To determine the band alignment at the GaSb1-xBix/GaSb interface, a set of GaSb1-xBix/GaSb quantum wells (QWs) of various widths (7, 11, and 15 nm) and contents (Bi ≤ 12%) were grown by molecular beam epitaxy and investigated by photoreflectance (PR) spectroscopy. In PR spectra, the optical transitions related to both the ground and the excited states in the QW were clearly observed. It is a direct experimental evidence that the GaSb1-xBix/GaSb QW is a type-I QW with a deep quantum confinement in both the conduction and valence bands. From the comparison of PR data with calculations of energies of QW transitions performed for the varying valence band offset (VBO), the best agreement between experimental data and theoretical calculations has been found for the VBO ∼50 ± 5%. A very similar VBO was obtained from ab initio calculations. These calculations show that the incorporation of Bi atoms into a GaSb host modifies both the conduction and valence band: the conduction-band position changes linearly at a rate of ∼15–16 meV per % Bi and the valence band position changes at a rate of ∼15–16 meV per % Bi. The calculated shifts of valence and conduction bands give the variation of VBO between GaSb1-xBix and GaSb in the range of ∼48%–52%, which is in good agreement with conclusions derived from PR measurements. In addition, it has been found that the electron effective mass reduces linearly with the increase in Bi concentration (x): , where is the electron effective mass of GaSb. Moreover, a strong photoluminescence (PL) was observed and a negligible Stokes shift (less than a few meV) between the PL peak and the fundamental transition in the PR spectrum was detected for all QWs at low temperatures. It means that the investigated QWs are very homogeneous, and the carrier localization for this alloy is very weak in contrast to other dilute bismides.
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