Using photovoltage (PV) spectroscopy we analyse the electronic structure of a series of GaBi x As x 1− /(Al)GaAs dilute bismide quantum well (QW) laser structures. The use of polarisation-resolved PV measurements allows us to separately identify transitions involving bound light-and heavy-hole states in the QWs, as well as bound-to-continuum transitions from the QWs to the barriers. Analysis of these transitions enables us to probe the GaBi x As x 1− /(Al) GaAs conduction and valence band offsets, thereby quantifying the band offsets. Using a 12band k p• Hamiltonian, we extract the band offsets in the QWs explicitly by constraining the Birelated parameters of the model against the experimentally measured transition energies. The PV measurements and k p• calculations we present provide the first explicit confirmation of a type-I band offset at the GaBi x As x 1− /GaAs heterointerface near x = 2%. This result, combined with the theory we present for calculating the band offsets at GaBi x As x 1− /(Al)GaAs heterointerfaces, can be used to determine the band offsets at arbitrary Bi composition x.
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