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High resolution x‐ray diffraction (HRXRD) has been used to determine the layer compositions and thicknesses of compressively strained InGaAs multiple‐quantum‐well (MQW) structures embedded in thick cladding layers that are nominally lattice matched to InP. The entire layer structure was accurately determined from the results of HRXRD measurements for a simple strained MQW structure in which barriers and claddings are of the same composition. The estimated margins of error are less than 1% for the quantum‐well indium composition and ±2.5 Å for well and barrier thicknesses. The layer structure of the active region in a complete InGaAlAs graded‐index separate confinement strained MQW laser diode has also been determined by HRXRD.