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During the last few decades, major advances have been made in photovoltaic systems based on Cu(In,Ga)Se2 chalcopyrite. However, the most efficient photovoltaic cells are processed under high-energy-demanding vacuum conditions. To lower the costs and facilitate high-throughput production, printing/coating processes are proving to be effective solutions. This work combined printing, coating, and chemical bath deposition processes of photoabsorber, buffer, and transparent conductive layers for the development of solution-processed photovoltaic systems. Using a sustainable approach, all inks were formulated using water and ethanol as solvents. Screen printing of the photoabsorber on fluorine-doped tin-oxide-coated glass followed by selenization, chemical bath deposition of the cadmium sulfide buffer, and final sputtering of the intrinsic zinc oxide and aluminum-doped zinc oxide top conductive layers delivered a 6.6% maximum efficiency solar cell, a record for screen-printed Cu(In,Ga)Se2 solar cells. On the other hand, the all-non-vacuum-processed device with spray-coated intrinsic zinc-oxide- and tin-doped indium oxide top conductive layers delivered a 2.2% efficiency. The given approaches represent relevant steps towards the fabrication of sustainable and efficient Cu(In,Ga)Se2 solar cells.

Cu(In,Ga)Se2 (CIGSe) thin-film solar cells are a commercial photovoltaic technology that provides sustainable power. Here, we study the formation of Zn1-xSnxOy (ZTO) thin films as Cd-free buffer layers by chemical bath deposition (CBD) suitable for CIGSe solar cell devices. ZTO films were obtained by CBD onto SLG, by modifying a reported procedure otherwise leading to columnar ZnO thin films. Our ZTO films show a flatter morphology compared to the reference ZnO due to inhibition of the columnar growth. In addition, a non-trivial increase of the band gap was observed by enhancing Sn concentration. When a concentration of 20% [Sn]/([Sn]+[Zn]) (where [Sn] and [Zn] are the molar concentrations of Sn and Zn, respectively) is employed in the chemical bath, the resulting buffer layer allowed the CIGSe solar cell to achieve similar performance as with a CdS buffer layer (average efficiency of (11 ± 2)% ), yielding a maximum efficiency of 10.4%, with an average of (9 ± 2) %.

Typical Cu(In,Ga)Se2 solar cells are deposited on an opaque molybdenum back contact. However, for applications such as bifacial, semi-transparent or tandem solar cells a transparent back contact is required, for which various transparent conductive oxides have been tested, such as indium- or fluorine-doped tin oxide, and hydrogen-doped indium oxide. Here, a radio-frequency magnetron sputtering deposition process for In2O3:H (IOH) is investigated, where H is supplied from a Ar/H2 (5%) mixed gas and oxygen is pulsed during the entire deposition at room temperature. After deposition, the films are post-annealed in vacuum to optimize their optoelectronic properties. The oxygen plays an important role for the optoelectronic properties, where a high content of oxygen allows higher transparency but also increases the film sheet resistance. Optimum oxygen and Ar/H2 partial pressures of 3.2 E-2 Pa and 13E-2 Pa, respectively, were found, producing IOH films with average visible transparency of 87% and sheet resistance after annealing of 19 Ohm/sq., This work was supported by the project “Semi-Transparent Solar cells for building integrated photovoltaics (STAR-SOL)”, funded by FCT – Fundação para a Ciência e a Tecnologia (FCT‐FNR/0001/2018). Marina Alves thanks the Fundação para a Ciência e a Tecnologia (FCT), Portugal for the PhD Grant (2020.06063.BD).

Cadmium-free buffer layers deposited by a dry vacuum process are mandatory for low-cost and environmentally friendly Cu(In1-xGax)Se2 (CIGS) photovoltaic in-line production. Zn(O,S) has been identified as an alternative to the chemical bath deposited CdS buffer layer, providing comparable power conversion efficiencies. Recently, a significant efficiency enhancement has been reported for sputtered Zn(O,S) buffers after an annealing treatment of the complete solar cell stack; the enhancement was attributed to interdiffusion at the CIGS/Zn(O,S) interface, resulting in wide-gap ZnSO4 islands formation and reduced interface defects. Here, we exclude interdiffusion or island formation at the absorber/buffer interface after annealing up to 200 °C using high-resolution scanning transmission electron microscopy (HR-STEM) and energy-dispersive X-ray spectroscopy (EDX). Interestingly, HR-STEM imaging reveals an epitaxial relationship between a part of the Zn(O,S) buffer layer grains and the CIGS grains induced by annealing at such a low temperature. This alteration of the CIGS/buffer interface is expected to lead to a lower density of interface defects, and could explain the efficiency enhancement observed upon annealing the solar cell stack, although other causes cannot be excluded.

High-efficiency Cu(In,Ga)Se2 (CIGSe) thin-film solar cells are typically fabricated by a multistage coevaporation process. The Cu-rich composition achieved during the second stage is known to favor the grain growth of the polycrystalline CIGSe film and has a beneficial effect on the solar cell performance. In this article, we analyze the effect of copper stoichiometry on the grain size of sputtered CIGSe absorbers and the efficiency of respective solar cells. CIGSe absorber layers were deposited on Mo-coated soda-lime glass substrates by pulsed hybrid reactive magnetron sputtering from Cu-poor and Cu-rich Cu-In-Ga targets and simultaneous Se evaporation. CIGSe films sputtered with the Cu-rich target show larger grain size and lead to better solar cell performance. Furthermore, we also introduce a two-stage process, which further increases the solar cell performance, consisting of an initial CIGSe layer deposited from the Cu-rich target followed by an indium-selenide postdeposition step. This two-stage process effectively eliminates the unwanted Cu2- x Se impurity phase and renders the otherwise required and toxic KCN etching unnecessary.

Topological insulators possess a non-conductive bulk and present surface states, henceforth, they are electrically conductive along their boundaries. Bismuth selenide ($Bi_2Se_3$) is one of the most promising topological insulators. However, a major drawback is its n-type nature arising from its natural doping, which makes the transport in the bulk dominant. This effect can be overcome by shifting the chemical potential into the bandgap, turning the transport of the surface states to be more pronounced than the bulk counterpart. In this work, $Bi_2Se_3$ was grown by molecular beam epitaxy and doped with 0.8, 2, 7, and 14 at. % of Ga, with the aim of shifting the chemical potential into the bandgap. The structural, morphological, and electronic properties of the Ga doped $Bi_2Se_3$ are studied. Raman and X-ray diffraction measurements confirmed the incorporation of the dopants into the crystal structure. Transport and magnetoresistance measurements in the temperature range of 1.5 to 300 K show that Ga-doped $Bi_2Se_3$ is n-type with a bulk charge carrier concentration of $10^{19} cm^{-3}$. Remarkably, magnetotransport of the weak antilocalization effect (WAL) measurements confirm the existence of surface states up to a doping percentage of 2 at. % of Ga and coherence length values between 50-800 nm, which envisages the possibility of topological superconductivity in this material., 17 pages, 8 figures, Supplementary Information included

Bandgap engineering and quantum confinement in semiconductor heterostructures provide the means to fine-tune material response to electromagnetic fields and light in a wide range of the spectrum. Nonetheless, forming semiconductor heterostructures on lattice-mismatched substrates has been a challenge for several decades, leading to restrictions for device integration and the lack of efficient devices in important wavelength bands. Here, we show that the van der Waals epitaxy of two-dimensional (2D) GaSe and InSe heterostructures occur on substrates with substantially different lattice parameters, namely silicon and sapphire. The GaSe/InSe heterostructures were applied in the growth of quantum wells and superlattices presenting photoluminescence and absorption related to interband transitions. Moreover, we demonstrate a self-powered photodetector based on this heterostructure on Si that works in the visible-NIR wavelength range. Fabricated at wafer-scale, these results pave the way for an easy integration of optoelectronics based on these layered 2D materials in current Si technology., 16 Pages, 5 figures. Supplementary Information included in the end (+10 pages, +10 Figures, + 2 Tables). Partially presented at 21st ICMBE - September 2021

We present the development of a small foot-print physical vapor deposition (PVD) system for in-situ deposition of all layers required in a complete Cu(In,Ga)Se (CIGS) solar cell. Seven sputtering magnetrons and one valved-cracker source have been custom designed and manufactured for this system, named SpuTtering for Advanced Research (STAR). The purpose of STAR is to develop a technique to fabricate a complete CIGS solar cell, including contacts, absorber, buffer, and window layers, under high vacuum with the aim to transfer this technology to a future industrial production line. The system's capabilities and its relatively high throughput place it somewhere in between research and industrial development levels. It is possible to work on the deposition of the back contact, the CIGS absorber, and the window layer of three solar cells simultaneously. Calibration data, selection of parameters for the deposition of the individual layers, and initial results of a complete CIGS solar cell developed with STAR are reported., We acknowledge financial support by the Spanish projects AIC-B-2011-0806 and MAT2015-67021-R, and by the “Micro-concentrator thin film solar cells (MiconCell)” project (028922), and the “Correlated Analysis of Inorganic Solar Cells in and outside an Electron Microscope (CASOLEM)” project (028917), both co-funded by FCT and the ERDF through COMPETE2020. We also acknowledge financial support by MCIU-AEI-FEDER-UE (ENE2017-91092-EXP, RTI2018-096937-B-C22) and Comunidad de Madrid (P2018/EMT-4308). We acknowledge the services at IMN-CNM from the X-SEM Laboratory (MINECO CSIC13-4E-1794) and from MiNa Laboratory (funding from CM under project S2013/ICE-2822, Space-Tec) both with support from EU (FEDER, FSE)”.

In this work, we investigate the effect of selenium-free annealing on cesium fluoride (CsF) treated Cu(In,Ga)Se2 (CIGS) thin films and evaluate their solar cell performance. Annealing of CsF-treated CIGS thin films changes the surface morphology, the chemical composition, and reduces the Urbach energies. However, the full benefit of the reduced Urbach energies of the annealed samples is not obtained, because of an increased buffer/CIGS interfacial recombination owing as a consequence of re-evaporation of the alkali-containing layer from the surface region after upon annealing. On the other hand, CsF-treated CIGS thin films without any annealing after the post deposition treatment (PDT) preserves the alkali-containing layer at the surface region, thereby leading to an improved buffer/CIGS interface. Consequently, the open-circuit voltage (VOC) and fill factor improve significantly in these devices. The Urbach energies of both annealed and non-annealed solar cells are calculated from external quantum efficiency measurement to understand their impact on VOC and VOC deficit. No correlation between the VOC deficit and the Urbach energies is observed.

Rhenium-based 2D transition metal dichalcogenides such as ReSe2 are suitable candidates as photoactive materials for optoelectronic devices. Here, photodetectors based on mechanically exfoliated ReSe2 crystals were fabricated using chemical vapor deposited (CVD) graphene single-crystal (GSC) as lateral contacts. A “pick & place” method was adopted to transfer the desired crystals to the intended position, easing the device fabrication while reducing potential contaminations. A similar device with Au was fabricated to compare contacts’ performance. Lastly, a CVD hexagonal boron nitride (hBN) substrate passivation layer was designed and introduced in the device architecture. Raman spectroscopy was carried out to evaluate the device materials’ structural and electronic properties. Kelvin probe force measurements were done to calculate the materials’ work function, measuring a minimal Schottky barrier height for the GSC/ReSe2 contact (0.06 eV). Regarding the electrical performance, I-V curves showed sizable currents in the GSC/ReSe2 devices in the dark and under illumination. The devices presented high photocurrent and responsivity, along with an external quantum efficiency greatly exceeding 100%, confirming the non-blocking nature of the GSC contacts at high bias voltage (above 2 V). When introducing the hBN passivation layer, the device under white light reached a photo-to-dark current ratio up to 106.

Advanced functional materials 31(41), 2103119 (2021). doi:10.1002/adfm.202103119, Published by Wiley-VCH, Weinheim

2D GaSe is a semiconductor belonging to the group of post-transition metal chalcogenides with great potential for advanced optoelectronic applications. The weak interlayer interaction in multilayer 2D materials allows the formation of several polymorphs. Here, the first structural observation of a new GaSe polymorph is reported, characterized by a distinct atomic configuration with a centrosymmetric monolayer (D-3d point group). The atomic structure of this new GaSe polymorph is determined by aberration-corrected scanning transmission electron microscopy. Density-functional theory calculations verify the structural stability of this polymorph. Furthermore, the band structure and Raman intensities are calculated, predicting slight differences to the currently known polymorphs. In addition, the occurrence of layer rotations, interlayer relative orientations, as well as translation shear faults is discussed. The experimental confirmation of the new GaSe polymorph indicates the importance of investigating changes in the crystal structure, which can further impact the properties of this family of compounds, This article has received support from the project Nanotechnology Based Functional Solutions (NORTE-01-0145-FEDER-000019), supported by Norte Portugal Regional Operational Programme (NORTE2020), under the PORTUGAL 2020 Partnership Agreement, through the European Regional Development Fund (ERDF). Additional support by National Funds through the Portuguese Foundation for Science and Technology (FCT) in the framework of the project "LA2D" -PTDC/FIS-NAN/3668/2014 is acknowledged. This work was supported by FCT, through IDMEC, under LAETA, project UIDB/50022/2020. A. M.-S. thanks the Marie-Curie-COFUND program Nano TRAIN for Growth II (Grant Agreement 713640) and the Ramon y Cajal programme (grant RYC2018-024024-I, MINECO, Spain). This work was carried out in part through the use of the INL Advanced Electron Microscopy, Imaging, and Spectroscopy Facility. The computations were performed on the Tirant III cluster of the Servei d'Informatica of the University of Valencia (project vlc82) and on Mare Nostrum cluster of the Barcelona Supercomputing Center (project FI-2020-2-033 and FI-2020-3-0021).

Micro-concentrator solar cells enable higher power conversion efficiencies and material savings when compared to large-area non-concentrated solar cells. In this study, we use materials-efficient area-selective electrodeposition of the metallic elements, coupled with selenium reactive annealing, to form Cu(In,Ga)Se2 semiconductor absorber layers in patterned microelectrode arrays. This process achieves significant material savings of the low-abundance elements. The resulting copper-poor micro-absorber layers’ composition and homogeneity depend on the deposition charge, where higher charge leads to greater inhomogeneity in the Cu/In ratio and to a patchy presence of a CuIn5Se8 OVC phase. Photovoltaic devices show open-circuit voltages of up to 525 mV under a concentration factor of 18 ×, which is larger than other reported Cu(In,Ga)Se2 micro-solar cells fabricated by materials-efficient methods. Furthermore, a single micro-solar cell device, measured under light concentration, displayed a power conversion efficiency of 5% under a concentration factor of 33 ×. These results show the potential of the presented method to assemble micro-concentrator photovoltaic devices, which operate at higher efficiencies while using light concentration.

A new approach to fabricate copper, indium, gallium diselenide (CIGSe) solar cells on conductive fluorine-doped tin oxide (FTO) reached an efficiency of over 6% for a champion photovoltaic device. ...

Chalcopyrite solar cells achieve efficiencies above 23%. The latest improvements are due to post-deposition treatments (PDT) with heavy alkalis. This study provides a comprehensive description of the effect of PDT on the chemical and electronic structure of surface and bulk of Cu(In,Ga)Se-2. Chemical changes at the surface appear similar, independent of absorber or alkali. However, the effect on the surface electronic structure differs with absorber or type of treatment, although the improvement of the solar cell efficiency is the same. Thus, changes at the surface cannot be the only effect of the PDT treatment. The main effect of PDT with heavy alkalis concerns bulk recombination. The reduction in bulk recombination goes along with a reduced density of electronic tail states. Improvements in open-circuit voltage appear together with reduced band bending at grain boundaries. Heavy alkalis accumulate at grain boundaries and are not detected in the grains. This behavior is understood by the energetics of the formation of single-phase Cu-alkali compounds. Thus, the efficiency improvement with heavy alkali PDT can be attributed to reduced band bending at grain boundaries, which reduces tail states and nonradiative recombination and is caused by accumulation of heavy alkalis at grain boundaries. This work was supported by the European Union's Horizon 2020 research and innovation program under grant agreement no. 641004 (Sharc25) and by the Swiss State Secretariat for Education, Research and Innovation (SERI) under contract number 15.0158. Siebentritt, S (reprint author), Univ Luxembourg, Lab Photovolta, Phys & Mat Sci Res Unit, 41 Rue Brill, L-4422 Belvaux, Luxembourg. susanne.siebentritt@uni.lu

Recent world record efficiencies for thin film solar cells based on Cu(In,Ga)Se2 (CIGS) have been realized with absorbers subject to alkali fluoride post deposition treatments (PDT). We investigated the effect of ambient air exposure on the electronic properties of CIGS with KF-PDT in a combined time-dependent Kelvin probe force microscopy and X-ray photoelectron spectroscopy study. We also studied the early stage formation of the absorber/buffer interface after the initial deposition of CdS in the chemical bath. Our study shows that the KF-PDT, as well as the CdS deposition process induce an increase in the overall surface work function, as compared to bare CIGS. A K-In-Se compound forms after the KF-PDT, accompanied by a stable In oxide which explains the remarkable stability of the contact potential difference to air exposure, confirming phenomenological observations in many laboratories. In clear contrast to the untreated CIGS, the KF-treated CIGS/CdS interface shows a significant variation in the sur...

Kelvin probe force microscopy (KPFM) has been used for the characterization of metals, insulators, and semiconducting materials on the nanometer scale. Especially in semiconductors, the charge dynamics are of high interest. Recently, several techniques for time-resolved measurements with time resolution down to picoseconds have been developed, many times using a modulated excitation signal, e.g., light modulation or bias modulation that induces changes in the charge carrier distribution. For fast modulation frequencies, the KPFM controller measures an average surface potential, which contains information about the involved charge carrier dynamics. Here, we show that such measurements are prone to artifacts due to frequency mixing, by performing numerical dynamics simulations of the cantilever oscillation in KPFM subjected to a bias-modulated signal. For square bias pulses, the resulting time-dependent electrostatic forces are very complex and result in intricate mixing of frequencies that may, in some cases, have a component at the detection frequency, leading to falsified KPFM measurements. Additionally, we performed fast Fourier transform (FFT) analyses that match the results of the numerical dynamics simulations. Small differences are observed that can be attributed to transients and higher-order Fourier components, as a consequence of the intricate nature of the cantilever driving forces. These results are corroborated by experimental measurements on a model system. In the experimental case, additional artifacts are observed due to constructive or destructive interference of the bias modulation with the cantilever oscillation. Also, in the case of light modulation, we demonstrate artifacts due to unwanted illumination of the photodetector of the beam deflection detection system. Finally, guidelines for avoiding such artifacts are given.

Using concentrated sunlight for photovoltaic energy conversion has long been identified as a way to make cost-intensive solar cell materials and devices more cost effective. The recently proposed micro-concentrator approach for Cu(In,Ga)Se2 brings concentrator photovoltaics from the centimeter and millimeter scale down to the micrometer scale, with the goal of reducing the amount of critical raw materials. We show here that the micro-concentrator approach has large benefits in terms of the heat dissipation and that heat management on the micro-scale allows the use of concentration factors as high as 1000× without any special cooling efforts. Specifically, we show that line-shaped micro-concentrator solar cells need to be either smaller than 50 μm wide, or be used at low concentration factors below 100×. In contrast, island-shaped micro-concentrator solar cells show improved efficiencies at cell sizes of (100 μm)2 and concentration factors up to 1000×. Additionally, we consider different materials for the substrate and the lens array for light concentration in view of their heat management capacities. The results presented here provide design guidelines for the further development of thin film micro-concentrator solar cells, applicable to a variety of materials systems, e.g. Cu(In,Ga)Se2, CdTe, or metal halide perovskite solar cells.

Hexagonal boron nitride (h-BN) is a critical 2D insulator used as a substrate, gate dielectric, or encapsulation layer for graphene and other 2D materials and their van der Waals heterostructures. It is also promising as an active layer in single-photon emitters and other photonic devices. With the chemical formula H3N-BH3, ammonia borane is the most attractive precursor for up-scalable growth of large-area h-BN, using chemical vapor deposition given its stoichiometric B:N ratio, high stability under ambient conditions, nontoxicity, and high solubility in common solvents. Here, the synthesis of large-area (100 × 150 mm2) crystalline hexagonal boron nitride layers by thermal activation and decomposition of the precursor ammonia borane is presented. We describe two different reaction pathways for h-BN synthesis, providing evidence for dissimilarities in the sublimation kinetics of ammonia borane and how these differences critically influence the growth of h-BN. This understanding helps us accelerate h-BN production, reuse precursors, and reduce machine runtime, paving the way for upscalability. Moreover, our work provides a consistent unified view explaining the diverse deposition conditions reported in the literature for h-BN grown by CVD using ammonia borane as a precursor., This work was supported by National Funds through the Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Funding No. UIDB/04650/2020 and Project Nos. PTDC/FIS-NAN/3668/2014 (LA2D) and PTDC/FIS-MAC/28114/2017 (POCI-01-0145-FEDER-028114) (GRAPHSENS).

Rhenium-based 2D transition metal dichalcogenides such as ReSe2 are suitable candidates as photoactive materials for optoelectronic devices. Here, photodetectors based on mechanically exfoliated ReSe2 crystals were fabricated using chemical vapor deposited (CVD) graphene single-crystal (GSC) as lateral contacts. A "pick & place" method was adopted to transfer the desired crystals to the intended position, easing the device fabrication while reducing potential contaminations. A similar device with Au was fabricated to compare contacts' performance. Lastly, a CVD hexagonal boron nitride (hBN) substrate passivation layer was designed and introduced in the device architecture. Raman spectroscopy was carried out to evaluate the device materials' structural and electronic properties. Kelvin probe force measurements were done to calculate the materials' work function, measuring a minimal Schottky barrier height for the GSC/ReSe2 contact (0.06 eV). Regarding the electrical performance, I-V curves showed sizable currents in the GSC/ReSe2 devices in the dark and under illumination. The devices presented high photocurrent and responsivity, along with an external quantum efficiency greatly exceeding 100%, confirming the non-blocking nature of the GSC contacts at high bias voltage (above 2 V). When introducing the hBN passivation layer, the device under white light reached a photo-to-dark current ratio up to 106., This research was funded by National Funds through the Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Funding UIDB/04650/2020 and projects PTDC/FIS-NAN/3668/2014 (LA2D) and PTDC/FIS-MAC/28114/2017 (POCI-01-0145-FEDER-028114) (GRAPHSENS). A.C. acknowledges the financial support of the project "GEMISGraphene-enhanced Electro-Magnetic Interference Shielding," with the reference POCI-01-0247-FEDER-045939, co-funded by COMPETE 2020-Operational Programme for Competitiveness and Internationalization and FCT-Science and Technology Foundation, under the Portugal 2020 Partnership Agreement, through the European Regional Development Fund (ERDF).

Thin-film solar cells based on Cu(In, Ga)Se2 chalcopyrite materials have achieved record power conversion efficiencies (PCE) above 22%, higher than any other thin film technology. Here, a proof-of-principle for Cu(In, Ga)Se2 solar cells with a reduced materials consumption by a factor of ~100 is demonstrated for which simulations indicate an even higher PCE potential. The concept is based on using micrometer-sized solar cells onto which sunlight is concentrated using a lens array. Thereby, all incoming sunlight is absorbed in solar cells that only cover a fraction (on the order of 1/100) of the surface, creating thus significant material savings. A fabrication process based on selective growth of CuInSe2 micro solar cells is presented, using electrodeposition into holes of an insulating SiO2 layer on a Mo back electrical contact. Proof-of-principle micro solar cells using this materials-savings approach are realized and characterized. Additionally, the heat management of micro-concentrator solar cells is studied using finite element simulations. For square micro solar cells up to 100 µm side length the temperature increase due to the concentrated sunlight can be kept below 4 °C above that of a flat panel solar cell. An increase of the PCE by 4.9% is estimated, considering the combined effect of the open circuit voltage increase due to concentrated sunlight, and the PCE decrease due to the temperature increase.

The currently most efficient polycrystalline solar cells are based on the Cu(In,Ga)Se compound as a light absorption layer. However, in view of new concepts of nanostructured solar cells, CuInSe nanostructures are of high interest. In this work, we report CuInSe nanodots grown through a vacuum-compatible co-evaporation growth process on an amorphous surface. The density, mean size, and peak optical emission energy of the nanodots can be controlled by changing the growth temperature. Scanning transmission electron microscopy measurements confirmed the crystallinity of the nanodots as well as chemical composition and structure compatible with tetragonal CuInSe. Photoluminescence measurements of CdS-passivated nanodots showed that the nanodots are optoelectronically active with a broad emission extending to energies above the CuInSe bulk bandgap and in agreement with the distribution of sizes. A blue-shift of the luminescence is observed as the average size of the nanodots gets smaller, evidencing quantum confinement in all samples. By using simple quantum confinement calculations, we correlate the photoluminescence peak emission energy with the average size of the nanodots., The authors would like to acknowledge the CAPES (CAPESINL 04/14), CNPq, and FAPEMIG funding agencies for financial support. We acknowledge the collaboration project with IMM-CSIC (AIC-B-2011-0806). P. M. P. S. acknowledges financial support from EU through the FP7 Marie Curie IEF 2012 Action No. 327367. The projects RECI/FIS-NAN/0183/ 2012 (COMPETE: FCOMP-01-0124-FEDER-027494) and UID/CTM/50025/2013 from the Fundação para a Ciência e a Tecnologia (Portugal) and the project Nanotechnology Based Functional Solutions (NORTE-01-0145-FEDER-000019) are also acknowledged.

Kesterite solar cells based on CuZnSnS4 and Cu2ZnSnSe4 (CZTSe) are potential future candidates to be used in thin-film solar cells. The technology still has to be developed to a great extent and for this to happen, high levels of confidence in the characterization methods are required, so that improvements can be made on solid interpretations. In this study, we show that the interpretations of one of the most used characterization techniques in kesterites, scanning transmission electron microscopy (STEM), might be affected by its specimen preparation when using focused ion beam (FIB). Using complementary measurements based on scanning electron microscopy and Raman scattering spectroscopy, compelling evidence shows that secondary phases of ZnSe mixed in the bulk of CZTSe are the likely cause of the appearance of voids in STEM lamellae. Sputtering simulations support this interpretation by showing that Zn in a ZnSe matrix is preferentially sputtered compared with any metal atom in a CZTSe matrix.

Large-scale industrial fabrication of Cu(In,Ga)Se (CIGS) photovoltaic panels would benefit significantly if the buffer layer chemical bath deposition could be replaced by a cadmium-free dry vacuum process suitable for in-line production. This Letter reports on the development of a Zn(O,S) buffer layer deposited by vacuum-based magnetron sputtering from a single target onto commercial CIGS absorbers cut from a module-size glass/Mo/CIGS stack. The buffer-window stack consisting of Zn(OS)/i-ZnO/ZnO:Al is optimized for layer thickness and optical and electronic properties, leading to an average device efficiency of 4.7%, which can be improved by annealing at 200 °C to a maximum of 10.5%, mainly due to a considerable increase in the open-circuit voltage (V). Temperature-dependent current density versus voltage (J–V) characteristics show a reduced interface recombination upon annealing, explaining the observed V boost. Quantum efficiency shows improvements in the long and short wavelength region, setting in at different annealing temperatures, and photoemission depth profiling indicates interdiffusion of all atomic species at the CIGS/Zn(O,S) interface. Electrical device simulations explain the observed effects by a modification of the band offset at the interface and defects passivation. Both effects are attributed to the observed interdiffusion during annealing., This work was partially supported by the European Union's Horizon 2020 research and innovation program under grant agreement No. 641004 (project Sharc25). The authors acknowledge additional support by the Spanish project AIC‐B‐2011‐0806, and by the “Micro‐concentrator thin film solar cells (MiconCell)” project (028922) and the “Correlated Analysis of Inorganic Solar Cells in and outside an Electron Microscope (CASOLEM)” project (028917), both co‐funded by FCT and ERDF through COMPETE2020. DC acknowledges the European Commission for funding the NanoTrainforGrowth II project No. 713640 through the Marie Curie Cofund programme.

For mass fabrication of highly-efficient photovoltaic modules based on Cu(In,Ga)Se2 (CIGSe) absorber layers the availability and cost of the critical raw materials In and Ga present a potential bottleneck. The micro-concentrator solar cell concept provides a solution by using micro lenses to concentrate incoming sun light on an array of micro-sized CIGSe solar cells. The challenge is to fabricate CIGSe micro islands in exactly the desired positions using only the required material. Here, we analyze the area-selective electrodeposition of CuInSe2 into holes in an insulating SiO2 template layer as a material-efficient fabrication approach. We observe that the deposition process shows a strong dependence on the hole size, with a faster deposition around the hole perimeter. Based on a model developed for electrochemical reactions at ultra-micro electrodes, we develop numerical simulations for the electrochemical deposition process. The simulations consider the changing micro-electrode geometry throughout the deposition process, and provide a reasonable fit to the experimental data. Finally, it is shown that CuInSe2 micro solar cells fabricated by electrodeposition reach efficiencies of 4.8% under 1 sun, providing a proof-of-concept demonstration meriting further development. Keywords: Electrodeposition, Ultra-micro electrodes, Cu(In,Ga)Se2, Solar cells

Effects related to alkali metal doping and grain boundaries have puzzled the chalcopyrite photovoltaics community for a long time. This study is the first to report reversible oxidation of grain boundaries in CuInSe2 thin films. The phenomenon is observed in sodium-doped films, but not in undoped ones. Cathodoluminescence imaging, secondary ion mass spectrometry and Kelvin probe force microscopy analyses are performed on CuInSe2 thin films before and after exposure to vacuum. The findings suggest the existence of yet unidentified solid-gas equilibria. Resolving the nature of such reactions will provide new insights into the mechanism of alkali metal doping and passivation in chalcopyrite solar cells.

The properties and performance of polycrystalline materials depend critically on the properties of their grain boundaries. Polycrystalline photovoltaic materials – e.g. hybrid halide perovskites, copper indium gallium diselenide (CIGSe) and cadmium telluride – have already demonstrated high efficiencies and promise cost-effective electricity supply. For CIGSe-based solar cells, an efficiency above 23% has recently been achieved using an alkali-fluoride post-deposition treatment; however, its full impact and functional principle are not yet fully understood. Here, we show direct evidence for the passivation of grain boundaries in CIGSe treated with three different alkali-fluorides through a detailed study of the nanoscale optoelectronic properties. We determine a correlation of the surface potential change at grain boundaries with the open-circuit voltage, which is supported by numerical simulations. Our results suggest that heavier alkali elements might lead to better passivation by reducing the density of charged defects and increasing the formation of secondary phases at grain boundaries.

The currently most efficient polycrystalline solar cells are based on the Cu(In,Ga)Se2 compound as a light absorption layer. However, in view of new concepts of nanostructured solar cells, CuInSe2 nanostructures are of high interest. In this work, we report CuInSe2 nanodots grown through a vacuum-compatible co-evaporation growth process on an amorphous surface. The density, mean size, and peak optical emission energy of the nanodots can be controlled by changing the growth temperature. Scanning transmission electron microscopy measurements confirmed the crystallinity of the nanodots as well as chemical composition and structure compatible with tetragonal CuInSe2. Photoluminescence measurements of CdS-passivated nanodots showed that the nanodots are optoelectronically active with a broad emission extending to energies above the CuInSe2 bulk bandgap and in agreement with the distribution of sizes. A blue-shift of the luminescence is observed as the average size of the nanodots gets smaller, evidencing quantum confinement in all samples. By using simple quantum confinement calculations, we correlate the photoluminescence peak emission energy with the average size of the nanodots.

The epitaxial growth of two-dimensional (2D) $\beta-In_2Se_3$ material was obtained over 2-inches c-sapphire wafers using molecular beam epitaxy (MBE). Excellent quality of thick (90 nm) and very thin films, down to two quintuple layers (2 nm), was confirmed by x-ray diffraction (XRD), Raman spectroscopy, and aberration-corrected scanning transmission electron microscopy (ac-STEM). Wafer-scale fabrication of photodetectors based on five quintuple layers was produced using photolithography and other standard semiconductor processing methods. The photodetectors exhibit responsivity of 3 mA/W, peak specific detectivity (D*) of $10^9$ Jones, external quantum efficiency (EQE) of 0.67 % at 550 nm, and response-time of ~7 ms, which is faster than any result previously reported for $\beta-In_2Se_3$ photodetectors. From the photocurrent measurements, an optical bandgap of 1.38 eV was observed. These results on wafer-scale deposition of 2D $In_2Se_3$, as well as its fabrication into optoelectronic devices provide the missing link that will enable the commercialization of 2D materials.