The capture cross-section, intersubband optical cross-section and non-radiative emission rates related to localized hole states are obtained for p-i-n solar cells containing GaSb/GaAs quantum rings embedded within the i-region of the device. The technique developed uses the intraband photoemission current to probe the charge state of the nanostructures during two-color excitation. Analysis of the excitation power dependence revealed a non-radiative hole capture lifetime of 12 ns under low excitation conditions, with high injection leading to the saturation of the hole occupancy within the quantum-rings. The decay characteristics of the optical hole emission current has also been exploited to determine the spectral and temperature dependence of the radiative and non-radiative hole escape mechanisms from the quantum-rings.