C.W. Yuan

Embedded Binary Eutectic Alloy Nanostructures: A New Class of Phase Change Materials

Phase change materials are essential to a number of technologies ranging from optical data storage to energy storage and transport applications. This widespread interest has given rise to a substantial effort to develop bulk phase change materials well suited for desired applications. Here, we suggest a novel and complementary approach, the use of binary eutectic alloy nanoparticles embedded within a matrix. Using GeSn nanoparticles embedded in silica as an example, we establish that the presence of a nanoparticle/matrix interface enables one to stabilize both nanobicrystal and homogeneous alloy morphologies. Further, the kinetics of switching between the two morphologies can be tuned simply by altering the composition.

Superheating and supercooling of Ge nanocrystals embedded in SiO2

Superheating and supercooling of Ge nanocrystals embedded in SiO 2 Q. Xu, 1,2 I.D. Sharp, 1,2 C.W. Yuan, 1,2 D.O. Yi, 1,2 C.Y. Liao, 1,2 A.M. Glaeser, 1,2 A.M. Minor, 4 J.W. Beeman, 1 M.C. Ridgway, 5 P. Kluth, 5 J.W. Ager III, 1 D.C. Chrzan, 1,2 and E.E. Haller 1,2,* Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA Department of Materials Science and Engineering, University of California, Berkeley, CA 94720 USA Lawrence Livermore National Laboratory, Livermore, CA 94550, USA National Center for Electron Microscopy , Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA Department of Electronic Materials Engineering, Research School of Physical Sciences and Engineering, Australian National University, Canberra ACT 0200, Australia Email: eehaller@lbl.gov Abstract. Free-standing nanocrystals exhibit a size-dependant thermodynamic melting point reduction relative to the bulk melting point that is governed by the surface free energy. The presence of an encapsulating matrix, however, alters the interface free energy of nanocrystals and their thermodynamic melting point can either increase or decrease relative to bulk. Furthermore, kinetic contributions can significantly alter the melting behaviours of embedded nanoscale materials. To study the effect of an encapsulating matrix on the melting behaviour of nanocrystals, we performed in situ electron diffraction measurements on Ge nanocrystals embedded in a silicon dioxide matrix. Ge nanocrystals were formed by multi-energy ion implantation into a 500 nm thick silica thin film on a silicon substrate followed by thermal annealing at 900 °C for 1 h. We present results demonstrating that Ge nanocrystals embedded in SiO 2 exhibit a 470 K melting/solidification hysteresis that is approximately symmetric about the bulk melting point. This unique behaviour, which is thought to be impossible for bulk materials, is well described using a classical thermodynamic model that predicts both kinetic supercooling and kinetic superheating. The presence of the silica matrix suppresses surface pre-melting of nanocrystals. Therefore, heterogeneous nucleation of both the liquid phase and the solid phase are required during the heating and cooling cycle. The magnitude of melting hysteresis is governed primarily by the value of the liquid Ge/solid Ge interface free energy, whereas the relative values of the solid Ge/matrix and liquid Ge/matrix interface free energies govern the position of the hysteresis loop in absolute temperature.