Strain effects on thermal conductivity of nanostructured silicon by Raman piezothermography

A fundamental problem facing the rational design of materials is the independent control of electrical and thermal properties, with implications for a wide range of applications including thermoelectrics, solar thermal power generation, and thermal logic. One strategy for controlling transport involves manipulating the length scales which affect it. For instance, Si thermal conductivity may be reduced with relatively little change in electrical properties when the confining dimension (e.g., nanowire diameter) is small enough that heat carriers are preferentially scattered at free surfaces. However, tailoring properties by geometry or chemistry alone does not allow for on-demand modification, precluding applications which require responsive behavior such as thermal transistors, thermoelectric modules which adapt to their environmental temperature, or switchable thermal barriers. One means of tuning transport is elastic strain, which has long been exploited to improve carrier mobility in electronic devices. Uniform strain is predicted to affect thermal conductivity primarily via changes in heat capacity and phonon velocity, and crystalline defects such as vacancies or dislocations—which induce large strain gradients—should lower thermal conductivity by decreasing the phonon mean free path. Nanowires are ideal for the study of strain and defect effects due to the availability of a range of elastic strain an order of magnitude larger than in bulk and due to their small volumes. However, experimental measurements of strainmediated thermal conductivity in nanowires have been limited due to the complexity of simultaneously applying and measuring stress or strain, heating, and measuring temperature. In this dissertation, we measure strain effects on thermal conductivity using a novel non-contact approach which we name Raman piezothermography. We apply a uniaxial load to individual Si nanowires, Si thin films, and Si micromeshes under a confocal μ-Raman microscope and, using the Raman laser as a heat source and the Raman spectrum as a measure of temperature, determine thermal transport properties. We show that uniaxial strain up to ∼1% has a weak effect on Si nanowire or thin film thermal conductivity, but irradiationinduced defects in nanowires yield dramatic reductions due to increased phonon scattering. Such defects are accompanied by large strain gradients, but decoupling the effect of these gradients from local changes in mass and interatomic potential is experimentally untenable. To isolate the effect of strain gradients, we extend our method to Si micromeshes, which exhibit nonuniform strains upon loading. The complex strain states achieved cause more drastic reductions of thermal conductivity due to enhanced phonon-phonon scattering in the presence of a strain gradient. The directions suggested by our experiments, as well as the development of the method, will allow for more robust understanding and control of thermal transport in nanostructures. Degree Type Dissertation Degree Name Doctor of Philosophy (PhD) Graduate Group Materials Science & Engineering This dissertation is available at ScholarlyCommons: http://repository.upenn. edu/edissertations/1381 First Advisor Daniel S. Gianola