Radio frequency glow discharge chemical vapor deposition has been used to deposit thin films ofa-Si1−xGex:Hwhich possess optoelectronic properties that are greatly improved over any yet reported in the range ofx⩾0.6.These films were deposited on the cathode (cathodic deposition) of an rf discharge. Their properties are assessed using a large variety of measurements and by comparison to the properties of alloys conventionally prepared on the anode (anodic deposition). Steady state photoconductivity measurements yield a quantum-efficiency-mobility-lifetime product, &eegr;&mgr;&tgr;, of (1–3)×10−7 cm2 V−1for1.00⩾x⩾0.75and(6–10)×10−8 cm2 V−1for0.75⩾x⩾0.50,and photocarrier grating measurements yield ambipolar diffusion lengths several times greater than previously obtained for alloys of largex.It is confirmed that the improvements in phototransport are not due to a shift in the Fermi level. In fact, results of recent measurements on lightly doped samples strongly suggest that for these cathodic alloys neither photocarrier is dominant[(&mgr;&tgr;)e≈(&mgr;&tgr;)h].The improvements are attributed in large part to the reduction of long range structural heterogeneity observed in x-ray scattering and electron microscopy, and partly to the reduction in midgap state density. In spite of the superior properties, an assessment of the data of the cathodic alloys suggests that alloying introduces mechanisms detrimental to transport which are not present ina-Si:Hora-Ge:H.The Urbach tail width is 42±2 meV for cathodica-Ge:Hand 45±2 meV for cathodica-Si1−xGex:Hand is constant withx.From differences in the band edges and tails we infer that the atomic bond ordering is different between the cathodic and anodic alloys. For a given composition the cathodic alloys have roughly an order of magnitude lower midgap state density than do the anodic alloys, and both midgap densities increase exponentially withx,consistent with defect creation models from which the lower midgap density can be attributed to a larger band gap and decreased valence band tail width. A photoluminescence peak is observed with an intensity roughly an order of magnitude greater than for the anodic alloys, and a significantly different peak energy. Section VII E provides an overview of the results and conclusions. The improved properties of these alloys have significant implications for current and future device applications. ©1997 American Institute of Physics.