We study the dependence of the quantum yield of photoluminescence of a dense, periodic array of semiconductor nanocrystals (NCs) on the level of doping and NC size. Electrons introduced to NCs via doping quench photoluminescence by the Auger process,
so that practically only NCs without electrons contribute to the photoluminescence. Computer simulation and analytical theory are used to find a fraction of such empty NCs as a function of the average number of donors per NC and NC size. For an array of small spherical NCs, the quantization gap between 1S and 1P levels leads to transfer of electrons from NCs with large number of donors to those without donors. As a result, empty NCs become extinct, and photoluminescence is quenched abruptly at an average number of donors per NC close to 1.8. The relative intensity of photoluminescence is shown to correlate with the type of hopping conductivity of an array of NCs.
We present a theoretical description of excitons and positively and negatively charged trions in giant CdSe/CdS core-shell nanocrystals (NCs). The developed theory provides the parameters describing the fine structure of excitons in CdSe/CdS core/thi
ck shell NCs as a function of the CdSe/CdS conduction band offset and the CdSe core radius. We have also developed a general theory describing the fine structure of positively charged trions created in semiconductor NCs with a degenerate valence band. The calculations take into account the complex structure of the CdSe valence band and inter-particle Coulomb and exchange interaction. Presented in this paper are the CdSe core size and CdSe/CdS conduction band offset dependences (i) of the positively charged trion fine structure, (ii) of the binding energy of the negatively charged trion, and (iii) of the radiative decay time for excitons and trions. The results of theoretical calculations are in qualitative agreement with available experimental data.
A theory of the electronic structure and excitonic absorption spectra of PbS and PbSe nanowires and nanorods in the framework of a four-band effective mass model is presented. Calculations conducted for PbSe show that dielectric contrast dramatically
strengthens the exciton binding in narrow nanowires and nanorods. However, the self-interaction energies of the electron and hole nearly cancel the Coulomb binding, and as a result the optical absorption spectra are practically unaffected by the strong dielectric contrast between PbSe and the surrounding medium. Measurements of the size-dependent absorption spectra of colloidal PbSe nanorods are also presented. Using room-temperature energy-band parameters extracted from the optical spectra of spherical PbSe nanocrystals, the theory provides good quantitative agreement with the measured spectra.
