Entropy-driven nonequilibrium phonon-stimulated electron-phonon coupling in tin dioxide nanorods

Nonequilibrium (NEQ) phonon fluctuation in a nanosystem has been studied through the statistical assessment of the entropy-production and -consumption events in ultrasmall tin dioxide (SnO_{2}) nanorods. Size- and shape-dependent alteration in free energy leading to modulation of the probability distribution function of the phonon dynamics has been observed from the x-ray diffraction and Raman scattering characterizations. The Gallavotti-Cohen nonequilibrium fluctuation theorem has been utilized to qualitatively describe the aforementioned behaviors under the influence of a global flux. The observation of entropy consumption and thermodynamically favorable entropy-production events indicates the presence of NEQ fluctuations in the phonon modes. The effective energy scale of fluctuation in driven phonon modes, dissipating energy faster than relaxation time, is quantified on the order of nanojoules. From optical absorption and photoluminescence studies, the observation of the electron-phonon coupled state confirms the interaction of the NEQ phonons with electrons. The strength of the coupling has been estimated from the temperature-independent Barry center shift and found to be enhanced to 5.35. Valence band x-ray photoelectron spectroscopy and Fourier transformed infrared spectroscopy analyses reconcile NEQ phonon mediated alteration of the valence band density of states, activation of silent phonon modes, and superior excitonic transitions, suitable for the new generation of ultrafast quantum device applications.