Negative Thermal Expansion of Sulphur-Doped Graphene Oxide

The sulfur content present in graphene oxide prepared by Hummers' method has only been addressed by few papers so far. By modified Hammers method we synthesized thermally stable in ambient environment multilayer sulphur-doped graphene oxide. The samples were heat treated in an electrical furnace setup at different ambient temperatures and their crystallite size and linear coefficient of thermal expansion were extracted from Raman band intensity peak ratio as a function of temperature. We found unusually large (in comparison with graphene oxide) contraction on heating of multilayer two weight percent sulphur-doped graphene oxide with carbon to oxygen ratio of 2.3 in a narrow temperature range (308-318 K) with the lowest value of the linear thermal expansion coefficient of -18 ppm 1/K. Based upon an examination of the synthesized sulphur-doped graphene diffractograms, it is suggested that negative thermal expansion stems from the phonon backscattering by the sulphur impurity sites and the edges of the layers. The obtained experimental results have potential practical applications for fabrication of solar cells, sensors, lubricators, thermal actuators and also wavelike (second sound) thermal transport structures.