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InAsP/InP strained multiple quantum wells (MQWs) with specular surfaces were grown on InP (111)B substrates by gas‐source molecular beam epitaxy. Cross‐sectional transmission electron microscopy and high‐resolution x‐ray rocking curves show that the InAsP/InP (111)B MQW structures possess sharp and uniform interfaces, excellent periodicity, and crystalline quality. Structural parameters were extracted accurately from a dynamical‐theory simulation by considering the anisotropy of the (111) strain tensor. Low‐temperature photoluminescence and photoluminescence excitation measurements revealed interband excitonic transitions, and the energies agree with a calculation with an internal piezoelectric field taken into account.