Browsing by Author "Cunha, A. F. da"
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- Admittance spectroscopy of Cu2ZnSnS4 based thin film solar cellsPublication . Fernandes, P. A.; Sartori, A. F.; Salomé, P. M. P.; Malaquias, J.; Cunha, A. F. da; Graça, M. P. F.; González, J. C.In this report, we propose an AC response equivalent circuit model to describe the admittance measurements of Cu2ZnSnS4 thin film solar cell grown by sulphurization of stacked metallic precursors. This circuit describes the contact resistances, the back contact, and the heterojunction with two trap levels. The study of the back contact resistance allowed the estimation of a back contact barrier of 246 meV. The analysis of the trap series with varying temperature revealed defect activation energies of 45 meV and 113 meV. The solar cell’s electrical parameters were obtained from the J-V curve: conversion efficiency, 1.21%; fill factor, 50%; open circuit voltage, 360 mV; and short circuit current density, 6.8 mA/cm2.
- Assessment of the potential of tin sulphide thin films prepared by sulphurization of metallic precursors as cell absorbersPublication . Malaquias, J.; Fernandes, P. A.; Salomé, P. M. P.; Cunha, A. F. daIn this work, SnxSy thin films have been grown on soda-lime glass substrates by sulphurization of metallic precursors in a nitrogen plus sulphur vapour atmosphere. Different sulphurization temperatures were tested, ranging from 300 °C to 520 °C. The resulting phases were structurally investigated by X-Ray Diffraction and Raman spectroscopy. Composition was studied using Energy Dispersive Spectroscopy being then correlated with the sulphurization temperature. Optical measurements were performed to obtain transmittance and reflectance spectra, from which the energy band gaps, were estimated. The values obtained were 1.17 eV for the indirect transition and for the direct transition the values varied from 1.26 eV to 1.57 eV. Electrical characterization using Hot Point Probe showed that all samples were p-type semiconductors. Solar cells were built using the structure: SLG/Mo/SnxSy/CdS/ZnO:Ga and the best result for solar cell efficiency was 0.17%.
- Comparison of fluctuating potentials and donor-acceptor pair transitions in a Cu-poor Cu2ZnSnS4 based solar cellPublication . Teixeira, J. P.; Sousa, R. A.; Sousa, M. G.; Cunha, A. F. da; Fernandes, P. A.; Salomé, P. M. P.; González, J. C.; Leitão, J. P.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.
- Cu2ZnSnS4 absorber layers obtained through sulphurization of metallic precursors: Graphite box versus sulphur fluxPublication . Sousa, M. G.; Cunha, A. F. da; Fernandes, P. A.; Teixeira, J. P.; Leitão, J. P.; Salomé, P. M. P.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%.
- Cu2ZnSnS4 solar cells prepared with sulphurized dc-sputtered stacked metallic precursorsPublication . Fernandes, P. A.; Salomé, P. M. P.; Cunha, A. F. da; Schubert, Björn-ArvidIn the present work we report the details of the preparation and characterization results of Cu2ZnSnS4 (CZTS) based solar cells. The CZTS absorber was obtained by sulphurization of dc magnetron sputtered Zn/Sn/Cu precursor layers. The morphology, composition and structure of the absorber layer were studied by scanning electron microscopy, energy dispersive spectroscopy, X-ray diffraction and Raman scattering. The majority carrier type was identified via a hot point probe analysis. The hole density, space charge region width and band gap energy were estimated from the external quantum efficiency measurements. A MoS2 layer that formed during the sulphurization process was also identified and analyzed in this work. The solar cells had the following structure: soda lime glass/Mo/CZTS/CdS/i-ZnO/ZnO:Al/Al grid. The best solar cell showed an opencircuit voltage of 345 mV, a short-circuit current density of 4.42 mA/cm2, a fill factor of 44.29% and an efficiency of 0.68% under illumination in simulated standard test conditions: AM 1.5 and 100 mW/cm2.
- CuxSnSx+1 (x = 2, 3) thin films grown by sulfurization of metallic precursors deposited by dc magnetron sputteringPublication . Fernandes, P. A.; Salomé, P. M. P.; Cunha, A. F. daWe 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.
- Detection of ZnS phases in CZTS thin-films by EXAFSPublication . Hartman, Katy; Newman, Bonna K.; Johnson, J. L.; Du, Hui; Fernandes, P. A.; Chawla, Vardaan; Bolin, Trudy; Clemens, Bruce M.; Cunha, A. F. da; Teeter, Glenn; Scarpulla, Michael A.; Buonassisi, TonioCopper zinc tin sulfide (CZTS) is a promising Earthabundant thin-film solar cell material; it has an appropriate band gap of ~1.45 eV and a high absorption coefficient. The most efficient CZTS cells tend to be slightly Zn-rich and Cu-poor. However, growing Zn-rich CZTS films can sometimes result in phase decomposition of CZTS into ZnS and Cu2SnS3, which is generally deleterious to solar cell performance. Cubic ZnS is difficult to detect by XRD, due to a similar diffraction pattern. We hypothesize that synchrotron-based extended X-ray absorption fine structure (EXAFS), which is sensitive to local chemical environment, may be able to determine the quantity of ZnS phase in CZTS films by detecting differences in the second-nearest neighbor shell of the Zn atoms. Films of varying stoichiometries, from Zn-rich to Cu-rich (Zn-poor) were examined using the EXAFS technique. Differences in the spectra as a function of Cu/Zn ratio are detected. Linear combination analysis suggests increasing ZnS signal as the CZTS films become more Zn-rich. We demonstrate that the sensitive technique of EXAFS could be used to quantify the amount of ZnS present and provide a guide to crystal growth of highly phase pure films.
- Effect of rapid thermal processing conditions on the properties of Cu2ZnSnS4 thin films and solar cell performancePublication . Sousa, M. G.; Cunha, A. F. da; Fernandes, P. A.; Teixeira, J.P.; Sousa, R.A.; Leitão, J.PIn the present work, we have studied the effect of several sulphurization conditions on the properties of Cu2ZnSnS4 thin films obtained through rapid thermal processing (RTP) of multi-period precursors with 8 periods of Zn/SnS2/CuS. In this study we varied the heating rate, the maximum sulphurization temperature, the time at maximum temperature and the amount of evaporated sulphur. The samples were characterized through scanning electron microscopy, energy dispersive spectroscopy, Raman scattering spectroscopy, X-ray diffraction, photoluminescence and I–V measurements. We have observed that at heating rates above 0.5 1C/s the samples delaminated severely. As a result further tests were carried out at 0.2 1C/s heating rate. The morphological studies revealed that the samples sulphurized at higher temperatures, shorter times and higher amount of evaporated sulphur exhibited larger grain sizes. The structural analysis based on Raman scattering and XRD did not lead to a clear distinction between the samples. Photoluminescence spectroscopy studies showed an asymmetric broad band characteristic of CZTS, which occurs in the range of 1.0–1.4 eV and a second band, on the high energy side of the previous one, peaking at around 1.41 eV. The intensity of this latter band varies from sample to sample revealing substantial differences in their optical properties. This band appears to originate either from the surface of the absorber or from the CdS layer and has a clear correlation with cell efficiency. The higher the intensity of this band the lower the cell efficiency, presumably due to the increase in recombination resulting from CZTS surface decomposition and eventually from the CdS with modified optoelectronic properties. The cell results hint toward a detrimental effect of long sulphuriza-tion times and a positive effect of higher sulphur vapour pressure and higher sulphurization temperature. Solar cell efficiencies improved with increased grain size in the absorber layer. The highest cell efficiency obtained in this study was 3.1%.
- Effect of selenization conditions on the growth and properties of Cu2ZnSn(S,Se)4 thin filmsPublication . Ranjbar, S.; Menon, M. R. Rajesh; Sousa, M. G.; Fernandes, P. A.; Cunha, A. F. daCu2ZnSn(S,Se)4 (CZTSSe) is a potentially cost effective candidate for future thin film solar cells (TFSCs). We report the growth of CZTSSe using a hybrid process involving the sequential evaporation of Zn and sputtering of the sulfide precursors of Cu and Sn, followed by a selenization step. Two approaches for selenization were followed, one using a tubular furnace (TF) and the other using a Rapid Thermal Processor (RTP). SEM and EDS were employed to investigate the morphology and composition of the films. Structural analyses were done using XRD and Raman spectroscopy. Structural analyses revealed the formation of CZTSSe. The effects of annealing conditions on the morphological and structural properties of the films were investigated.
- Effects of sulphurization time on Cu2ZnSnS4 absorbers and thin films solar cells obtained from metallic precursorsPublication . Fernandes, P. A.; Salomé, P. M. P.; Sartori, A. F.; Malaquias, J.; Cunha, A. F. da; Schubert, Björn-Arvid; González, J. C.; Ribeiro, G. M.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.
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