Theoretical and experimental studies have confirmed that the GaAs1-yBiy semiconductor alloy system has potential for long wavelength applications and devices with improved performance over other materials emitting at similar wavelengths. The growth of GaAs1-yBiy by metal organic vapor phase epitaxy (MOVPE) remains a challenge; bismuth is not easily incorporated into the GaAs matrix due the large difference in electronegativity and covalent radii between As and Bi. These differences often lead to Bi surface segregation or very low incorporation rates of Bi into the GaAs matrix. We have studied the growth of GaAs, Bi, quantum well structures using trimethyl bismuth as the Bi source. A reduced growth rate is observed with increasing Bi precursor flux into the growth reactor. Additionally, an increase in the growth time for the Bi-containing layer at very low growth temperatures does not lead to a corresponding increase in layer thickness, which is indicative of a near self-limiting growth. Complex compositional profiles deduced born combining x-ray diffraction analysis with the transmission electron microscopy investigations are used to develop a phenomenological model of the MOVPE growth of GaAs1-yBiy heterostructures which includes a complex interplay of the chemical surface species. The presence of a methyl-terminated surface, associated with the use of trimethyl Bi, particularly at low growth temperatures, leads to an effective "site blocking" by Bi precursor inhibiting the growth of GaAs1-yBiy hetero-structures. (C) 2014 Elsevier B.V. All rights reserved.