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We report a comprehensive temperature dependent Raman measurements on threedifferent phases of monolayer WS2 from 4K to 330K in a wide spectral range. Ourstudies revels the anomalous nature of the first as well as the higher ordercombination modes reflected in the disappearance of the few modes and anomaloustemperature evaluation of the phonon self-energy parameters attributed to thedetuning of resonance condition and development of strain due to thermalexpansion mismatch with the underlying substrate. Our detailed temperaturedependence studies also decipher the ambiguity about assignment of the twomodes in literature near ~ 297 cm-1 and 325 cm-1. Mode near 297 cm-1 isassigned as first order Raman mode, which is forbidden in the backscatteringgeometry and 325 cm-1 is assigned to the combination of and mode. We alsoestimated thermal expansion coefficient by systematically disentangling thesubstrate effect in the temperature range of 4K to 330K and probed itstemperature dependence in 1H, 1T and 1T' phases.

Thermal Expansion Coefficient and Phonon Dynamics in Coexisting Allotropes of Monolayer WS2 Probed by Raman Scattering