Mechanism of plasmon-mediated enhancement of photovoltaic efficiency

Metallic nanospheres (Au, Ag, Cu) deposited on a photovoltaic (PV)-active semiconductor surface can act as light converters, collecting energy of incident photons in plasmon oscillations. This energy can be next transferred to a semiconductor substrate via a near-field channel, in a more efficient manner in comparison with the direct photo-effect. We explain this enhancement by inclusion of indirect interband transitions in a semiconductor layer due to the near-field coupling with plasmon radiation in nanoscale of the metallic components, where the momentum is not conserved as the system is not translationally invariant. The model of the nanosphere plasmons is developed (random phase approximation, analytical version, adjusted to description of large metallic clusters, with a radius of 10–60 nm) including surface and volume modes. Damping of plasmons is analysed via Lorentz friction, and irradiation losses in the far- and near-field regimes. Resulting resonance shifts are verified experimentally for Au and Ag colloidal water solutions with respect to particle size. Probability of the electron interband transition (within the Fermi golden rule) in the substrate semiconductor induced by coupling to plasmons in the near-field regime turns out to be significantly larger than for coupling of electrons to planar-wave photons. This is of practical importance for enhancement of thin-film solar cell efficiency, both for semiconductor type (such as III–V semiconductor based cells) and for conjugate-polymer-based or dye organic plastic cells, intensively developed at present. We have described also a non-dissipative collective mode of surface plasmons in a chain of near-field-coupled metallic nanospheres, for particular size, separation parameters and wavelengths. This would find an application in sub-diffraction electro-photonic circuit arrangement and for possible energy transport in solar cells, in particular in organic materials with low mobility of carriers.