Use of transmission electron microscopy in the characterization of GaInNAs(Sb) quantum well structures grown by molecular beam epitaxyEnhanced band-gap blueshift due to group V intermixing in InGaAsP multiple quantum well laser structures induced by low temperature grown InP High-resolution x-ray diffractometry ͑HRXRD͒ and transmission electron microscopy ͑TEM͒ are employed to characterize a quaternary III x III 1Ϫx V y V 1Ϫy AlGaAsSb/GaInAsSb multiple quantum well ͑MQW͒ heterostructure. A method for uniquely determining the chemical composition of the strained quaternary quantum well, information previously thought to be unattainable using HRXRD, is thoroughly described. The misconception that HRXRD can separately find the well and barrier thickness of a MQW from the pendellosung fringe spacing is corrected and, thus, the need for TEM is motivated. Computer simulations show that the key in finding the well composition is the intensity of the higher order satellite peaks in the diffraction pattern. For the AlGaAsSb/InGaAsSb MQWs analyzed in this work, the variation in the intensity of the third-order satellite peak is identified as a sensitive measure of the quantum well composition. Using HRXRD on an MQW semiconductor laser device layer, the ability to resolve this higher order peak and interpret the information contained in it is demonstrated for the first time.