Over 10% efficient wide bandgap CIGSe solar cells on transparent substrate with Na predeposition treatment

With the recent rise of new photovoltaic applications, it has become necessary to develop specific optoelectronic properties for thin-film technologies such as Cu(In,Ga)Se2 and to take advantage of their high degree of tunability. The feasibility of efficient wide bandgap absorbers on transparent conductive oxide substrates is, in that context, of critical importance. Using an original approach based on a predeposition sodium treatment, Cu(In,Ga)Se2 absorbers fabricated by sputtering and reactive annealing with a Ga to (Ga + In) content over 0.7 and an optical bandgap above 1.4 eV are deposited on transparent fluorine-doped tin oxide films, with the insertion of an ultrathin MoSe2 layer preserving the contact's ohmicity. Different material characterizations are carried out, and a thorough Raman analysis of the absorber reveals that the sodium pretreatment significantly enhances the Ga incorporation into the chalcopyrite matrix, along with markedly improving the film's morphology and crystalline quality. This translates to a spectacular boost of the photovoltaic performance for the resulting solar cell as compared with a reference device without Na, specifically in the voltage and fill factor. Eventually, an efficiency exceeding 10% is obtained without antireflection coating, a record value bridging the gap with the state of the art on nontransparent substrates.Peer ReviewedPostprint (author's final draft

Life cycle assessment of different chalcogenide thin-film solar cells

Thin-film photovoltaics (PV) cells offer several benefits over conventional first-generation PV technologies, including lighter weight, flexibility, and lower power generation cost. Among the competing thin-film technologies, chalcogenide solar cells offer promising performance on efficiency and technological maturity level. However, in order to appraise the performance of the technology thoroughly, issues such as raw materials scarcity, toxicity, and environmental impacts need to be investigated in detail. This paper therefore, for the first time, presents a cradle to gate life cycle assessment for four different emerging chalcogenide PV cells, and compares their results with copper zinc tin sulfide (CZTS) and the commercially available CIGS to examine their effectiveness in reducing the environmental impacts associated with PV technologies. To allow for a full range of indicators, life cycle assessment methods CML 2001, IMPACT 2002+, and ILCD 2011 were used to analyse the results. The results identify environmental hotspots associated with different materials and components and demonstrate that using current efficiencies, the environmental impact of copper indium gallium selenide (CIGS) for generating 1kWh electricity was lower than that of the other studied cells. However, at comparable efficiencies the antimony-based cells offered the lowest environmental impacts in all impact categories. The effect of materials used was also found to be lower than the impact of electricity consumed throughout the manufacturing process, with the absorber layer contributing the most to the majority of the impact categories examined. In terms of chemicals consumed, cadmium acetate contributed significantly to the majority of the environmental impacts. Stainless steel in the substrate/insulating layer and molybdenum in the back contact both contributed considerably to the toxicity and ozone depletion impact categories. This paper demonstrates considerable environmental benefits associated with non-toxic chalcogenide PV cells suggesting that the current environmental concerns can be addressed effectively using alternative materials and manufacturing techniques if current efficiencies are improved.Peer ReviewedPostprint (published version

Progress and perspectives of thin film kesterite photovoltaic technology: a critical review

The latest progress and future perspectives of thin film photovoltaic kesterite technology are reviewed herein. Kesterite is currently the most promising emerging fully inorganic thin film photovoltaic technology based on critical raw-material-free and sustainable solutions. The positioning of kesterites in the frame of the emerging inorganic solar cells is first addressed, and the recent history of this family of materials briefly described. A review of the fast progress achieved earlier this decade is presented, toward the relative slowdown in the recent years partly explained by the large open-circuit voltage (VOC) deficit recurrently observed even in the best solar cell devices in the literature. Then, through a comparison with the close cousin Cu(In,Ga)Se2 technology, doping and alloying strategies are proposed as critical for enhancing the conversion efficiency of kesterite. In the second section herein, intrinsic and extrinsic doping, as well as alloying strategies are reviewed, presenting the most relevant and recent results, and proposing possible pathways for future implementation. In the last section, a review on technological applications of kesterite is presented, going beyond conventional photovoltaic devices, and demonstrating their suitability as potential candidates in advanced tandem concepts, photocatalysis, thermoelectric, gas sensing, etc.Peer ReviewedPostprint (published version

Numerical investigation of interface passivation strategies for Sb2Se3/CdS solar cells

Sb2Se3 is an emerging earth-abundant material praised for its promising optoelectronic properties, although the presence of interfacial defects at the vicinity of the p–n junction limit its performance as photovoltaic absorber. Using a device modeling approach and a realistic set of material parameters, it unravels pathways mitigating the impact of interfacial defects with a baseline Sb2Se3/CdS. Two straightforward strategies are devised and tested against the baseline. First, a thin front surface sulfurization of the Sb2Se3 absorber allowing a local lowering of the valence band and creating a “front surface field,” resulting in an increased carrier selectivity and limiting the density of holes available for interface recombination, leading to a significant efficiency improvement for optimized conditions. Second, the use of an ultrathin insulating Al2O3 layer between the absorber and the buffer layer is considered, helping in preventing detrimental chemical interdiffusion at the junction. This strategy provides a direct interface passivation, though the interlayer thickness needs a fine tuning to balance the benefits of reduced interface recombination and a detrimental Al2O3 low-conductivity layer. In each case, an analysis covering a broad range of parameters is presented, and conclusions are made in the frame of past numerical and experimental results.The authors thank Prof. Marc Burgelman, for his invaluable contribution to the field of photovoltaics by designing the program SCAPS, now widely used by various research groups around the world. The authors acknowledge the European Research Council ERC-CoG grant SENSATE (grant agreement ID: 866018) for the financial support of this work. This work is part of the R+D+i MaterOne project ref. PID 2020-116719RB-C41 funded by MCIN/AEI/10.13039/5011000110033. M.P. acknowledges the Spanish Ministry of Science and Innovation (MCIN) for the financial support in the frame of the Ramon y Cajal program (RYC-2017-23758).Peer ReviewedPostprint (author's final draft

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

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

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

A new approach for alkali incorporation in Cu2ZnSnS4 solar cells

The addition of alkali elements has become mandatory for boosting solar cell performance in chalcogenide thin films based on kesterites (Cu2ZnSnS4, CZTS). A novel doping process is presented here, that consists in the incorporation of sodium or lithium during the deposition of the CdS buffer layer, followed by a post-deposition annealing (PDA). As the doping route leads to more efficient devices in comparison with the undoped reference sample, the influence of PDA temperature was also investigated. Compositional profiling techniques, time-of-flight secondary ion mass spectrometry (TOF-SIMS) and glow discharge optical mission spectroscopy (GDOES), revealed a dependence of the alkaline distribution in kesterites with the PDA temperature. Although the doping process is effective in that it increases the alkaline concentration compared to the undoped sample, the compositional profiles indicate that a significant proportion of Li and Na remains 'trapped' within the CdS layer. In the 200 °C–300 °C range the alkali profiles registered the higher concentration inside the kesterite. Despite this, an additional alkali accumulation close to the molybdenum/fluorine doped tin oxide substrate was found for all the samples, which is frequently related to alkali segregation at interfaces. The addition of both, lithium and sodium, improves the photovoltaic response compared to the undoped reference device. This is mainly explained by a substantial improvement in the open-circuit potential (Voc) of the cells, with best devices achieving efficiencies of 4.5% and 3% for lithium and sodium, respectively. Scanning-electron microscopy images depicted a 'bilayer structure' with larger grains at the top and small grains at the bottom in all samples. Moreover, the calculated bandgap energies of the CZTS films account for changes in the crystallographic order-disorder of the kesterites, more related to the PDA treatment rather than alkali incorporation. Even if further optimization of the absorber synthesis and doping process will be required, this investigation allowed the evaluation of a novel strategy for alkali incorporation in kesterite based solar cells.Peer ReviewedPostprint (published version

Does Sb2Se3 admit nonstoichiometric conditions? How modifying the overall se content affects the structural, optical, and optoelectronic properties of Sb2Se3 thin films

Sb2Se3 is a quasi-one-dimensional (1D) semiconductor, which has shown great promise in photovoltaics. However, its performance is currently limited by a high Voc deficit. Therefore, it is necessary to explore new strategies to minimize the formation of intrinsic defects and thus unlock the absorber’s whole potential. It has been reported that tuning the Se/Sb relative content could enable a selective control of the defects. Furthermore, recent experimental evidence has shown that moderate Se excess enhances the photovoltaic performance; however, it is not yet clear whether this excess has been incorporated into the structure. In this work, a series of Sb2Se3 thin films have been prepared imposing different nominal compositions (from Sb-rich to Se-rich) and then have been thoroughly characterized using compositional, structural, and optical analysis techniques. Hence, it is shown that Sb2Se3 does not allow an extended range of nonstoichiometric conditions. Instead, any Sb or Se excesses are compensated in the form of secondary phases. Also, a correlation has been found between operating under Se-rich conditions and an improvement in the crystalline orientation, which is likely related to the formation of a MoSe2 phase in the back interface. Finally, this study shows new utilities of Raman, X-ray diffraction, and photothermal deflection spectroscopy combination techniques to examine the structural properties of Sb2Se3, especially how well-oriented the material is.Postprint (published version

Challenges and improvement pathways to develop quasi-1D (Sb1-xBix)2Se3-based materials for optically tuneable photovoltaic applications. Towards chalcogenide narrow-bandgap devices

Quasi-1D chalcogenides have shown great promises in the development of emerging photovoltaic technologies. However, most quasi-1D semiconductors other than Sb2Se3 and Sb2S3 have been seldom investigated for energy generation applications. Indeed, cationic or anionic alloying strategies allow changing the bandgap of these materials, opening the door to the development of an extended range of chalcogenides with tuneable optical and electrical properties. In this work, Bi incorporation into the Sb2Se3 structure has been proved as an effective approach to modulate the bandgap between 0.1. In order to better understand the underlying mechanisms leading to the formation of (Sb1-xBix)2Se3, and thus design specific strategies to enhance its properties, thin films with different annealing time and temperature have been synthesized and characterized. Interestingly, it has been observed that Sb2Se3 and Bi2Se3 are formed first, with Bi melting at 300 ¿C and diffusing rapidly towards the surface of the film. At higher temperature, the binary compounds combine to form the solid solution, however as the dwell time increases, (Sb1-xBix)2Se3 decomposes again into Bi2Se3 and Sb. This study has shown that the material is essentially limited by compositional disorder and recombination via defects. Likewise, routes have been proposed to improve morphology and uniformity of the layer, achieving efficiencies higher than 1% for x > 0.2Postprint (published version