Revealing the beneficial effects of Ge doping on Cu2ZnSnSe4 thin film solar cells

Kesterite (CZTSe) is a promising thin film photovoltaic absorber material due to its composition of more earth abundant materials compared to mature thin film photovoltaic technologies. Up to now, power conversion efficiencies are still lower and its main problem is the low open circuit voltage (Voc). Recently, a novel sintering approach using a nanometric Ge layer showed a large increase in device performance and especially in Voc. In this work, in-depth solar cell characterization as well as Raman and Photoluminescence studies of devices employing different Ge doped CZTSe absorber layers is presented. The main focus is to reveal the beneficial effects of Ge doping and furthermore investigate the interaction of Ge and Na. For low Ge doping an increase in charge carrier concentration is observed, resulting in devices with Voc of 460 mV, which corresponds to Voc deficits (Eg/q–Voc) of 596 mV a value comparable to current record devices. For high Ge amounts admittance spectroscopy measurements identified the appearance of a deep defect which can explain the observed deterioration of solar cell performance. Additional Na provided during crystallization of high Ge doped devices can reduce the density of this deep defect and recover device performance. These results indicate that Na plays an important role in defect passivation and we propose a defect model based in the interaction of group IV elements and Na with Cu vacancies

Resonant Raman scattering based approaches for the quantitative assessment of nanometric ZnMgO layers in high efficiency chalcogenide solar cells

This work reports a detailed resonant Raman scattering analysis of ZnMgO solid solution nanometric layers that are being developed for high efficiency chalcogenide solar cells. This includes layers with thicknesses below 100 nm and compositions corresponding to Zn/(Zn + Mg) content rations in the range between 0% and 30%. The vibrational characterization of the layers grown with different compositions and thicknesses has allowed deepening in the knowledge of the sensitivity of the different Raman spectral features on the characteristics of the layers, corroborating the viability of resonant Raman scattering based techniques for their non-destructive quantitative assessment. This has included a deeper analysis of different experimental approaches for the quantitative assessment of the layer thickness, based on (a) the analysis of the intensity of the ZnMgO main Raman peak; (b) the evaluation of the changes of the intensity of the main Raman peak from the subjacent layer located below the ZnMgO one; and (c) the study of the changes in the relative intensity of the first to second/third order ZnMgO peaks. In all these cases, the implications related to the presence of quantum confinement effects in the nanocrystalline layers grown with different thicknesses have been discussed and evaluated

Polarized Raman scattering study of kesterite type Cu2ZnSnS4 single crystals

A non-destructive Raman spectroscopy has been widely used as a complimentary method to X-ray diffraction characterization of Cu2ZnSnS4 (CZTS) thin films, yet our knowledge of the Raman active fundamental modes in this material is far from complete. Focusing on polarized Raman spectroscopy provides important information about the relationship between Raman modes and CZTS crystal structure. In this framework the zone-center optical phonons of CZTS, which is most usually examined in active layers of the CZTS based solar cells, are studied by polarized resonant and non-resonant Raman spectroscopy in the range from 60 to 500 cm(-1) on an oriented single crystal. The phonon mode symmetry of 20 modes from the 27 possible vibrational modes of the kesterite structure is experimentally determined. From in-plane angular dependences of the phonon modes intensities Raman tensor elements are also derived. Whereas a strong intensity enhancement of the polar E and B symmetry modes is induced under resonance conditions, no mode intensity dependence on the incident and scattered light polarization configurations was found in these conditions. Finally, Lyddane-Sachs-Teller relations are applied to estimate the ratios of the static to high-frequency optic dielectric constants parallel and perpendicular to c-optical axis

Effect of Na and the back contact on Cu2Zn(Sn,Ge)Se4 thin-film solar cells : towards semi-transparent solar cells

Cu2ZnSn1-xGexSe4 (CZTGSe) thin films have been grown onto Mo/SLG and Mo/V2O5/FTO/SLG substrates using thermal co-evaporation followed by a subsequent thermal annealing. A NaF precursor layer was evaporated prior to the deposition of the kesterite absorber layer. In the samples grown on Mo/SLG, it has been found that Na promotes Ge incorporation into the Cu2ZnSnSe4 lattice. The high concentration of incorporated Ge leads to the segregation of Sn-Se secondar y phases as we l l as to an accumulation of Sn next to the Mo layer. The use of 12 and 16 nm NaF thick precursor layers prior to the CZTGSe deposition leads to absorber band gaps of 1.30 and 1.34 eV, and to device performances of 4.7 and 4.0%, respectively. A higher Na content, furthermore, caused the formation of bigger grains, a higher charge carrier concentration and a shorter depletion width. A 12 nm NaF precursor layer was used for the devices grown on FTO-based substrates, producing an optimal back contact that allows achieving efficiencies of 5.6% and transmittance of 30% in the near infrared range. This enhanced performance can be associated with the absence of secondary phases and Ge distribution through the absorber layer. The formation of a MoSe2 layer at the back interface in al l the investigated devices seems to play a crucial role to improve the solar cell efficiency

Towards low cost and sustainable thin film thermoelectric devices based on quaternary chalcogenides

This is the peer reviewed version of the following article: Isotta, E. [et al.]. Towards low cost and sustainable thin film thermoelectric devices based on quaternary chalcogenides. "ADVANCED FUNCTIONAL MATERIALS", 20 Maig 2022, núm. 2202157, which has been published in final form at https://onlinelibrary.wiley.com/doi/10.1002/adfm.202202157. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions. This article may not be enhanced, enriched or otherwise transformed into a derivative work, without express permission from Wiley or by statutory rights under applicable legislation. Copyright notices must not be removed, obscured or modified. The article must be linked to Wiley’s version of record on Wiley Online Library and any embedding, framing or otherwise making available the article or pages thereof by third parties from platforms, services and websites other than Wiley Online Library must be prohibited.A major challenge in thermoelectrics (TEs) is developing devices made of sustainable, abundant, and non-toxic materials. Furthermore, the technological drive toward low sizes makes crucial the study of nano and micro configurations. In this work, thin film TE devices based on p-type Cu2+xZn1-xSnS4 and Cu2+xZn1-xSnSe4, and n-type AlyZn1-yO are fabricated by physical vapor deposition. The kesterite phases show good purity and promising TE power factor, likely enhanced by the copper–zinc order–disorder transition. Thin film generators in planar configuration are assembled by a sequential deposition of the p-type, n-type, and contact materials. The power per unit planar area reaches 153 and 279 nW cm-2 for the sulphur- and selenium-based generators, respectively. These values significantly outperform any other literature attempt based on sustainable and low-cost thin films. Furthermore, if compared with traditional TEs often made of scarce and toxic materials, these devices offer a cost reduction above 80%. This allows reaching comparable values of power density per unit material cost, representing a first real step toward the development of sustainable and non-toxic thin film TE devices. These can find applications in micro energy harvesters, microelectronics coolers, and temperature controllers for wearables, medical appliances, and sensors for the internet of things.A.J. thanks the European Social Fund+ for the FI fellowship. The authors would like to acknowledge the help of Dr. Mirco D’Incau, Dr. Narges Ataollahi, and Prof. Della Volpe for the design of the measuring setup, as well as useful discussion with Prof. Dario Narducci. This research has received funding from the Spanish Ministry of Science, Innovation and Universities under the MATER-ONE projects (PID2020-116719RB-C41). Authors from IREC belong to the SEMS (Solar Energy Materials and Systems) Consolidated Research Group of the “Generalitat de Catalunya” (ref. 2017 SGR 862) and are grateful to European Regional Development Funds (ERDF, FEDER Programa Competitivitat de Catalunya 2007–2013). M.G. acknowledges the financial support from Spanish Ministry of Science, Innovation and Universities within the Juan de la Cierva fellowship (IJC2018-038199-I). E.S. acknowledges the ICREA Academia Program. Open Access Funding provided by Universita degli Studi di Trento within the CRUI-CARE Agreement.Peer ReviewedPostprint (published version

2-step process for 5.4% CuGaSe2 solar cell using fluorine doped tin oxide transparent back contacts

As single-junction solar cells are approaching theoretical limits, multijunction solar cells are becoming increasingly relevant, and low-cost wider bandgap light harvesters in tandem with silicon are the next frontier in thin film photovoltaic research. Cu-based chalcogenide compounds have achieved great success as standard absorbers, but performance for bandgaps above 1.5¿eV is still lacking. Additionally, the use of transparent back contacts remains challenging for this class of materials. In this work, we report on the fabrication of wide bandgap CuGaSe2 absorbers by a combination of metallic sputtering and reactive thermal annealing grown on transparent fluorine-doped tin oxide-coated glass substrate. The annealing temperature is carefully tuned in regard to material and photovoltaic device properties. The introduction of an ultrathin Mo interlayer at the CuGaSe2/back interface favors a higher contact's ohmicity and results in an important improvement of all figures of merit. A record conversion efficiency of 5.4% is obtained, which is the highest value reported for this class of absorber on transparent back contact. Fundamental material characterization of the as-grown CuGaSe2 films reveals a better homogeneity in Cu distribution throughout the absorber's thickness when using a Mo interlayer, along with an enhanced crystalline quality. The sub-bandgap transparency of the final device remains perfectible, and improvement pathways are proposed using transfer matrix-based optical modeling, suggesting to use more specular interfaces to enhance optical transmission.Peer ReviewedPostprint (published version

Point defects, compositional fluctuations, and secondary phases in non-stoichiometric kesterites

The efficiency of kesterite-based solar cells is limited by various non-ideal recombination paths, amongst others by a high density of defect states and by the presence of binary or ternary secondary phases within the absorber layer. Pronounced compositional variations and secondary phase segregation are indeed typical features of non-stoichiometric kesterite materials. Certainly kesterite-based thin film solar cells with an off-stoichiometric absorber layer composition, especially Cu-poor/Zn-rich, achieved the highest efficiencies, but deviations from the stoichiometric composition lead to the formation of intrinsic point defects (vacancies, anti-sites, and interstitials) in the kesterite-type material. In addition, a non-stoichiometric composition is usually associated with the formation of an undesirable side phase (secondary phases). Thus the correlation between off-stoichiometry and intrinsic point defects as well as the identification and quantification of secondary phases and compositional fluctuations in non-stoichiometric kesterite materials is of great importance for the understanding and rational design of solar cell devices. This paper summarizes the latest achievements in the investigation of identification and quantification of intrinsic point defects, compositional fluctuations, and secondary phases in non-stoichiometric kesterite-type materials

Characterization of the stability of indium tin oxide and functional layers for semitransparent back-contact applications on Cu(in,Ga)Se2 solar cells

Herein, a detailed study of the stability of different ITO-based back-contact configurations (including bare ITO contacts and contacts functionalized with nanometric Mo, MoSe2, and MoS2 layers) under the coevaporation processes developed for the synthesis of high-efficiency Cu(In,Ga)Se2 (CIGSe) solar cells is reported. The results show that bare ITO layers can be used as efficient back contacts for coevaporation process temperatures of 480¿ºC. However, higher temperatures produce an amorphous In–Se phase at the ITO surface that reduces the contacts transparency in the visible region. This is accompanied by degradation of the solar cells’ efficiency. Inclusion of a Mo functional layer leads to the formation of a MoSe2 interfacial phase during the coevaporation process, which improves the cells’ efficiency, achieving device efficiencies similar to those obtained with reference solar cells fabricated with standard Mo back contacts. Optimization of the initial Mo layer thickness improves the contact transparency, achieving contacts with an optical transparency of 50% in the visible region. This is accompanied by a relevant decrease in back reflectivity in the CIGSe devices, confirming the potential of these contact configurations for the development of semitransparent CIGSe devices with improved optical aesthetic quality without compromising the device performance.Peer ReviewedPostprint (published version

Sulfurization of co-evaporated Cu2ZnGeSe4 layers: Influence of the precursor cation’s ratios on the properties of Cu2ZnGe(S,Se)4 thin films

Cu2ZnGe(S,Se)4 (CZGSSe) thin films were fabricated by sulfurization of co-evaporated Cu2ZnGeSe4 (CZGSe) thin films. The goal of this work is to investigate the effect of the composition of CZGSe layers on the structural, vibrational and morphological properties of CZGSSe compounds. Different CZGSe layers with different cation's ratios (Cu-poor, Zn-rich; Cu-poor, Zn-stoichiometric and Cu-poor, Ge-rich) were investigated before and after the sulfurization process. Break-off and different cooling experiments during sulfurization of CZGSe were also carried out. Break-off experiments revealed that 440 °C is the key temperature to incorporate S into CZGSe lattice, being required 480 °C to enhance the interdiffusion of the elements. Fast cooling experiments during sulfurization appeared to be a promising strategy to avoid the formation of secondary phases. All the samples showed the CZGSSe kesterite phase, as well as higher S content and different secondary phases at the surface. These experiments demonstrate that a minimum Ge content in CZGSe is required to assist the growth of CZGSSe grains and develop a compact structure. These results indicate the importance of controlling the cation's ratio of CZGSe to develop high quality wide band gap CZGSSe compounds, which can be very attractive for different applicationsThis work was supported by Spanish Ministry of Science, Innovation and Universities Project (CELL2WIN: PID2019-104372RB-C32) and European Project INFINITE-CELL (H2020-MSCA-RISE-2017-777968). DPL acknowledges the financial support from Spanish Ministry of Science and Innovation within FPI Program. MG acknowledges the financial support from Spanish Ministry of Science, Innovation and Universities within the Juan de la Cierva Program (IJC2018-038199-I). Authors from IREC belong to the SEMS (Solar Energy Materials and Systems) Consolidated Research Group of the “Generalitat de Catalunya” (Ref. 2017 SGR 862). The authors acknowledge the service from the MiNa Laboratory at IMN-CSIC, and funding from CM (project S2018/NMT-4291 TEC2SPACE), MINECO (project CSIC13-4E-1794) and European Union (FEDER, FSE

Insights into interface and bulk defects in a high efficiency kesterite-based device

This work provides a detailed analysis of a high efficiency Cu2ZnSnSe4 device using a combination of advanced electron microscopy and spectroscopy techniques. In particular, a full picture of the different defects present at the interfaces of the device and in the bulk of the absorber is achieved through the combination of high resolution electron microscopy techniques with Raman, X-ray fluorescence and Auger spectroscopy measurements at the macro, micro and nano scales. The simultaneous investigation of the bulk and the interfaces allows assessing the impact of the defects found in each part of the device on its performance. Despite a good crystalline quality and homogeneous composition in the bulk, this work reports, for the first time, direct evidence of twinning defects in the bulk, of micro and nano-voids at the back interface and of grain-to-grain non-uniformities and dislocation defects at the front interface. These, together with other issues observed such as strong absorber thickness variations and a bilayer structure with small grains at the bottom, are shown to be the main factors limiting the performance of CZTSe devices. These results open the way to the identification of new solutions to further developing the kesterite technology and pushing it towards higher performances. Moreover, this study provides an example of how the advanced characterization of emergent multilayer-based devices can be employed to elucidate their main limitations.Peer ReviewedPostprint (author's final draft