A comprehensive assessment of the low-temperature thermal properties and thermodynamic functions of CeO2.

Reported is an experimental and computational investigation of the low temperature heat capacity, thermodynamic functions, and thermal conductivity of stoichiometric, polycrystalline CeO2. The experimentally measured heat capacity at T < 15 K provides an important correction to the historically accepted experimental values, and the low temperature thermal conductivity serves as the most comprehensive data set at T < 400 K available. Below 10 K, the heat capacity is observed to obey the Debye T3 law, with a Debye temperature of ΘD = 455 K. The entropy, enthalpy, and Gibbs free energy functions are obtained from the experimental heat capacity and compared with predictions from Hubbard-corrected density functional perturbation theory calculations using the Perdew, Burke, and Ernzerhof parameterization revised for solids. The thermal conductivity is determined using the Maldonado continuous measurement technique, along with laser flash analysis, and analyzed according to the Klemens-Callaway model.

Liquid-assisted tip manipulation: fabrication of twisted bilayer graphene superlattices on HOPG.

We use the tip of a scanning tunneling microscope (STM) to manipulate single weakly bound nanometer-sized sheets on a highly oriented pyrolytic graphite (HOPG) surface through artificially increasing the tip and sample interaction by pretreatment of the surface using a liquid thiol molecule. By this means it is possible to tear apart a graphite sheet against a step and fold this part onto the HOPG surface and thus generate graphene superlattices with hexagonal symmetry. The tip and sample surface interactions, including the van der Waals force, electrostatic force and capillary attraction force originating from the Laplace pressure due to the formation of a highly curved fluid meniscus connecting the tip and sample, are discussed quantitatively to understand the formation mechanism of a graphene superlattice induced by the STM tip. The capillary force plays a key role in manipulating the graphite surface sheet under humid conditions. Our approach provides a simple and feasible route to prepare controllable superlattices and graphene nanoribbons and also to better understand the process of generation of a graphene superlattice on the surface of HOPG with the tip.