Mechanically stiffened and thermally softened Raman modes of ZnO crystal.

An analytical form connecting the energy shift of Raman modes directly to the bonding identities (order, nature, length, energy) of a specimen and the response of the bonding identities to the applied stimuli of temperature and pressure was presented for a deeper understanding of the atomistic origin of the ZnO Raman shift. Theoretical reproduction based on the BOLS correlation theory [Sun, C. Q. Prog. Solid State Chem. 2007, 35, 1] and the local bond average (LBA) approach [Sun, C. Q. Prog. Mater. Sci. 2009, 54, 179] of the measurements revealed that the thermally softened ZnO Raman modes arise from bond expansion and bond weakening due to vibration and that the pressure-stiffened Raman modes result from bond compression and bond strengthening due to mechanical work hardening. The developed approach could be useful in generalizing the lattice dynamics directly to the process of vibration and relaxation of a representative bond of the specimen under external stimuli.