Semiconducting thin films of zinc selenide quantum dots

A novel chemical route for deposition of zinc selenide quantum dots in thin film form is developed. The deposited films are characterized with very high purity in crystallographic sense, and behave as typical intrinsic semiconductors. Evolution of the average crystal size, lattice constant, lattice strain and the optical properties of the films upon thermal treatment is followed and discussed. The band gap energy of as-deposited ZnSe films is blue-shifted by ≈0.50 eV with respect to the bulk value, while upon annealing treatment it converges to 2.58 eV. Two discrete electronic states which originate from the bulk valence band are observed in the UV-VIS spectra of ZnSe 3D quantum dots deposited in thin film form via allowed electronic transitions to the 1S electronic state arising from the bulk conduction band—appearing at 3.10 and 3.50 eV. The splitting between these two states is approximately equal to the spin-orbit splitting in the case of bulk ZnSe. The electronic transitions in the case of non-quantized annealed films are discussed in terms of the direct allowed band-to-band transitions with the spin-orbit splitting of the valence band of 0.40 eV. The effective mass approximation model (i.e., the Brus model) with the static relative dielectric constant of bulk ZnSe fails to predict correctly the size dependence of the band gap energy, while only a slight improvement is obtained when the hyperbolic band model is applied. However, when substantially smaller value for ε_r (2.0 instead of 8.1) is used in the Brus model, an excellent agreement with the experimental data is obtained, which supports some earlier indications that the quantum dots ε_r value could be significantly smaller than the bulk material value. The ionization energy of a deep donor impurity level calculated on the basis of the temperature dependence of the film resistivity is 0.82 eV at 0 K.