Effects of sulphurization time on Cu2ZnSnS4 absorbers and thin films solar cells obtained from metallic precursors

We report the results of a study of the sulphurization time effects on Cu2ZnSnS4 absorbers and thin film solar cells prepared from dc-sputtered tackedmetallic precursors. Three different time intervals, 10 min, 30min and 60 min, at maximum sulphurization temperature were considered. The effects of this parameter' change were studied both on the absorber layer properties and on the final solar cell performance. The composition, structure, morphology and thicknesses of the CZTS layers were analyzed. The electrical characterization of the absorber layer was carried out by measuring the transversal electrical resistance of the samples as a function of temperature. This study shows an increase of the conductivity activation energy from 10 meV to 54meV for increasing sulphurization time from 10min to 60min. The solar cells were built with the following structure: SLG/Mo/CZTS/CdS/i-ZnO/ZnO:Al/Ni:Al grid. Several ac response equivalent circuit models were tested to fit impedance measurements. The best results were used to extract the device series and shunt resistances and capacitances. Absorber layer's electronic properties were also determined using the Mott–Schottky method. The results show a decrease of the average acceptor doping density and built-in voltage, from 2.0 1017 cm−3 to 6.5 1015 cm−3 and from 0.71 V to 0.51 V, respectively, with increasing sulphurization time. These results also show an increase of the depletion region width from approximately 90 nm–250 nm.

Cu2ZnSnS4 absorber layers obtained through sulphurization of metallic precursors: Graphite box versus sulphur flux

In this work we employed a hybrid method, combining RF-magnetron sputtering with evaporation, for the deposition of tailor made metallic precursors, with varying number of Zn/Sn/Cu (ZTC) periods and compared two approaches to sulphurization. Two series of samples with 1×, 2× and 4× ZTC periods have been prepared. One series of precursors was sulphurized in a tubular furnace directly exposed to a sulphur vapour and N2+5% H2 flux at a pressure of 5.0×10+4 Pa. A second series of identical precursors was sulphurized in the same furnace but inside a graphite box where sulphur pellets have been evaporated again in the presence of N2+5% H2 and at the same pressure as for the sulphur flux experiments. The morphological and chemical analyses revealed a small grain structure but good average composition for all three films sulphurized in the graphite box. As for the three films sulphurized in sulphur flux grain growth was seen with the increase of the number of ZTC periods whilst, in terms of composition, they were slightly Zn poor. The films' crystal structure showed that Cu2ZnSnS4 is the dominant phase. However, in the case of the sulphur flux films SnS2 was also detected. Photoluminescence spectroscopy studies showed an asymmetric broad band emission whichoccurs in the range of 1–1.5 eV. Clearly the radiative recombination efficiency is higher in the series of samples sulphurized in sulphur flux. We have found that sulphurization in sulphur flux leads to better film morphology than when the process is carried out in a graphite box in similar thermodynamic conditions. Solar cells have been prepared and characterized showing a correlation between improved film morphology and cell performance. The best cells achieved an efficiency of 2.4%.

CuxSnSx+1 (x = 2, 3) thin films grown by sulfurization of metallic precursors deposited by dc magnetron sputtering

We report the results of the growth of Cu-Sn-S ternary chalcogenide compounds by sulfurization of dc magnetron sputtered metallic precursors. Tetragonal Cu2SnS3 forms for a maximum sulfurization temperature of 350 ºC. Cubic Cu2SnS3 is obtained at sulfurization temperatures above 400 ºC. These results are supported by XRD analysis and Raman spectroscopy measurements. The latter analysis shows peaks at 336 cm-1, 351 cm-1 for tetragonal Cu2SnS3, and 303 cm-1, 355 cm-1 for cubic Cu2SnS3. Optical analysis shows that this phase change lowers the band gap from 1.35 eV to 0.98 eV. At higher sulfurization temperatures increased loss of Sn is expected in the sulphide form. As a consequence, higher Cu content ternary compounds like Cu3SnS4 grow. In these conditions, XRD and Raman analysis only detected orthorhombic (Pmn21) phase (petrukite). This compound has Raman peaks at 318 cm-1, 348 cm-1 and 295 cm-1. For a sulfurization temperature of 450 ºC the samples present a multi-phase structure mainly composed by cubic Cu2SnS3 and orthorhombic (Pmn21) Cu3SnS4. For higher temperatures, the samples are single phase and constituted by orthorhombic (Pmn21) Cu3SnS4. Transmittance and reflectance measurements were used to estimate a band gap of 1.60 eV. For comparison we also include the results for Cu2ZnSnS4 obtained using similar growth conditions.

Development of fractional order capacitors based on electrolyte processes

In recent years, significant research in the field of electrochemistry was developed. The performance of electrical devices, depending on the processes of the electrolytes, was described and the physical origin of each parameter was established. However, the influence of the irregularity of the electrodes was not a subject of study and only recently this problem became relevant in the viewpoint of fractional calculus. This paper describes an electrolytic process in the perspective of fractional order capacitors. In this line of thought, are developed several experiments for measuring the electrical impedance of the devices. The results are analyzed through the frequency response, revealing capacitances of fractional order that can constitute an alternative to the classical integer order elements. Fractional order electric circuits are used to model and study the performance of the electrolyte processes.