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The incorporation of Ge into kesterite thin-film absorbers for photovoltaic (PV) applications is thoroughly reviewed. Kesterite materials constitute a promising and critical raw material-free alternative to other inorganic thin-film PV compounds such as Cu(In,Ga)Se2and CdTe. The interest in Ge alloying is to solve the critical open-circuit voltage (Voc) deficit for kesterite solar cells, which is still unresolved and under strong debate. First, the substitution of Sn with Ge from 0 to 100% in the composition of Cu2Zn(Sn1−x,Gex)(Sy,Se1−y)4absorbers is largely discussed, with a complete overview on the existing literature. It is concluded that fine composition tuning is essential to ensure the Ge-induced enhancement of morphology and single-phase growth through a modified reaction pathway. In this regard, choosing between vacuum- and non vacuum-based deposition methods also plays a crucial role, since the former allows further up-scaling whereas the latter leads to higher thin-film quality. Second, at the solar cell level, Se-rich devices with less than 40% Ge currently exhibit the lowestVocand fill factor deficits with the highest efficiencies beyond 13%. This is mainly due to defect and band tail compensation as well as a graded bandgap and enlarged crystalline grains. This study unveils encouraging prospects for Ge-boosted kesterite PV devices.

The charge carrier balance in organic light-emitting diodes (OLEDs) is crucial for optimizing external quantum efficiency (EQE). This is typically achieved by using charge injection and blocking layers deposited by vacuum deposition, which increases the fabrication time and cost. This study investigates the potential of polyethylenimine ethoxylated (PEIE), Zinc oxide (ZnO) nanoparticles and a PEIE-ZnO nanocomposite as functional layers for OLEDs with improved electron injection and hole blocking properties fabricated by solution processing. The PEIE-ZnO nanocomposite improves OLED performance: (a) a 28 % increase in current density and enhanced electron mobility, (b) two times increase in electron mobility of the electron injection/transport layer, and (c) a reduction in surface and interface trap density. Consequently, the PEIE-ZnO nanocomposite shows an 84 % increase in electroluminescence, 52.5 % increase in luminous efficacy, 35.5 % increment in external quantum efficiency, and increased stability as measured by degradation studies. Employing these interlayers fabricated by the novel and roll-to-roll compatible Spray-on-Screen deposition technique show a comparable OLED performance as that of spin coated and vacuum deposited electron injection layers, which makes the large area fabrication of optoelectronic devices with high efficiencies, high output, low cost, and long lifetime a possible reality.

Relatively fast achievements in the kesterite solar cell technology have been made over the last decade, but the experimental efficiency is still ∼13%. One proposed reason is an inappropriate band alignment with Cu2ZnSnS4 (CZTS) and CdS that results in strong interface recombination losses. Results of this work show that the temperature and duration of air annealing of the CZTS/CdS heterojunction are essential for device performance. Soft annealing slightly improved the device efficiency due to the elemental intermixing at the interface. On the other hand, extended annealing increased absorber band gap energy, resulting in higher VOC values, indicating the improved Cu–Zn ordering in the CZTS structure, which also could be expected to have a beneficial influence on the device performance. However, interface analysis revealed that the CZTS absorber surface layer was Cu-rich, providing the reason for the reduction in CZTS solar cell performance. The effect of annealing on the interface defects was analyzed by the capacitance–frequency–voltage (C–V–f) analysis combined with SCAPS simulations. C–V–f-based loss maps showed that air annealing modifies the density distribution of asymmetrical interface states at the CZTS/CdS interface, which becomes fully symmetrical for longer annealing times at 200 °C.

The implementation of anoxide layerwith contact openings to the Cu(In,Ga)Se2(CIGS) interfaces has become especially popular to reduce the recombination losses, resulting in a higher open-circuit voltage. While implementing this approach on the back surface is straightforward, it is more complicated for the front surface due to the roughness of the absorber as well as material selection constraints imposed by further processing steps. In this contribution, an AlOx/HfOxmulti-stack oxide layer with contact openings is applied between the CIGS and CdS layers. Two different approaches to create contact openings in multi-stack oxide layer are presented, and their advantages and disadvantages are investigated. In the bottom-up approach (BU), a NaCl salt pattern is created on the CIGS absorber surface, while in the top-down approach (TD), the pattern is created on the AlOxlayer surface. Time-resolved photoluminescence (TR-PL) shows that the multi-stack design improves the PL decay time regardless of the approach, but when the CdS layer is deposited, the PL decay time decreases. A more severe decrease is observed in case of the BU approach. Capacitance-Voltage measurements show that there is no impact on doping level when the NaCl pattern is created on an AlOxsurface. This work shows that any oxide material, even if not chemically resistant to the chemical bath deposition, can be applied at the CIGS/buffer layer interface, and additionally, any template can be used to create contact openings while preventing interaction between the material used for patterning and the CIGS, using the TD approach.

In the present contribution, we have measured and simulated room temperature bias- and frequency-dependent capacitances of thin-film solar cell devices. The results of both the simulations and experimental measurements are represented as 2-D contour plots showing the derivative of the capacitance with respect to the frequency multiplied by the frequency. These plots are called “loss maps,” because responses in these contour plots correspond to responses of different nonidealities in the devices. Using a 1-D drift-diffusion solver (SCAPS), we have simulated the responses of different nonidealities of the solar cell devices, such as series resistance, bulk defects, interface defects, back contact barrier, and absorber-buffer barrier. We have shown that some nonidealities have a quite recognizable trace in the loss map. Other nonidealities on the other hand show responses that look quite similar in the bias voltage and frequency space, making exact conclusions on the nature and position of the defect responses in thin-film solar cells most of the times difficult. We have compared the simulated results with experimental measurements of one of our Cu(In,Ga)Se2 (CIGS) solar cell devices and came to the conclusion that there is likely a bulk defect or a spike-like barrier at the CIGS-CdS interface present in our particular device. The loss map can, in some cases, be useful in order to analyze admittance spectroscopy data in a graphical and relatively intuitive way.

Current state-of-the-art Cu2ZnSn(S,Se)(4) kesterite solar cells are limited by low open-circuit voltages (V-OC). In order to evaluate to what extent the substitution of Sn by Ge is able to result in higher V oc values, this article focuses on Cu2ZnGeSe4 "CZGSe" devices. To reveal their full potential, different strategies are explored that, in particular, aim at the optimization of the CZGSe/buffer heterojunction. Here, employing hard X-ray photoelectron spectroscopy, it is evidenced that only a combination of different surface treatments is able to remove all detrimental secondary phases. Further improvements are achieved by establishing a solar cell heat treatment in air. A systematic study of the impact of different annealing temperatures and durations determines the best heat treatment parameters to be 60 min at 200 degrees C. Also, Zn(O,S,OH) as a more transparent alternative to the heavy-metal compound CdS buffer layer has been realized. Combining all of the strategies, solar cells with 8.5 and 7.5% total area efficiency have been prepared, which is a record for Sn-free kesterite solar cells and any kesterite solar cell with a Zn(O,S,OH) buffer, respectively. Beyond these records, this work clearly confirms the emerging trend that Ge-for-Sn substitution is a successful strategy to improve the V-OC of kesterite solar cells. This project has received funding from the European Union's Horizon 2020 Research and Innovation Program under grant agreement no. 640868. Choubrac, L (corresponding author), Univ Nantes, UMR6502, CNRS, Inst Mat Jean Rouxel IMN, F-44300 Nantes, France; Helmholtz Zentrum Berlin Mat & Energie GmbH, Dept Struct & Dynam Energy Mat, D-14109 Berlin, Germany. leo.choubrac@helmholtz-berlin.de

The open circuit voltage (VOC) deficit of Cu2ZnSn(S,Se)4 (CZTSSe) kesterite solar cells is higher than that of the closely related Cu(InGa)Se2 solar cells. One of the most promising strategies to overcome the large VOC deficit of kesterite solar cells is by reducing the recombination losses through appropriate cation substitution. In fact, replacing totally or partially Zn or Cu by an element with larger covalent radius one can significantly reduce the concentration of I–II antisite defects in the bulk. In this study, an investigation of the impact of partial substitution of Cu by Ag in CZTSSe solid solution monograins is presented. A detailed photoluminescence study is conducted on Ag-incorporated CZTSSe monograins and a radiative recombination model is proposed. The composition and structural quality of the monograins in dependence of the added Ag amount are characterized using Energy Dispersive X-ray Spectroscopy and X-Ray Diffraction method, respectively. The Ag-incorporated CZTSSe monograin solar cells are characterized by temperature dependent current-voltage and electron beam induced current methods. It was found, that low Ag contents (x ≤ 0.02) in CZTSSe lead to higher solar cell device efficiencies.

Thin (640 mV were achieved after the KF treatment. From SCAPS simulations and temperature dependent current voltage-measurements, it is concluded that the V-oc of these cells are limited by backcontact surface recombination and, thus, further improvements require passivation of the back contact. This work was supported by the European Union’s H2020 Research and Innovation Program under Grant 715027.

Cu(In,Ga)Se-2 (CIGSe) solar cells are among the most efficient thin-film solar cells on lab scale. However, this thin-film technology has relatively large upscaling losses for commercial technology. To tackle this, paradigm shifts are proposed that allow for simpler, cost-effective, and efficient CIGSe solar cells. Front passivation using dielectric layers is one of the options being investigated as this is widely used in Si technology. Research on front passivation for CIGSe is in an early stage and no improvements are made yet. A close comparison with silicon technology is made to understand why it seems to be more difficult for CIGSe solar cells. In general, chemical passivation is less effective, resulting in higher interface defect densities than seen for Si. Also, field-effect passivation requires positive charges, which have not been implemented yet on the CIGSe front surface. Finally, for Si passivation, often a high-temperature annealing step is applied, which is not possible for CIGSe. It is proposed to apply a dielectric tunneling layer with positive fixed charges in combination with an electron transport layer to move forward. A list of potential dielectric layers that could be suitable for CIGSe is provided. Dr. J.D.W., Dr. G.B., and Professor B.V. received funding from the European Union’s H2020 research and innovation programme under grant agreement no. 715027 for this work. G.B acknowledges FWO postdoctoral fellowship 1219423N and R.S FWO Ph.D. fellowship fundamental research 1178022N.

This report highlights the combination of the MicroTime 100 upright confocal fluorescence lifetime microscope with a Single Quantum Eos Superconducting Nanowire Single-Photon Detector (SNSPD) system as a powerful tool for photophysical research and applications. We focus on an application in materials science, photoluminescence imaging, and lifetime characterization of Cu(InGa)Se-2 (CIGS) devices intended for solar cells. We demonstrate improved sensitivity, signal-to-noise ratio, and time-resolution in combination with confocal spatial resolution in the near-infrared (NIR) range, specifically in the 1000-1300 nm range. The MicroTime 100-Single Quantum Eos system shows two orders of magnitude higher signal-to-noise ratio for CIGS devices' photoluminescence imaging compared to a standard NIR-photomultiplier tube (NIR-PMT) and a three-fold improvement in time resolution, which is now limited by the laser pulse width. Our results demonstrate the advantages in terms of image quality and time resolution of SNSPDs technology for imaging in materials science.(c) 2023 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/). PicoQuant and Single Quantum thank the European Union’s Horizon 2020 research and innovation program [ATTRACT Phase 2 (Grant Agreement No. 101004462), project: MicroQuaD] for the financial support of this work.

Interface recombination is one of the factors limiting the performance of Cu(In,Ga)Se2(CIGS). Especially in the absence of band grading at the front and rear surface, interface passivation approaches become important to improve device performance. The integration of an oxide layer as passivation layer at the front surface of the CIGS requires meticulous considerations in order not to impact the further steps of the solar cell production. In this article, a novel approach is reported to try to tackle the problem of interface recombination at the front surface of CIGS without affecting further solar cell production steps. In this approach, an Al2O3/HfO2multi-stack layer with contact openings is applied. NaCl template patterning with preliminarily selected parameters was used to create a homogeneous pattern of contact opening on the CIGS surface and allow the current flow in the device. After the removal of the NaCl islands, the holes in the multi-stack (openings) were visualized by scanning electron microscopy. In addition, energy-dispersive X-ray spectroscopy (EDS) was performed before and after chemical bath deposition of the buffer layer. The EDS result confirmed that the undesired etching of the Al2O3layer during buffer layer deposition was prevented by using a thin HfO2layer. Solar cells were produced by using preliminarily selected parameters for the multi-stack design. As a result, without having a significant negative impact on the solar cell parameters, a device design was achieved which is almost comparable with the reference device. In addition, options for future improvement and development are discussed.

Pure sulfide CIGS solar cells are interesting candidates for standalone solar cells or top cells in a tandem configuration. To understand the limits and improve the power conversion efficiency of these devices, a comprehensive approach aimed at composition, interface, and process engineering should be employed. Here, the latter was explored. Using a two-step fabrication technique and one-variable-at-a-time methodology, we found the four processing factors affecting the absorber the most. While two were already backed by the previous literature, we found new and statistical evidence for two other important factors as well. The impact of alkali barrier diffusion was also established with statistical significance and under various processing conditions. Furthermore, the absorber roughness for samples without a barrier indicated a significant negative linear correlation with the devices' efficiency. This contribution could aid engineers in more efficient process designs. European Union's Horizon 2020 Research and Innovation Program [640868]

Presented (oral presentation) at the Virtual Workshop on Transparent PV: Challenges and Opportunities that was co-organised on June 11th 2021 by the Impressive and Tech4Win European projects. The presentation reviewed the main results achieved in Tech4Win (at June 2021) on the development of inorganic UV multifunctional coatings combining UV filtering and PV functionalities

Presented (as oral contribution) at the 11th European Kesterite Workshop, 26-27 November2020. Transparent photovoltaics (PV) could be a solution for integrating large amount of PV in buildings. A possible approach could be a tandem cell using the combination of IR-absorbing organic bottom cells with UV-absorbing top cells. The UV top cell would then serve as a solar cell, converting UV light into electrical energy, as well as a UV filter to protect the bottom organic PV cell from degradation from the UV light. We have developed three potential UV absorber materials: ZnS, ZnSe and Zn(S,Se). All layers were fabricated by annealing an evaporated or sputtered Zn layer in an atmosphere of H2S for sulfurization, H2Se for selenization or a mix of the two for the mixed sulfo-selenization. Typical annealing temperatures and times for this crystallization process are 450°C and 10 minutes. In this presentation we report on the optoelectronic properties of the layers and we show that the combined Zn(S,Se) shows the ideal band gap of about 3 eV combining both decent colour and good UV filtering properties. Analysis of the conductivity of the layers is also presented, together with some initial solar cell structures with transparent front and back contacts.

Ultrathin Cu(In,Ga)Se-2 (CIGS) absorber layers of 550 nm were grown on Ag/AlOx stacks. The addition of the stack resulted in solar cells with improved fill factor, open circuit voltage and short circuit current density. The efficiency was increased from 7% to almost 12%. Photoluminescence (PL) and time resolved PL were improved, which was attributed to the passivating properties of AlOx. A current increase of almost 2 mA/cm(2) was measured, due to increased light scattering and surface roughness. With time of flight-secondary ion mass spectroscopy, the elemental profiles were measured. It was found that the Ag is incorporated through the whole CIGS layer. Secondary electron microscopic images of the Mo back revealed residuals of the Ag/AlOx stack, which was confirmed by energy dispersive X-ray spectroscopy measurements. It is assumed to induce the increased surface roughness and scattering properties. At the front, large stains are visible for the cells with the Ag/AlOx back contact. An ammonia sulfide etching step was therefore applied on the bare absorber improving the efficiency further to 11.7%. It shows the potential of utilizing an Ag/AlOx stack at the back to improve both electrical and optical properties of ultrathin CIGS solar cells. This research was funded by European Union H2020 research and innovation program grant number 715027.

A simplified Cu(In, Ga)Se-2 (CIGS) solar cell structure based on a 500 nm thin CIGS layer is presented. The absorber layers are grown with a single-stage coevaporation process, and various KF post-deposition treatments (KF-PDT) are performed. The KF-PDT leads to an efficiency increase from 7% to 12%. For all cells an increase in open circuit voltage (V-oc) and fill factor is measured, which is attributed to an improved pn junction. By changing the annealing conditions, an additional V-oc increase is measured. This increase is attributed to the reduction of light-induced defects at the CIGS/CdS interface in addition to the improved pn junction. A reduction of defects is confirmed by reduced sub band gap emission in the photoluminescence spectra, an increased decay time, and increased quasi Fermi level splitting. With SCAPS the results are simulated, and it is concluded that after KF-PDT the V-oc is limited to 640 mV due to recombination at the back contact. A higher V-oc can then only be achieved by applying a passivation layer at the back. There are no indications that the single-stage process is limiting the efficiency, revealing the potential of the proposed simplified CIGS structure and the importance of interfaces for ultrathin CIGS solar cells. J. de Wild, D.G. Buldu, T. Kohl, G. Birant, and B. Vermang received funding from the European Union’s H2020 research and innovation program under grant agreement no. 715027.

This work reports on developments in the field of wide band gap Cu2ZnXY4 (with X = Sn, Si or Ge, and Y = S, Se) kesterite thin film solar cells. An overview on recent developments and the current understanding of wide band gap kesterite absorber layers, alternative buffer layers, and suitable transparent back contacts is presented. Cu2ZnGe(S,Se)(4) absorbers with absorber band gaps up to 1.7 eV have been successfully developed and integrated into solar cells. Combining a CdS buffer layer prepared by an optimized chemical bath deposition process with a 1.36 eV band gap absorber resulted in a record Cu2ZnGeSe4 cell efficiency of 7.6%, while the highest open-circuit voltage of 730 mV could be obtained for a 1.54 eV band gap absorber and a Zn(O,S) buffer layer. Employing InZnOx or TiO2 protective top layers on SnO2:In transparent back contacts yields 85-90% of the solar cell performance of reference cells (with Mo back contact). These advances show the potential as well as the challenges of wide band gap kesterites for future applications in high-efficiency and low-cost tandem photovoltaic devices. This project has received funding from the European Union's Horizon 2020 Research and Innovation Program under grant agreement No. 640868. The synchrotron radiation experiments were performed at the SPring-8 beamline BL15XU with the approval of the NIMS Synchrotron X-ray Station (Proposals 2016A4600, 2016B4601, and 2017A4600) and at BESSY II with the approval of HZB. B. Vermang has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 Research and Innovation Programme (grant agreement no. 715027).

A new multi-stack approach with contact openings was investigated for front surface of Cu(In,Ga)Se 2 thin film solar cells. In this multi-stack design, a thin HfO x layer was used to protect a thicker AlO x layer from the presence of ammonia in the chemical bath deposition. The contact openings were created by using alkali solution. The lifetime decay was improved by implementing multi-stack passivation layer between CIGS/buffer layer interface. It was shown that open circuit voltage was increased by up to 30mV.

In this contribution, a cost- and time- effective contacting approach is presented for dielectric-based rear surface passivation layers up to 30 nm. Nano-size and homogenously distributed openings are realized in AlOx passivation layer by selenization of LiF salt on top, and monitored via SEM. Further, this layer was implemented into sub-micron thick CIGS solar cells. Consequently, contact openings facilitate the current collection through the dielectric layer up to 30 nm thick. However, solar cell parameters remain the same, even worse than the reference. Thus, this approach is still open for optimizations.

In modern Cu(In,Ga)Se2 (CIGS) solar cell production, alkali-poor substrates are becoming increasingly common. Thus, understanding the effect of alkali atoms on the growth of the CIGS absorber has become crucial. We studied this impact by comparing the bias dependent admittance spectroscopy response of CIGS solar cells grown with varying amounts of sodium using two different growth processes. The absence of sodium led to an intense response which is progressively replaced by other response domains as the sodium supply increases. We linked these new domains to Na accumulation and a resulting increase in band bending at the CIGS/CdS interface.

Several optoelectronic issues, such as poor optical absorption and recombination, limit the power conversion efficiency of ultrathin Cu(In,Ga)Se

In Cu(In,Ga)Se2(CIGS) thin-film solar cells, interface recombination is one of the most important limiting factors with respect to device performance. Herein, metal–insulator–semiconductor samples are used to investigate and compare the passivation effects of Al2O3and HfO2at the interface with CIGS. Capacitance–voltage–frequency measurements allow to qualitatively and quantitatively assess the existence of high negative charge density (Qf ≈ −1012 cm−2) and low interface-trap density (Dit ≈ 1011 cm−2 eV−1). At the rear interface of CIGS solar cells, these, respectively, induce field-effect and chemical passivation. A trade-off is highlighted between stronger field-effect for HfO2and lower interface-trap density for Al2O3. This motivates the usage of Al2O3to induce chemical passivation at the front interface of CIGS solar cells but raises the issue of its processing compatibility with the buffer layer. Therefore, an innovative Al2O3/HfO2multistack design is proposed and investigated for the first time. Effective chemical passivation is similarly demonstrated for this novel design, suggesting potential decrease in recombination rate at the front interface in CIGS solar cells and increased efficiency. 300 °C annealing in N2environment enable to enhance passivation effectiveness by reducingDitwhile surface cleaning may reveal useful for alternative CIGS processing methods.

Cu2ZnGeSe4 (CZGSe) is a promising earth-abundant and non-toxic semiconductor material for large-scale thin-film solar cell applications. Herein, we have employed a joint computational and experimental approach to characterize and assess the structural, optoelectronic, and heterojunction band offset and alignment properties of a CZGSe solar absorber. The CZGSe films were successfully prepared using DC-sputtering and e-beam evaporation systems and confirmed by XRD and Raman spectroscopy analyses. The CZGSe films exhibit a bandgap of 1.35 eV, as estimated from electrochemical cyclic voltammetry (CV) measurements and validated by first-principles density functional theory (DFT) calculations, which predicts a bandgap of 1.38 eV. A fabricated device based on the CZGSe as a light absorber and CdS as a buffer layer yields power conversion efficiency (PCE) of 4.4% with VOC of 0.69 V, FF of 37.15, and Jsc of 17.12 mA cm-2. Therefore, we suggest that interface and band offset engineering represent promising approaches to improve the performance of CZGSe devices by predicting a type-II staggered band alignment with a small conduction band offset of 0.18 eV at the CZGSe/CdS interface.

Cu2ZnGeSe4 (CZGSe) is a promising earth-abundant and non-toxic semiconductor material for large-scale thin-film solar cell applications. Herein, we have employed a joint computational and experimental approach to characterize and assess the structural, optoelectronic, and heterojunction band offset and alignment properties of a CZGSe solar absorber. The CZGSe films were successfully prepared using DC-sputtering and e-beam evaporation systems and confirmed by XRD and Raman spectroscopy analyses. The CZGSe films exhibit a bandgap of 1.35 eV, as estimated from electrochemical cyclic voltammetry (CV) measurements and validated by first-principles density functional theory (DFT) calculations, which predicts a bandgap of 1.38 eV. A fabricated device based on the CZGSe as a light absorber and CdS as a buffer layer yields power conversion efficiency (PCE) of 4.4% with V-OC of 0.69 V, FF of 37.15, and J(sc) of 17.12 mA cm(-2). Therefore, we suggest that interface and band offset engineering represent promising approaches to improve the performance of CZGSe devices by predicting a type-II staggered band alignment with a small conduction band offset of 0.18 eV at the CZGSe/CdS interface. SRR and NYD acknowledge the UK Engineering and Physical Sciences Research Council (EPSRC) for funding (Grant No. EP/S001395/1). This work has also used the Advanced Research Computing computational facilities at Cardiff (ARCCA) Division, Cardiff University, and HPC Wales. This work also made use of ARCHER facilities (http://www.archer.ac.uk), the UK's national supercomputing service via the membership of the UK's HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202). YAJ is thankful to Savitribai Phule Pune University Post Doctorate Fellowship (SPPU-PDF) program (Grant No. SPPU PDF/ST/CH/2019/0004) and School of Energy Studies for financial support and laboratory facilities. DGB, GB, and BV acknowledge the European Union's Horizon 2020 Research and Innovation Program (Grant agreement No. 640868). SRR and BV acknowledge UHasselt-BOF for the mobility grant project R-8751 (https://www.uhasselt.be/UH/Research-groups/en-projecten_DOC/en-project_details.html?pid=16044&t=en). Rondiya, SR; Dzade, NY (corresponding author), Cardiff Univ, Sch Chem, Main Bldg,Pk Pl, Cardiff CF10 3AT, S Glam, Wales. Vermang, B (corresponding author), Hasselt Univ Partner Solliance, Inst Mat Res IMO, Wetenschapspk 1, B-3590 Diepenbeek, Belgium ; Imec Div IMOMEC Partner Solliance, Wetenschapspk 1, B-3590 Diepenbeek, Belgium ; EneryVille, Thorpk,Poort Genk 8310 & 8320, B-3600 Genk, Belgium. rondiyas@cardiff.ac.uk; dzadeny@cardiff.ac.uk; bart.vermang@uhasselt.be

This work presents a novel method of local contact openings formation in an aluminum oxide (Al2O3) rear surface passivation layer by the selenization of the lithium fluoride (LiF) salt on top of the Al2O3for ultra-thin copper indium gallium (di)selenide (CIGS) solar cells (SCs). This study introduces the potentially cost-effective, fast, industrially viable, and environmentally friendly way to create the nano-sized contact openings with the homogeneous distribution in the thick, i.e. up to 30 nm, Al2O3passivation layer. The passivation layer is deposited by atomic layer deposition, while the LiF layer is spin-coated. Selenization is done in the H2Se atmosphere and the optimal process parameters are deduced to obtain nano-sized and uniformly allocated openings as confirmed by scanning electron microscopy images. The contact openings were produced in the different thicknesses of the alumina layer from 6 nm to 30 nm. Furthermore, the Al2O3rear surface passivation layer with the contact openings was implemented into ultra-thin CIGS SC design, and one trial set was produced. We demonstrated that the created openings facilitate the effective current collection through the dielectric Al2O3layer up to 30 nm thick. However, the upper limit of Al2O3thickness in which the contact openings can be created by the described method is not established yet. The produced passivated CIGS SCs show increased external quantum efficiency response due to the optical enhancement of the passivated cells. However, the production of SCs on the Al2O3passivation layer with the openings created by selenization of LiF is not optimized yet.

Wide band gap thin-film kesterite solar cell based on non-toxic and earth-abundant materials might be a suitable candidate as a top cell for tandem configuration in combination with crystalline silicon as a bottom solar cell. For this purpose and based on parameters we have extracted from electrical and optical characterization techniques of Cu2ZnGeSe4 absorbers and solar cells, a model has been developed to describe the kesterite top cell efficiency limitations and to investigate the different possible configurations with transparent back contact for fourterminal tandem solar cell application. Furthermore, we have studied the tandem solar cell performance in view of the band gap and the transparency of the kesterite top cell and back contact engineering. Our detailed analysis shows that a kesterite top cell with efficiency > 14%, a band gap in the range of 1.5-1.7 eV and transparency above 80% at the sub-band gaps photons energies are required to achieve a tandem cell with higher efficiency than with a single silicon solar cell. The authors would like to acknowledge the SWInG project financed by the European Union's Horizon 2020 research and innovation programme under grant agreement No 640868 and the Research Foundation Flanders-Hercules Foundation (FWO-Vlaanderen, project No AUGE/13/16:FT-IMAGER). Khelifi, S (corresponding author), Univ Ghent, Dept Solid State Sci, Krijgslaan S1, B-9000 Ghent, Belgium. samira.khelifi@ugent.be

Several optoelectronic issues, such as poor optical absorption and recombination, limit the power conversion efficiency of ultrathin Cu(In,Ga)Se-2 (CIGS) solar cells. To mitigate recombination losses, two combined strategies were implemented: a potassium fluoride (KF) post-deposition treatment (PDT) and a rear interface passivation strategy based on an aluminum oxide (Al2O3) point contact structure. The simultaneous implementation of both strategies is reported for the first time on ultrathin CIGS devices. Electrical measurements and 1D simulations demonstrate that in specific conditions, devices with only KF-PDT may outperform rear interface passivation based devices. By combining KF-PDT and rear interface passivation, an enhancement in an open-circuit voltage of 178 mV is reached over devices that have a rear passivation only, and of 85 mV over devices with only a KF-PDT process. Time-Resolved Photoluminescence measurements showed the beneficial effects of combining KF-PDT and the rear interface passivation at decreasing recombination losses in the studied devices, enhancing charge carrier lifetime. X-ray photoelectron spectroscopy measurements indicate the presence of an In and Se-rich layer that we linked to be a KInSe2 layer. Our results suggest that when bulk and front interface recombination values are very high, they dominate, and individual passivation strategies work poorly. Hence, this work shows that for ultrathin devices, passivation mitigation strategies need to be implemented in tandem. Funding Fundaca̧ o para a Cie ̃ ncia e Tecnologia through grants IF/ ̂00133/2015, PD/BD/142780/2018, and SFRH/BD/146776/2019 and projects PDTC/CTM-CTM/28075/2017, PTDC/FISMAC/29696/2017, and UIDB/04730/2020 is acknowledged. European Union’s Horizon 2020 through grant nos. 720887 and 715027 and the Special Research Fund (BOF) of Hasselt University are also acknowledged. ACKNOWLEDGMENTS Fundaca̧ o para a Cie ̃ ncia e a Tecnologia (FCT) is acknowledged through the project IF/00133/2015, PD/BD/142780/2018, and SFRH/BD/146776/2019. The authors want to acknowledge the European Union’s Horizon 2020 research and innovation program under the agreement nos. 720887 (ARCIGS-M project) and 715027. The Special Research Fund (BOF) of Hasselt University, the FCT through the project NovaCell (PDTC/CTM-CTM/28075/2017), and InovSolarCells (PTDC/FISMAC/29696/2017) co-funded by FCT and the ERD through COMPETE2020 is also acknowledged. P. A. Fernandes would like to acknowledge FCT for the support of the project FCT UIDB/04730/2020.

To reduce the prominent VOC-deficit that limits kesterite-based solar cells efficiencies, Ge has been proposed over the recent years with encouraging results, as the reduction of the non-radiative recombination rate is considered as a way to improve the well-known Sn-kesterite world record efficiency. To gain further insight into this mechanism, we investigate the physical behaviour of intrinsic point defects both upon Ge doping and alloying of Cu2ZnSnS4 kesterite. Using a first-principles approach, we confirm the p-type conductivity of both Cu2ZnSnS4 and Cu2ZnGeS4, attributed to the low formation energies of the VCu and CuZn acceptor defects within the whole stable phase diagram range. Via doping of the Sn-kesterite matrix, we report the lowest formation energy for the substitutional defect GeSn. We also confirm the detrimental role of the substitutional defects XZn (X=Sn,Ge) acting as recombination centres within the Sn-based, the Ge-doped and the Ge-based kesterite. Finally, we highlight the reduction of the lattice distortion upon Ge incorporation resulting in a reduction of the carrier capture cross section and consequently a decrease of the non-radiative recombination rate within the bulk material., Comment: 14 pages, 6 figures, Journal of Materials Chemistry A (2022)

In this work, first principle calculations of Cu$_2$ZnSnS$_4$ (CZTS), Cu$_2$ZnGeS$_4$ (CZGS) and Cu$_2$ZnSiS$_4$ (CZSS) are performed to highlight the impact of the cationic substitution on the structural, electronic and optical properties of kesterite compounds. Direct bandgaps are reported with values of 1.32, 1.89 and 3.06 eV respectively for CZTS, CZGS and CZSS. In addition, absorption coefficient values of the order of $10^4$ cm$^{-1}$ are obtained, indicating the applicability of these materials as absorber layer for solar cell applications. In the second part of this study, ab initio results are used as input data to model the electrical power conversion efficiency of kesterite-based solar cell. In that perspective, we used an improved version of the Shockley-Queisser theoretical model including non-radiative recombination via an external parameter defined as the internal quantum efficiency. Based on predicted optimal absorber layer thicknesses, the variation of the solar cell maximal efficiency is studied as a function of the non-radiative recombination rate. Maximal efficiencies of 25.88, 19.94 and 3.11% are reported respectively for CZTS, CZGS and CZSS for vanishing non-radiative recombination rate. Using an internal quantum efficiency providing $V_{OC}$ values comparable to experimental measurements, solar cell efficiencies of 15.88, 14.98 and 2.66% are reported respectively for CZTS, CZGS and CZSS (for an optimal thickness of 1.15 $\mu$m). With this methodology, we confirm the suitability of CZTS in single junction solar cells, with a possible efficiency improvement of 10% enabled through the reduction of the non-radiative recombination rate. In addition, CZGS appears to be an interesting candidate as top cell absorber layer for tandem approaches whereas CZSS might be interesting for transparent PV windows., Comment: 11 pages, 6 figures and 3 tables

In ultrathin Cu(In,Ga)Se2(CIGS) film solar cells, the CdS/CIGS interface may become one of the limiting factors for efficiency. The first step toward reducing the impact of this problem could be a surface treatment process to improve the quality of the front interface. The purpose of this study is to have a better understanding of the effect of wet chemical surface treatment, using ammonium sulfide ((NH4)2S), on CIGS thin film layers with different Cu/(Ga + In) (CGI) ratios. Herein, photoluminescence (PL) and time-resolved PL (TRPL) studies are conducted on bare CIGS, ammonium sulfide–treated CIGS thin films, and samples with CdS. In bare CIGS, CGI ratio–dependent changes in PL are observed on both a low-energy (defect related transition) and a high-energy peak (band-to-band transition). After the surface treatment, the PL maximum increases by factors ranging from 4 to 11 depending on the CGI ratio, accompanied by a slower decay. Trends with similar improvement as in the PL study are observed in the performance of the solar cells. It is shown that the impact of the surface treatment is beneficial independently of the CGI ratio of the absorber layers. In all cases, the treatment is shown to improve the efficiency.

Current state-of-the-art Cu2ZnSn(S,Se)4kesterite solar cells are limited by low open-circuit voltages (VOC). In order to evaluate to what extent the substitution of Sn by Ge is able to result in higherVOCvalues, this article focuses on Cu2ZnGeSe4“CZGSe” devices. To reveal their full potential, different strategies are explored that, in particular, aim at the optimization of the CZGSe/buffer heterojunction. Here, employing hard X-ray photoelectron spectroscopy, it is evidenced that only a combination of different surface treatments is able to remove all detrimental secondary phases. Further improvements are achieved by establishing a solar cell heat treatment in air. A systematic study of the impact of different annealing temperatures and durations determines the best heat treatment parameters to be 60 min at 200 °C. Also, Zn(O,S,OH) as a more transparent alternative to the heavy-metal compound CdS buffer layer has been realized. Combining all of the strategies, solar cells with 8.5 and 7.5% total area efficiency have been prepared, which is a record for Sn-free kesterite solar cells and any kesterite solar cell with a Zn(O,S,OH) buffer, respectively. Beyond these records, this work clearly confirms the emerging trend that Ge-for-Sn substitution is a successful strategy to improve theVOCof kesterite solar cells.

In this work, hafnium oxide layer is investigated as rear surface passivation layer for ultra-thin (550 nm) CIGS solar cells. Point contact openings in the passivation layer are realized by spin-coating potassium fluoride prior to absorber layer growth. Contacts are formed during absorber layer growth and visualized with scanning electron microscopy (SEM). To assess the passivating qualities, HfOx was applied in a metal-insulator-semiconductor (MIS) structure, and it demonstrates a low interface trap density in combination with a negative density of charges. Since we used ultra-thin devices that are ideal to probe improvements at the rear, solar cell results indicated improvements in all cell parameters by the addition of 2 nm thick HfOx passivation layer with contact openings.

To determine if Cu(In, Ga)Se-2 (CIGS) can be submitted to the constraints that will be imposed on the solar materials of the future by an ever growing demand and necessity, we produced ultrathin (500 nm) single-stage coevaporated CIGS solar cells doped with varying amounts and types of alkali atoms. We subjected them to accelerated lifetime testing. In the present work, we observed the seeping of water into the grain boundaries which could be identified as one of the main culprits for performance degradation. In addition, this phenomenon could only be observed when alkali atoms were present in the absorber layer. This work received funding from the European Union’s H2020 research and innovation program under grant agreement 715027. We acknowledge the use of a LEAP 5000 HR at APT Flanders, KU Leuven (Hercules Foundation under contract ZW/13/09)

Numerical models are proposed that are able to describe the current-voltage (I-V) behaviour of two Cu2ZnGeSe4(CZGSe) solar cells measured under different illuminations at 300 K. In the model, the doping density of the CZGSe layer and the mobility of carriers are determined by capacitance-voltage (C-V) profiling and AC field Hall effect measurement, respectively. Some of the other parameters in the solar cells, including the series and the shunt resistance, the metal work function of the back contact, defect properties and absorption coefficient in the absorber layer, are determined using a differential evolution algorithm by fitting of the model with the experimentally measured I-V curves. Sensitivity analysis of our proposed model with SCAPS-1D demonstrates that the low metal work function, which results in a hole barrier at the back contact, the low shunt resistance and the high series resistance of the cell can explain the low fill factor and the low efficiency in these cells. This work is supported by the Special Research Fund (BOF) of Ghent Univeristy and the European Union 'Horizon 2020 research' and Innovation programme under Grant Agreement No. 640868. Yang, S (corresponding author), Univ Ghent, Dept Elect & Informat Syst, Technol Pk 126, B-9052 Zwijnaarde, Belgium. Sheng.Yang@ugent.be

In this work, an industrially viable and novel rear surface passivation approach for Copper Indium Gallium di-Selenide, Cu(In,Ga)Se2, CIGS, ultra-thin (500nm) solar cells is developed. The passivation layer was deposited by atomic layer deposition (ALD), and an alkali treatment was applied via spin coating. It was observed that selenization of the samples is required to create contact openings. The openings were visualized by SEM, and these results were supported by EDS. The impact of the oxide layer’s thickness, as well as the alkali solution’s molarity, was studied. Solar cells were produced for the optimal combination of these two parameters. As a result, with a relative 13% increase, the highest Vocof 623mV was achieved. Hence, the efficiency of the passivated solar cell was relatively increased by one-third, by using an industrially feasible, fast, and repeatable technique.

We review the stability and reliability results of kesterite (Cu2ZnSn(S,Se)4, CZTSSe)-based solar cells and we complete the reviewed data with additional as yet unpublished data on these matters. We also review published and new data on upscaling and the possible technological applications for this material. Kesterite material is composed of mainly earth-abundant elements and is therefore very attractive for large-scale applications. Stability data are so far quite scarce and the main results are the accelerated aging tests carried out for CZTSSe monograin technology, as well as yet unpublished data on long indoor and outdoor irradiance tests carried out on thin-film CZTSSe technology deposited by a wet processing method. On upscaling and technological applications we point out the works on three main large-scale photovoltaic technologies (monograin, in-line vacuum thin film, and wet-deposited thin film), as well as some work on water-splitting applications. IMRA Europe and crystalsol thank their numerous co-workers for contributing to this work. The work carried out at cyrstalsol was partly supported by the European Union through the European Regional Development Fund and Archimedes/DoRa project TK141. IMRA Europe, Midsummer and Ayesa acknowledge the European Commision for the funding of the kesterite research from 2017 by the H2020 program under the project STARCELL (H2020-NMBP-03-2016-720907).

Interface quality plays a key role in solar cell applications. Interface recombination at the front and rear surfaces, which determine this quality, have significant effects on open circuit voltage and fill factor values. In this work, several surface treatments were applied on Cu(In,Ga)Se2 (CIGS) surfaces to improve the interface quality. Besides, the passivation layer implementation was investigated to reduce interface recombination between the buffer and absorber layers.

This research reveals the missing or often undisclosed experimental data on processing conditions of Cu(In,Ga)(S,Se)2 absorbers by the two-step sequential technique. Accordingly, by employing a one-variable-at-a-time approach- where each factor is exclusively changed with respect to a defined center point, we identified a handful of significant parameters which play the most significant role in an absorber's properties and consequently, prospective high-performing solar cells. This was done by analyzing their impact on a few most important metrics. Hence, the vast processing window with numerous factors and levels for development of Cu(In,Ga)(S,Se)2 by this method becomes constrained and feasible to optimize in future endeavours.