Heat dissipation from 3D chip stacks can cause large thermal gradients due to the accumulation of dissipated heat and thermal interfaces from each integrated die. To reduce the overall thermal resistance and thereby the thermal gradients, this publication will provide an overview of several studies on the formation of sequential thermal underfills that result in percolation and quasi-areal thermal contacts between the filler particles in the composite material. The quasi-areal contacts are formed from nanoparticles self-assembled by capillary bridging, so-called necks. Thermal conductivities of up to 2.5 W/m-K and 2.8 W/m-K were demonstrated experimentally for the percolating and the neck-based underfills, respectively. This is a substantial improvement with respect to a state-of-the-art capillary thermal underfill (0.7 W/m-K).