InAs/AlSb/GaSb/AlSb/InAs interband‐tunneling structures have been analyzed with respect to the composition and structural quality of the AlSb tunneling barriers. The addition of AlAs monolayers at the interfaces between the AlSb barriers and the InAs and GaSb layers was found to result in the expected reduction in the valley current density of the resonant interband‐tunneling diode. Vibrational mode Raman spectroscopy showed that the introduction of AlAs monolayers led to the formation of pseudoternary Al(SbAs) barriers, which cause the observed reduction of the valley current density. Ellipsometric measurements indicate that the structural quality of both types of barrier layers, with and without AlAs monolayers added to the interfaces, is inferior to that of thick bulklike AlSb layers. The observation of Raman scattering from a coupled hole plasmon‐phonon mode indicates the formation of a hole gas in the GaSb quantum well at the center of the tunneling structure. ©1995 American Institute of Physics.