Reduced dimensionality of structures such as 0D quantum dots, 1D nanorods, and 2D nanoplatelets is predicted to favor the creation of tightly bound excitons stable at room temperature, making experimental determination of the exciton binding energy (R x ) crucial for evaluating the performance of semiconductor nanoparticles. We propose a fully optical approach for R x determination based on a complementary combination of photoacoustic and transmission spectra, using 5.5, 4.5, and 3.5 ML CdSe nanoplatelets as a benchmark system. The absence of excitonic features in photoacoustic spectra allows for probing the band-to-band transition, leading to the band gap determination. Such an unusual effect is explained by efficient re-emission of the absorbed radiation typical for high quantum yield structures, keeping the crystal lattice from excess phonon generation. The determined exciton binding energy for CdSe nanoplatelets ranges from 130 to 230 meV, confirming the presence of robust excitons in highly confined 2D systems.
Band gap alignment in GaAs1−xBix/GaAs quantum wells (QWs) was studied experimentally by photoreflectance (PR) and theoretically, ab initio, within the density functional theory in which the supercell based calculations are combined with the alchemical mixing approximation applied to a single atom in a supercell. In PR spectra, the optical transitions related to the excited states in the QW (i.e., the transition between the second heavy-hole and the second electron subband) were clearly observed in addition to the ground state QW transition and the GaAs barrier transition. This observation is clear experimental evidence that this is a type I QW with a deep quantum confinement in the conduction and valence bands. From the comparison of PR data with calculations of optical transitions in GaAs1−xBix/GaAs QW performed for various band gap alignments, the best agreement between experimental data and theoretical calculations has been found for the valence band offset of 52 ± 5%. A very similar valence band offset was obtained from ab initio calculations. These calculations show that the incorporation of Bi atoms into GaAs host modifies both the conduction and the valence band. For GaAs1−xBix with 0 < x < 0.074, the conduction band shifts lineary at a rate of ∼33 meV per % Bi, which only slightly decreases with Bi concentration. Whereas the valance band shift is clearly non-linear. Reducing initially at a rate of ∼51 meV per % Bi for low concentrations of Bi and then at a significantly reduced rate of ∼20 meV per % Bi near the end of the studied composition range. The overall reduction rate of the band gap is parabolic and the reduction rates change from ∼84 to ∼53 meV per % Bi for lower and higher Bi concentrations, respectively. The calculated shifts of valence and conduction bands give the variation of valence (conduction) band offset between GaAs1−xBix and GaAs in the range of ∼60%–40% (∼40%–60%), which is in good agreement with our conclusion derived from PR measurements.
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