M. G. Sousa

Thermodynamic pathway for the formation of SnSe and SnSe2 polycrystalline thin films by selenization of metal precursors

In this work, tin selenide thin films (SnSex) were grown on soda lime glass substrates by selenization of dc magnetron sputtered Sn metallic precursors. Selenization was performed at maximum temperatures in the range 300 °C to 570 °C. The thickness and the composition of the films were analysed using step profilometry and energy dispersive spectroscopy, respectively. The films were structurally and optically investigated by X-ray diffraction, Raman spectroscopy and optical transmittance and reflectance measurements. X-Ray diffraction patterns suggest that for temperatures between 300 °C and 470 °C, the films are composed of the hexagonal-SnSe2 phase. By increasing the temperature, the films selenized at maximum temperatures of 530 °C and 570 °C show orthorhombic-SnSe as the dominant phase with a preferential crystal orientation along the (400) crystallographic plane. Raman scattering analysis allowed the assignment of peaks at 119 cm−1 and 185 cm−1 to the hexagonal-SnSe2 phase and those at 108 cm−1, 130 cm−1 and 150 cm−1 to the orthorhombic-SnSe phase. All samples presented traces of condensed amorphous Se with a characteristic Raman peak located at 255 cm−1. From optical measurements, the estimated band gap energies for hexagonal-SnSe2 were close to 0.9 eV and 1.7 eV for indirect forbidden and direct transitions, respectively. The samples with the dominant orthorhombic-SnSe phase presented estimated band gap energies of 0.95 eV and 1.15 eV for indirect allowed and direct allowed transitions, respectively.

Comparison of fluctuating potentials and donor-acceptor pair transitions in a Cu-poor Cu2ZnSnS4 based solar cell

The structure of the electronic energy levels of a single phase Cu2ZnSnS4 film, as confirmed by Raman Scattering and x-ray diffraction, is investigated through a dependence on the excitation power of the photoluminescence (PL). The behavior of the observed asymmetric band, with a peak energy at ∼1.22 eV, is compared with two theoretical models: (i) fluctuating potentials and (ii) donor-acceptor pair transitions. It is shown that the radiative recombination channels in the Cu-poor film are strongly influenced by tail states in the bandgap as a consequence of a heavy doping and compensation levels. The contribution of the PL for the evaluation of secondary phases is also highlighted.

On the properties of Cu2ZnSn(S,Se)4 thin films prepared by selenization of binary precursors using rapid thermal processing

Cu2ZnSn(S,Se)4 thin films were grown on molybdenum coated glass substrates by selenization of stacked precursor layers of zinc, tin disulfide and copper sulfide. Selenization was performed using a rapid thermal processor at maximum temperatures in the range of 400 °C to 550 °C and at heating rates of 1 °C /s and 2 °C /s. The compositional, morphological and structural characterization of the films was carried out using energy dispersive x-ray spectroscopy, scanning electron microscopy, x-ray diffraction and Raman spectroscopy. X-ray diffraction and Raman scattering analysis suggests the formation of Cu2ZnSn(S,Se)4 only at lower temperatures, whereas Cu2ZnSnSe4 was formed at higher temperatures regardless of the heating rate used. Compositional analysis revealed that the films were Zn-poor and Sn-rich. However, the samples approach a near stoichiometric composition due to the loss of tin at a selenization temperature and heating rate of 550 °C and 2 °C /s, respectively. Large grains with an average lateral dimension of 4.5 μm were observed for films prepared at these conditions which are very desirable for an absorber for solar cells.

Muonium states in Cu2ZnSnS4 solar cell material

We investigated bulk and thin-film samples of the quaternary p-type semiconductor Cu2ZnSnS4 (CZTS) by μSR, in order to characterize the existing muonium signals. We find that the majority of the implanted muons form a diamagnetic state broadened by an interaction with the Cu nuclear moments, which we interpret as Mu+ bound to sulphur. A paramagnetic fraction is also present at low temperatures and the ratio between the two muon charge states, Mu+ and Mu0, varies between 20 and 40% prior to the onset of muon diffusion, which occurs at around 150 K. The fraction of Mu0 is found to be sensitive to the defect content of the sample. The paramagnetic fraction has two different contributions and their origin is discussed and related with the muon role as a probe for charge carriers in the material.