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Dependence of structural parameters on the size of nanoparticles is a topicof general interest where the effect of shape is often neglected. We report acomprehensive study on size dependent structural parameters of ZnOnanostructures (NS) having a wide range of aspect ratios (length/diameter). Itreveals that with increase in size, ZnO NS undergo a shape transition fromspherical to rod like morphology that induces sudden change in internalparameter (u) which represents relative position of two hexagonal close-packedsublattices. The change in u introduces concomitant changes in anion-cation(Zn-O) bond lengths as well as bond angles and thereby bears a lineardependence with the aspect ratio (AR). Further, the unit cell volume andmicrostrain decrease with increase in particle size and show a drasticreduction when flat crystal faces begin to appear at the spherical surface(AR~1.3). The significant change in structural parameters associated with theshape transition arises due to surface dipole induced electrostatic relaxationthat may be further influenced by interaction with the ambient gases asevidenced from the Extended X-ray Absorption Fine Structure (EXAFS)measurement. The present study addresses the underlying reasons of shapeinduced change in structural and electronic properties of ZnO NS.

Effect of size and aspect ratio on structural parameters and evidence of shape transition in zinc oxide nanostructures