Single crystals of Cu2ZnSnS4 have been produced within sealed quartz ampoules via the chemical vapour transport technique using I-2 as the transporting agent. The effects of temperature gradient and I-2 load on the crystal habit and composition are considered. Crystals have been analyzed with XRD, SEM, and TEM for compositional and structural uniformities at both microscopic and nanoscopic levels. The synthesized crystals have suitable (I-2-load dependent) properties and are useful for further solar absorber structural and physical characterizations. A new chemical vapour transport method based on longitudinally isothermal treatments is attempted. Based on a proposed simplistic mechanism of crystal growth, conditions for crystal enlargement with the new method are envisaged. (C) 2012 Elsevier B.V. All rights reserved.