improve the TGO surface quality and give better device properties compared to TGO grown directly onto the Si substrate, including a higher specific detectivity on the order of 1012 Jones.