Pseudo-Anomalous Size-Dependent Electron-Phonon Interaction in Graded Energy Band: Solving the Fano Paradox

Manushree Tanwar, Devesh K. Pathak, Anjali Chaudhary, Alexander S. Krylov, Herbert Pfnür, Ashutosh Sharma*, Byungmin Ahn*, Sangyeob Lee*, and Rajesh Kumar. JOURNAL OF PHYSICAL CHEMISTRY LETTERS . DOI: 10.1021/acs.jpclett.1c00217

Quantum size effects on interferons (electron-phonon bound states), confined in fractal silicon (Si) nanostructures (NSs), have been studied by using Raman spectromicroscopy. A paradoxical size dependence of Fano parameters, estimated from Raman spectra, has been observed as a consequence of longitudinal variation of nanocrystallite size along the Si wires leading to local variations in the dopants' density which actually starts governing the Fano coupling, thus liberating the interferons to exhibit the typical quantum size effect. These interferons are more dominated by the effective reduction in dopants' density rather than the quantum confinement effect. Detailed experimental and theoretical Raman line shape analyses have been performed to solve the paradox by establishing that the increasing size effect actually is accompanied by receding Fano coupling due to the weakened electronic continuum. The latter has been validated by observing a consequent variation in the Raman signal from dopants which was found to be consistent with the above conclusion.