Origins of significant reduction of lattice thermal conductivity in graphene allotropes

Abstract

Coherent wave effects of thermal phonons hold promise of transformative opportunities in thermal transport control but remain largely unexplored due to the small wavelength of thermal phonons, typically below a few nanometers. This small length scale indicates that, instead of artificial phononic crystals, a more promising direction is to examine the coherent phonon effects in natural materials with hierarchical superstructures matching the thermal phonon wavelength. In this work, we use first-principles simulations to characterize the previously unstudied thermal properties of D-graphene and T-graphene, two-dimensional carbon allotropes based upon the traditional graphene structure but containing a secondary, in-plane periodicity. We find that despite very similar atomic structure and bonding strength, D-graphene and T-graphene possess significantly different thermal properties than that of pristine graphene. At room temperature, the calculated thermal conductivity of D-graphene and T-graphene is 600 Wm-1K-1 and 800 Wm-1K-1 compared to over 3000 Wm-1K-1 for graphene. We attribute these distinct properties to the presence of naturally occurring, low frequency optical phonon modes that display characteristics of phonon coherence and arise from a folding of the acoustic modes and the associated frequency gap opening, a phenomenon also found in superlattices where an out of plane periodicity is introduced. Furthermore, we observe significantly enhanced Umklapp scatterings in D- and T-graphene that largely suppress the hydrodynamic phonon transport in pristine graphene. Our study presents D-graphene and T-graphene as ideal model systems to explore the coherent phonon effects in 2D and demonstrates the potential of using coherent phonon effects to significantly modify thermal transport of 2D materials without making drastic changes to their fundamental compositions.