AbstractThe optical and electronic properties of semiconducting materials are of great importance to a vast range of contemporary technologies. Diamond-cubic germanium is a well-known semiconductor, although other ‘exotic’ forms may possess distinct properties. In particular, there is currently no consensus for the band gap and electronic structure of ST12-Ge (tP12, P4₃2₁2) due to experimental limitations in sample preparation and varying theoretical predictions. Here we report clear experimental and theoretical evidence for the intrinsic properties of ST12-Ge, including the first optical measurements on bulk samples. Phase-pure bulk samples of ST12-Ge were synthesized, and the structure and purity were verified using powder X-ray diffraction, transmission electron microscopy, Raman and wavelength/energy dispersive X-ray spectroscopy. Optical measurements indicate that ST12-Ge is a semiconductor with an indirect band gap of 0.59 eV and a direct optical transition at 0.74 eV, which is in good agreement with electrical transport measurements and our first-principles calculations.