The authors used differential scanning calorimetry and high temperature oxide melt calorimetry to investigate the interface energies in various multilayer systems. For yttria stabilized zirconia (YSZ)/Al2O3 multilayers, the presence of interfaces is shown to affect the temperature and the enthalpy of crystallization; and therefore these interfaces play an important role in phase stability. From the thermal analysis results, it can be concluded that in YSZ/Al2O3 multilayers, the Al2O3 crystallization temperature increases and the enthalpy becomes less exothermic compared to the values for single alumina films. It is also shown that crystalline perovskite films of La(Sr)MnO3 can be deposited on NaCl substrates and can be collected from the substrate after the deposition which makes them suitable for high temperature calorimetry. (C) 2010 American Vacuum Society. [DOI: 10.1116/1.3420396]