Abstract: Heat is one of the most fundamental forms of energy, and the ability to control heat plays a critical role in most current and future energy applications. Recently, nanoscale engineering has provided new approaches to manipulate heat transport at the scales of the heat carriers in solids. Despite these advances, we still lack a comprehensive understanding of energy carriers in solids, which would allow us to achieve precise control of energy transport at the nanoscale. My research interests lie in furthering our knowledge of energy carriers, especially electrons and phonons (quantized lattice vibrations). In the first part of my talk, I will give a brief introduction to ultrafast laser spectroscopies that allow us to simultaneously characterize macroscopic thermal properties and microscopic thermal processes of energy carriers in bulk crystals as well as nanometer-thick thin films. In the second part of my talk, I will discuss a generalized Fourier’s law derived from the Boltzmann transport equation that is valid from diffusion to ballistic regimes. This generalized Fourier’s law contains two parts, nonlocality of thermal conductivity, which has been previously hypothesized, and nonlocality of boundary conditions, which has long been ignored in literatures. We apply the derived generalized Fourier’s law to predict the surface temperature responses of an ultrafast laser spectroscopic technique called time-domain thermoreflanctance (TDTR) under various conditions, demonstrating an excellent match between the theoretical predictions and experimental results. Furthermore, by exploiting the generalized Fourier’s law in a synthetic TDTR experiment on a single crystal boron arsenide, we show that in the non-diffusive thermal transport regime, simply interpreting the observation using a Fourier’s law with a modified thermal conductivity, a common practice in the community, would lead to erroneous results. To map the macroscopic observations to intrinsic phonon properties, it is crucial to appropriately take account into the microscopic boundary conditions. Our work shows that in a non-diffusive regime, the two parts of the generalized Fourier’s law are equally important to accurately describing the thermal transport, and we can take advantage of the nonlocal nature of the boundary conditions as an extra knob to manipulate the heat.