RESUMEN
As is well-known, the phonon and electron thermal conductivity of a thin film generally decreases as its thickness scales down to nanoscales due to size effects, which have dramatic engineering effects, such as overheating, low reliability, and reduced lifetime of processors and other electronic components. However, given that thinner films have higher surface-to-volume ratios, the predominant surface effects in these nanomaterials enable the transport of thermal energy not only inside their volumes but also along their interfaces. In polar nanofilms, this interfacial transport is driven by surface phonon polaritons, which are electromagnetic waves generated at mid-infrared frequencies mainly by the phonon-photon coupling along their surfaces. Theory predicts that these polaritons can enhance the in-plane thermal conductivity of suspended silica films to values higher than the corresponding bulk one, as their thicknesses decrease through values smaller than 200 nm. In this work, we experimentally demonstrate this thermal conductivity enhancement. The results show that the in-plane thermal conductivity of a 20 nm thick silica film at room temperature is nearly twice its lattice vibration counterpart. Additional thermal diffusivity measurements reveal that the diffusivity of a silica film also increases as its thickness decreases, such that the ratio of thermal conductivity/thermal diffusivity (volumetric heat capacity) remains nearly independent of the film thickness. The experimental results obtained here will enable one to build on recent interesting theoretical predictions, highlight the existence of a new heat channel at the nanoscale, and provide a new avenue to engineer thermally conductive nanomaterials for efficient thermal management.
RESUMEN
We present a study on the many-body exciton interactions in a Ruddlesden-Popper tin halide, namely, (PEA)2SnI4 (PEA = phenylethylammonium), using coherent two-dimensional electronic spectroscopy. The optical dephasing times of the third-order polarization observed in these systems are determined by exciton many-body interactions and lattice fluctuations. We investigate the excitation-induced dephasing (EID) and observe a significant reduction of the dephasing time with increasing excitation density as compared to its lead counterpart (PEA)2PbI4, which we have previously reported in a separate publication [J. Chem. Phys.2020, 153, 164706]. Surprisingly, we find that the EID interaction parameter is four orders of magnitude higher in (PEA)2SnI4 than that in (PEA)2PbI4. This increase in the EID rate may be due to exciton localization arising from a more statically disordered lattice in the tin derivative. This is supported by the observation of multiple closely spaced exciton states and the broadening of the linewidth with increasing population time (spectral diffusion), which suggests a static disordered structure relative to the highly dynamic lead-halide. Additionally, we find that the exciton nonlinear coherent lineshape shows evidence of a biexcitonic state with low binding energy (<10 meV) not observed in the lead system. We model the lineshapes based on a stochastic scattering theory that accounts for the interaction with a nonstationary population of dark background excitations. Our study provides evidence of differences in the exciton quantum dynamics between tin- and lead-based Ruddlesden-Popper metal halides (RPMHs) and links them to the exciton-exciton interaction strength and the static disorder aspect of the crystalline structure.