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Chalcopyrite Cu(In,Ga)Se

The chalcopyrite Cu(In,Ga)S${_2}$ has gained renewed interest in recent years due to the potential application in tandem solar cells. In this contribution, a combined theoretical and experimental approach is applied to investigate stable and metastable phases forming in CuInS${_2}$ (CIS) thin films. Ab initio calculations are performed to obtain formation energies, X-ray diffraction patterns, and Raman spectra of CIS polytypes and related compounds. Multiple CIS structures with zinc-blende and wurtzite-derived lattices are identified and their XRD/Raman patterns are shown to contain overlapping features, which could lead to misidentification. Thin films with compositions from Cu-rich to Cu-poor are synthesized with a two-step approach based on sputtering from binary targets followed by high-temperature sulfurization. It is discovered that several CIS polymorphs are formed when growing the material with this approach. In the Cu-poor material, wurtzite CIS is observed for the first time in sputtered thin films along with chalcopyrite CIS and CuAu-ordered CIS. Once the wurtzite CIS phase has formed, it is difficult to convert into the stable chalcopyrite polymorph. CuIn${_5}$S${_8}$ and NaInS${_2}$ accommodating In-excess are found alongside the CIS polymorphs. It is argued that the metastable polymorphs are stabilized by off-stoichiometry of the precursors, hence tight composition control is required.

Atomic Layer Deposition of Ternary Compounds on Cu(In,Ga)Se2 : An In Situ Quartz Crystal Microbalance Study

This contribution concerns the effect of the Ag content in wide‐gap Agw Cu1‐w In1‐x Gax Se2 (ACIGS) absorber films and its impact on solar cell performance. First‐principles calculations are conduc ...

International audience; We report on the development of highly reflective back contacts (RBCs) made of multilayer stacks for ultrathin CIGS solar cells. Two architectures are compared: they are made of a silver mirror coated either with a single layer of In2O3:Sn (ITO) or with a bilayer of ZnO:Al/ITO. Due to the improvement of CIGS rear reflectance, both back contacts result in a significant external quantum efficiency enhancement, in agreement with optical simulations. However, solar cells fabricated with Ag/ITO back contacts exhibit a strong shunting behavior. The key role of the ZnO:Al layer to control the morphology of the top ITO layer and to avoid silver diffusion through the back contact is highlighted. For a 500-nm-thick CIGS layer, this optimized RBC leads to a best cell with a short-circuit current of 27.8 mA/cm2 (+2.2 mA/cm2 as compared to a Mo back contact) and a 12.2%-efficiency (+2.5% absolute).

Gallium alloying and grading in Cu(In,Ga)Se-2 (CIGS) are well-established strategies for improving performance of thin-film solar cells by tailoring band profiles within the absorber. Similarly, Ag incorporation is considered to be an effective complementary route towards further advancement of the field. Herein, we explore thermodynamics of the formation of (Ag,Cu)(In,Ga)Se-2 (ACIGS) alloy. Using first-principles methods, we reveal the existence of a miscibility gap in the Ga-rich alloys at temperatures close to those employed for the co-evaporation growth. We demonstrate that this property can result in phase separation and the formation of Ag gradients throughout the film thickness. We prove experimentally that the phase separation can indeed occur during low-temperature growth and/or post-deposition treatments. Furthermore, we uncover the anticorrelation between Ag and Ga contents, and demonstrate thermodynamically-driven formation of [Ag]/([Ag] + [Cu]) gradients in films with a steep [Ga]/([Ga] + [In]) profile. Finally, we discuss how these phenomena can influence solar cell devices. The presented results are expected to provide fundamental insight into the physics of growth and processing of ACIGS absorbers, which could be utilized to further boost the efficiency of thin-film solar cells.

(Ag,Cu)(In,Ga)Se2 solar cells with bandgaps of ≈1.45 eV with a large spread in absorber stoichiometry are characterized with the intention of assessing the effect of composition on the stability of the devices. This material is observed to have a poor diffusion length, leading to very strong dependence upon the depletion region width for charge carrier collection. The depletion width is observed to depend strongly upon the stoichiometry value and shrinks significantly after an initial period of dark storage. It is also seen that the depletion width can be varied strongly through light-soaking and dry-heat treatments, with prolonged annealing leading to detrimental contraction and light soaking leading to expansion which increases current collection. The extent of depletion width variation in response to the treatments is also clearly linked to absorber stoichiometry. Consequently, the device performance, particularly the current output, exhibits a stoichiometry dependence and is considerably affected after each round of treatment. Possible causes of this behavior are discussed.

It is attractive to alloy Cu(In,Ga)Se2 solar-cell absorbers with Ag (ACIGSe), since they lead to similar device performances as the Ag-free absorber layers, while they can be synthesized at much lower deposition temperatures. However, a KF post-deposition treatment (PDT) of the ACIGSe absorber surface is necessary to achieve higher open-circuit voltages (Voc). The present work provides microscopic insights to the effects of this KF PDT, employing correlative scanning-electron microscope techniques on identical positions of cross-sectional specimens of the cell stacks. We found that the increase in Voc after the KF PDT can be explained by the removal of Cu-poor, Ag-poor, and Ga-rich regions near the ACIGSe/CdS interface. The KF PDT leads, when optimally doped, to a very thin K-Ag-Cu-Ga-In-Se layer between ACIGSe and CdS. If the KF dose is too large, we find that Cu-poor and K-rich regions form near the ACIGSe/CdS interface with enhanced nonradiative recombination which explains a decrease in the Voc. This effect occurs in addition to the presence of a (K,Ag,Cu)InSe2 intermediate layer, that might be responsible for limiting the short-current density of the solar cells due to a current blocking behavior. Title in Web of Science: Microscopic insight into the impact of the KF post-deposition treatment on optoelectronic properties of (Ag,Cu)(In,Ga)Se-2 solar cells

Herein, a new route of sulfur grading in CuInSe2 (CISe) thin-film solar absorbers by introducing an ultrathin (

Chalcopyrite Cu(In,Ga)Se-2 (CIGSe) solar absorbers are renowned for delivering high solar power conversion efficiency despite containing high concentration of lattice defects amounting to copper deficiencies of several atomic percent. The unique ability to incorporate this deficiency without triggering decomposition (i.e. "tolerance to off-stoichiometry") is viewed by many as the key feature of CIGSe. In principle, this property could benefit any solar absorber, but remarkably little attention has been paid to it so far. In this study, we assess the tolerance to off-stoichiometry of thin-film photovoltaic materials by carrying out ab initio analysis of group-I-poor ordered defect compounds (ODCs) in the extended family of I-III-VI systems (where I = Cu, Ag, III = Al, Ga, In, and VI = S, Se, Te). We analyze convex hulls and structural evolution with respect to group-I content, link them with experimental phase diagrams, and determine two empirical principles for the future identification of solar energy materials with high tolerance to off-stoichiometry. Practical implications for the deposition of I-III-VI absorbers are also discussed in light of our computational results and recent experimental findings.

As devices become smaller and more complex, the interfaces between adjacent materials become increasingly important and are often critical to device performance. An important research goal is to improve the interface between the absorber and the window layer by inserting buffer layers to adjust the transition. Depth-resolved studies are key for a fundamental understanding of the interface. In the present experiment, the interface between the chalcopyrite Cu(In,Ga)Se2 absorber and various buffer layers are investigated using low-energy muon spin rotation (μSR) spectroscopy. Depth resolution in the nm range is achieved by implanting the muons with different energies so that they stop at different depths in the sample. Near the interface, a region about 50 nm wide is detected where the lattice is more distorted than further inside the absorber. The distortion is attributed to the long-range strain field caused by defects. These measurements allow a quantification of the corresponding passivation effect of the buffer layer. Bath-deposited cadmium sulfide provides the best defect passivation in the near interface region, in contrast to the dry-deposited oxides, which have a much smaller effect. The experiment demonstrates the great potential of low energy μSR spectroscopy for microscopic interfacial studies of multilayer systems., This work is based on experiments performed at the Swiss Muon Source (SμS), Paul Scherrer Institute, Villigen, Switzerland. A.W. thanks Prof. Klaus Lips for the invitation to the Helmholtz-Zentrum Berlin für Materialien und Energie. This work was supported with funds from FEDER (Programa Operacional Factores de Competitividade COMPETE) and by national funds from FCT - Fundação para a Ciância e Tecnologia, I. P. (Portugal) under projects PTDC/FIS-MAC/29696/2017, PD/BD/142780/2018, UID/04564/2020, UIDB/04730/2020, UIDP/04730/2020, UIDB/50025/2020, and UIDP/50025/2020.

Photovoltaic (PV) electrolysis is an important and powerful technology for environmentally-friendly fuel production based on solar energy. By directly coupling solar cell materials to electrochemical systems to perform water electrolysis, solar energy can be converted into hydrogen fuel utilizing locally-generated heat and avoid losses from DC-DC convertors and power grid transmission. Although there have been significant contributions to the photoelectrochemical and PV-electrolysis field using isolated laboratory cells, the capacity to upscale and retain high levels of efficiency in larger modules remains a critical issue for widespread use and application. In this study, we develop thermally-integrated, solar-driven water-splitting device modules using AgCu(In,Ga)Se-2 (ACIGS) and an alkaline electrolyzer system with NiFe-layered double hydroxide (LDH) nanocatalysts with devices of 82-100 cm(2) area. The Ga-content in the ACIGS solar cells is tuned to achieve an optimal voltage for the catalyst system, and the average efficiencies and durability of the PV-electrolyzer were tested in up to seven-day indoor and 21 day outdoor operations. We achieved a solar-to-hydrogen (STH) module efficiency of 13.4% from gas volume measurements for the system with a six-cell CIGS-electrolyzer module with an active area of 82.3 cm(2) and a 17.27% PV module efficiency under 100 mW cm(-2) illumination, and thus 77% electricity-to-hydrogen efficiency at one full sun. Outdoor tests under mid-Europeen winter conditions exhibited an STH efficiency between 10 and 11% after the initial activation at the installation site in Julich, Germany, in December 2020, despite challenging outdoor-test weather conditions, including sub-zero temperatures.

Direct solar hydrogen generation via a combination of photovoltaics PV and water electrolysis can potentially ensure a sustainable energy supply while minimizing greenhouse emissions. The PECSYS project aims at demonstrating a solar driven electrochemical hydrogen generation system with an area gt;10 amp; 8201;m2 with high efficiency and at reasonable cost. Thermally integrated PV electrolyzers ECs using thin film silicon, undoped, and silver doped Cu In,Ga Se2 and silicon heterojunction PV combined with alkaline electrolysis to form one unit are developed on a prototype level with solar collection areas in the range from 64 to 2600 amp; 8201;cm2 with the solar to hydrogen StH efficiency ranging from amp; 8776;4 to 13 . Electrical direct coupling of PV modules to a proton exchange membrane EC to test the effects of bifaciality 730 amp; 8201;cm2 solar collection area and to study the long term operation under outdoor conditions 10 amp; 8201;m2 collection area is also investigated. In both cases, StH efficiencies exceeding 10 can be maintained over the test periods used. All the StH efficiencies reported are based on measured gas outflow using mass flow meters

Herein, the performance of wide-gap Cu(In,Ga)Se-2 (CIGS) and (Ag,Cu)(In,Ga)Se-2 (ACIGS) solar cells with In2O3:Sn (ITO) and In2O3:H (IOH) as transparent back contact (TBC) materials is evaluated. Since both TBCs restrict sodium in-diffusion from the glass substrate, fine-tuning of a NaF precursor layer is crucial. It is found that the optimum Na supply is lower for ACIGS than for CIGS samples. An excessive sodium amount deteriorates the solar cell performance, presumably by facilitating GaOx growth at the TBC/absorber interface. The efficiency (eta) further depends on the absorber stoichiometry, with highest fill factors (and eta) reached for close-stoichiometric compositions. An ACIGS solar cell with eta = 12% at a bandgap of 1.44 eV is processed, using IOH as a TBC. The best CIGS device reaches eta = 11.2% on ITO. Due to its very high infrared transparency, IOH is judged superior to ITO for implementation in a top cell of a tandem device. However, while ITO layers maintain their conductivity, IOH films show an increased sheet resistance after absorber deposition. Chemical investigations indicate that incorporation of Se during the initial stage of absorber processing may be responsible for the deteriorated conductivity of the IOH back contact in the final device.

In this work, we evaluate the effect of NaF layers on the properties of Al2O3 and HfO2 rear contact passivation layers in ultra-thin Cu(In,Ga)Se2 solar cells. The 6 nm thin passivation layers were ...

Surface sulfurization of Cu(In,Ga)Se2 (CIGSe) absorbers is a commonly applied technique to improve the conversion efficiency of the corresponding solar cells, via increasing the bandgap towards the heterojunction. However, the resulting device performance is understood to be highly dependent on the thermodynamic stability of the chalcogenide structure at the upper region of the absorber. The present investigation provides a high-resolution chemical analysis, using energy dispersive X-ray spectrometry and laser-pulsed atom probe tomography, to determine the sulfur incorporation and chemical re-distribution in the absorber material. The post-sulfurization treatment was performed by exposing the CIGSe surface to elemental sulfur vapor for 20 min at 500°C. Two distinct sulfur-rich phases were found at the surface of the absorber exhibiting a layered structure showing In-rich and Ga-rich zones, respectively. Furthermore, sulfur atoms were found to segregate at the absorber grain boundaries showing concentrations up to ~7 at% with traces of diffusion outwards into the grain interior.

The effects of introducing a passivation layer at the rear of ultrathin Copper Indium Gallium di-Selenide Cu(In,Ga)Se2 (CIGS) solar cells is studied. Point contact structures have been created on 25 nm Al2O3 layer using e-beam lithography. Reference solar cells with ultrathin CIGS layers provide devices with average values of light to power conversion efficiency of 8.1% while for passivated cells values reached 9.5%. Electronic properties of passivated cells have been studied before, but the influence of growing the CIGS on Al2O3 with point contacts was still unknown from a structural and morphological point of view. Scanning Electron Microscopy, X-ray Diffraction and Raman spectroscopy measurements were performed. These measurements revealed no significant morphological or structural differences in the CIGS layer for the passivated samples compared with reference samples. These results are in agreement with the similar values of carrier density (~8 × 1016 cm-3) and depletion region (~160 nm) extracted using electrical measurements. A detailed comparison between both sample types in terms of current-voltage, external quantum efficiency and photoluminescence measurements show very different optoelectronic behaviour which is indicative of a successful passivation. SCAPS simulations are done to explain the observed results in view of passivation of the rear interface., P.M.P. Salomé acknowledges the funding of Fundação para a Ciência e a Tecnologia (FCT) through the project IF/00133/2015. The European Union's Horizon 2020 research and innovation programme ARCIGS-M project (grant agreement no. 720887) is acknowledged. J. M. V. Cunha acknowledges the funding of Fundação para a Ciência e a Tecnologia (FCT) through the project PD/BD/142780/2018. J. P. Teixeira and J. P. Leitão acknowledge the funding of FCT through the project UID/CTM/50025/2013.

Silver alloying of Cu(In,Ga)Se2 absorbers for thin film photovoltaics offers improvements in open-circuit voltage, especially when combined with optimal alkali-treatments and certain Ga concentrations. The relationship between alkali distribution in the absorber and Ag alloying is investigated here, combining experimental and theoretical studies. Atom probe tomography analysis is implemented to quantify the local composition in grain interiors and at grain boundaries. The Na concentration in the bulk increases up to ∼60 ppm for [Ag]/([Ag] + [Cu]) = 0.2 compared to ∼20 ppm for films without Ag and up to ∼200 ppm for [Ag]/([Ag] + [Cu]) = 1.0. First-principles calculations were employed to evaluate the formation energies of alkali-on-group-I defects (where group-I refers to Ag and Cu) in (Ag,Cu)(In,Ga)Se2 as a function of the Ag and Ga contents. The computational results demonstrate strong agreement with the nanoscale analysis results, revealing a clear trend of increased alkali bulk solubility with the Ag concentration. The present study, therefore, provides a more nuanced understanding of the role of Ag in the enhanced performance of the respective photovoltaic devices.

High-end organic–inorganic lead halide perovskite semitransparent p–i–n solar cells for tandem applications use a phenyl-C61-butyric acid methyl ester (PCBM)/atomic layer deposition (ALD)-SnOx electron transport layer stack. Omitting the PCBM would be preferred for manufacturing, but has in previous studies on (FA,MA)Pb(Br,I)3 and (Cs,FA)Pb(Br,I)3 and in this study on Cs0.05FA0.79MA0.16PbBr0.51I2.49 (perovskite) led to poor solar cell performance because of a bias-dependent light-generated current. A direct ALD-SnOx exposure was therefore suggested to form a nonideal perovskite/SnOx interface that acts as a transport barrier for the light-generated current. To further investigate the interface formation during the initial ALD SnOx growth on the perovskite, the mass dynamics of monitor crystals coated by partial p–i–n solar cell stacks were recorded in situ prior to and during the ALD using a quartz crystal microbalance. Two major finds were made. A mass loss was observed prior to ALD for growth temperatures above 60 °C, suggesting the decomposition of the perovskite. In addition, a mostly irreversible mass gain was observed during the first exposure to the Sn precursor tetrakis(dimethylamino)tin(IV) that is independent of growth temperature and that disrupts the mass gain of the following 20–50 ALD cycles. The chemical environments of the buried interface were analyzed by soft and hard X-ray photoelectron spectroscopy for a sample with 50 ALD cycles of SnOx on the perovskite. Although measurements on the perovskite bulk below and the SnOx film above did not show chemical changes, additional chemical states for Pb, Br, and N as well as a decrease in the amount of I were observed in the interfacial region. From the analysis, these states and not the heating of the perovskite were concluded to be the cause of the barrier. This strongly suggests that the detrimental effects can be avoided by controlling the interfacial design.

Summary In this work, a trimetallic NiMoV catalyst is developed for the hydrogen evolution reaction and characterized with respect to structure, valence, and elemental distribution. The overpotential to drive a 10 mA cm−2 current density is lowered from 94 to 78 mV versus reversible hydrogen electrode by introducing V into NiMo. A scalable stand-alone system for solar-driven water splitting was examined for a laboratory-scale device with 1.6 cm2 photovoltaic (PV) module area to an up-scaled device with 100 cm2 area. The NiMoV cathodic catalyst is combined with a NiO anode in alkaline electrolyzer unit thermally connected to synthesized (Ag,Cu) (In,Ga)Se2 ((A)CIGS) PV modules. Performance of 3- and 4-cell interconnected PV modules, electrolyzer, and hydrogen production of the PV electrolyzer are examined between 25°C and 50°C. The PV-electrolysis device having a 4-cell (A)CIGS under 100 mW cm−2 illumination and NiMoV-NiO electrolyzer shows 9.1% maximum and 8.5% averaged efficiency for 100 h operation., Graphical Abstract, Highlights • A new catalyst NiMoV is reported for the hydrogen evolution reaction • A scalable thermally integrated PV-electrolyzer is designed for solar water splitting • Interconnected PV-electrolyzer modules provide STH efficiency between 8 and 11% • An upscaled CIGS-NiMoV-NiO device provides 8.5% STH for 100 h operation, Chemistry; Electrochemistry; Engineering; Materials Science; Energy Materials

Silver alloying of Cu(In,Ga)Se-2 absorbers for thin film photovoltaics offers improvements in open-circuit voltage, especially when combined with optimal alkali-treatments and certain Ga concentrations. The relationship between alkali distribution in the absorber and Ag alloying is investigated here, combining experimental and theoretical studies. Atom probe tomography analysis is implemented to quantify the local composition in grain interiors and at grain boundaries. The Na concentration in the bulk increases up to similar to 60 ppm for [Ag]/([Ag] + [Cu]) = 0.2 compared to similar to 20 ppm for films without Ag and up to similar to 200 ppm for [Ag]/([Ag] + [Cu]) = 1.0. First-principles calculations were employed to evaluate the formation energies of alkali-on-group-I defects (where group-I refers to Ag and Cu) in (Ag,Cu)(In,Ga)Se-2 as a function of the Ag and Ga contents. The computational results demonstrate strong agreement with the nanoscale analysis results, revealing a clear trend of increased alkali bulk solubility with the Ag concentration. The present study, therefore, provides a more nuanced understanding of the role of Ag in the enhanced performance of the respective photovoltaic devices.

International audience; We present a simulation strategy using ATLAS-2D to optimize the back-contact hole grid (i.e. size and pitch of openings) of the Al2O3-rear-passivation layer in ultra-thin CIGS photovoltaic cells. We first discuss and compare our simulation model with a series of experimental reference (i.e. non passivated) and passivated UT-CIGS cells to decouple the crucial parameters of the passivation. The simulation results follow the experimental trends both for the current in the dark and for the PV parameters under illumination, highlighting the beneficial effects of the passivation on the cell performances. Furthermore, it stresses the influence of the passivation quality at the Al2O3/CIGS interface and of the contact resistance at the Mo/CIGS interface within the openings. Further simulations quantify significant improvements in short-circuit current and open-circuit voltage for different sizes of openings in the Al2O3 layer, relative to an excellent passivation quality (i.e. high density of negative charges in the passivation layer). However, a degradation of performances is predicted for a poor passivation (i.e. low density of such charges) or a high contact resistance, when compared to reference cells. Consequently, we point out an optimum in efficiency when varying the opening widths at fixed hole pitch and fixed contact resistance. At equivalent contact resistance, simulations predict that the sizes of the pitch and openings can be increased without optimal performance losses when maintaining a width to pitch ratio around 0.2. This simulation trend has been confirmed by a series of experiments, indicating that it is crucial to care about the dimensions of the opening grid and the contact resistance of passivated cells apart from different material properties. These simulation results provide significant insights for optimal cell design and characterizations of passivated UT-CIGS PV cells.

This contribution studies the potential of an RbF postdeposition treatment (RbF-PDT) of wide-gap (Ag,Cu)(In,Ga)Se-2 (ACIGS) absorbers to improve the corresponding solar cell performance. While a higher open-circuit voltage (V-OC) and short-circuit current density are achieved, a lower fill factor (FF) is observed for most of the devices subjected to an RbF-PDT. However, the drop in FF can be avoided for some close-stoichiometric samples, leading to maximum efficiencies beyond 16% (without antireflection coating) at a bandgap energy (E-g) of 1.43 eV. For off-stoichiometric ACIGS, a record V-OC value of 926 mV at E-g = 1.44 eV is reached. Lower V-OC deficits likely require enhanced bulk quality of wide-gap chalcopyrite absorbers. Extensive material analysis shows that the heavy alkali PDT of ACIGS with high Ag and Ga contents leads to similar absorber modifications as commonly observed for low-gap Cu(In,Ga)Se-2 (CIGS). Rubidium is continuously distributed at "internal" (grain boundaries) and "external" (buffer and back contact) absorber interfaces. The results indicate that Rb diffusion into the absorber bulk (including 1:1:2 and 1:3:5 compounds) is restricted. Furthermore, the formation of a very thin RbInSe2 surface layer is suggested. It remains open, which effects alter the device characteristics after RbF-PDT.

High-end organic–inorganic lead halide perovskite semitransparent p–i–n solar cells for tandem applications use a phenyl-C61-butyric acid methyl ester (PCBM)/atomic layer deposition (ALD)-SnOx electron transport layer stack. Omitting the PCBM would be preferred for manufacturing, but has in previous studies on (FA,MA)Pb(Br,I)3 and (Cs,FA)Pb(Br,I)3 and in this study on Cs0.05FA0.79MA0.16PbBr0.51I2.49 (perovskite) led to poor solar cell performance because of a bias-dependent light-generated current. A direct ALD-SnOx exposure was therefore suggested to form a nonideal perovskite/SnOx interface that acts as a transport barrier for the light-generated current. To further investigate the interface formation during the initial ALD SnOx growth on the perovskite, the mass dynamics of monitor crystals coated by partial p–i–n solar cell stacks were recorded in situ prior to and during the ALD using a quartz crystal microbalance. Two major finds were made. A mass loss was observed prior to ALD for growth temperatures above 60 °C, suggesting the decomposition of the perovskite. In addition, a mostly irreversible mass gain was observed during the first exposure to the Sn precursor tetrakis(dimethylamino)tin(IV) that is independent of growth temperature and that disrupts the mass gain of the following 20–50 ALD cycles. The chemical environments of the buried interface were analyzed by soft and hard X-ray photoelectron spectroscopy for a sample with 50 ALD cycles of SnOx on the perovskite. Although measurements on the perovskite bulk below and the SnOx film above did not show chemical changes, additional chemical states for Pb, Br, and N as well as a decrease in the amount of I were observed in the interfacial region. From the analysis, these states and not the heating of the perovskite were concluded to be the cause of the barrier. This strongly suggests that the detrimental effects can be avoided by controlling the interfacial design.

We present a 2D model of an Al 2 O 3 -passivated ultrathin Cu(In, Ga)Se 2 photovoltaic cell with rear-contact pattern. Simulation results follow the experimental trends, highlighting the significant effects of the passivation quality and of the Mo/CIGS contact resistance. Improvements in Jsc and Voc are discussed for different sizes of openings, relative to an excellent passivation quality (i.e. high density of negative charges in the passivation layer). However, a degradation is predicted for a poor passivation (i.e. low density of such charges) or a high contact resistance. We point out an optimum in efficiency when varying the opening widths at fixed hole-pitch and fixed contact resistance for a width to pitch ratio around 0.2. These simulation results provide significant insights for optimal cell design and characterizations of passivated UT-CIGS PV cells.

Depth bandgap profiles via a [Ga]/([Ga]+[In]) variation in the Cu(In,Ga)Se2 (CIGS) absorber layer have been implemented as a strategy to enhance the performance of CIGS solar cells. Since the [Ga]/([Ga]+[In]) determines to a large extent the position of the conduction band minimum, different Ga-profiles lead to different electronic energy levels structures throughout the CIGS layer. In this paper, from the investigation of the dependence of the photoluminescence (PL) on excitation power and temperature, we critically analyse the impact of a notch or a linear Ga-profiles on the CIGS electronic energy levels structure and subsequent dominant recombination channels. Notwithstanding two radiative transitions involving fluctuating potentials were observed for each sample, significant differences in the luminescence resultant from the two Ga-profiles were identified. For the CIGS absorber with a notch Gaprofile, two tail-impurity radiative transitions involving equivalent donors cluster and the same deep acceptor level were ascribed to the near CIGS/CdS interface and the notch regions. The probability of radiative recombination in the two regions is discussed. For the CIGS absorber with a linear Ga-profile, two band-impurity radiative transitions involving an acceptor, with an ionization energy compatible with the VCu defect were ascribed to the region near the CIGS/CdS interface. Our results shows that the dominant acceptor defects are dependent on the Ga-profile and they also highlight the complexity of the radiative and non-radiative recombination channels revealed by a tight control of the parameters in the experiment. published

Depth bandgap profiles via a [Ga]/([Ga]+[In]) variation in the Cu(In,Ga)Se2 (CIGS) absorber layer have been implemented as a strategy to enhance the performance of CIGS solar cells. Since the [Ga]/([Ga]+[In]) determines to a large extent the position of the conduction band minimum, different Ga-profiles lead to different electronic energy levels structures throughout the CIGS layer. In this paper, from the investigation of the dependence of the photoluminescence (PL) on excitation power and temperature, we critically analyse the impact of a notch or a linear Ga-profiles on the CIGS electronic energy levels structure and subsequent dominant recombination channels. Notwithstanding two radiative transitions involving fluctuating potentials were observed for each sample, significant differences in the luminescence resultant from the two Ga-profiles were identified. For the CIGS absorber with a notch Ga profile, two tail-impurity radiative transitions involving equivalent donors cluster and the same deep acceptor level were ascribed to the near CIGS/CdS interface and the notch regions. The probability of radiative recombination in the two regions is discussed. For the CIGS absorber with a linear Ga-profile, two band-impurity radiative transitions involving an acceptor, with an ionization energy compatible with the VCu defect were ascribed to the region near the CIGS/CdS interface. Our results shows that the dominant acceptor defects are dependent on the Ga-profile and they also highlight the complexity of the radiative and non-radiative recombination channels revealed by a tight control of the parameters in the experiment.

This paper focuses on the development of 2-terminal CIGS-perovskite tandem solar cells by exploring a range of stack sequences and synthetic procedures for depositing the associated layers. In the end, we converged at a stack sequence composed of SLG/Mo/CIGS/CdS/i-ZnO/ZnO:Al/NiO/PTAA/Perovskite/LiF/PCBM/SnO2/ITO. With this architecture, we reached performances only about 1% lower than the corresponding 4-terminal tandem cells, thus demonstrating functional interconnects between the two sub-cells while grown monolithically on top of each other. We go through the stack, layer-by-layer, discussing their deposition and the results, from which we can conclude what works, what does not work, and what potentially could work after additional modifications. The challenges for a successful 2-terminal tandem device include: how to deal with, or decrease, the surface roughness of the CIGS-stack, how to obtain uniform coverage of the layers between the CIGS and the perovskite while also obtaining a benign interface chemistry, and how to tune the band gaps of both the CIGS and the perovskite to obtain good optical matching. The investigation was based on CIGS with a power conversion efficiency around 14%, and perovskites with an efficiency around 12%, resulting in 2-terminal tandem cells with efficiencies of 15–16%. The results indicate that by using higher performing CIGS and perovskite sub-cells, it should be possible to manufacture highly efficient 2-terminal CIGS-perovskite tandem devices by using the protocols, principles, and procedures developed and discussed in this paper. (Less)

The Horizon 2020 project PECSYS aims to build a large area demonstrator for hydrogen production from solar energy via integrated photovoltaic (PV) and electrolysis systems of different types. In this study, Si- and CIGS-based photovoltaics are developed together with three different electrolyzer systems for use in the corresponding integrated devices. The systems are experimentally evaluated and a general model is developed to investigate the hydrogen yield under real climatic conditions for various thin film and silicon PV technologies and electrolyser combinations. PV characteristics using a Si heterojunction (SHJ), thin film CuInxGa1-xSe2, crystalline Si with passivated emitter rear totally diffused and thin film Si are used together with temperature dependent catalyst load curves from both acidic and alkaline approaches. Electrolysis data were collected from (i) a Pt-IrO2-based acidic electrolysis system, and (ii) NiMoW-NiO-based and (iii) Pt-Ni foam-based alkaline electrolysis systems. The calculations were performed for mid-European climate data from Julich, Germany, which will be the installation site. The best systems show an electricity-to-hydrogen conversion efficiency of 74% and over 12% solar-to-hydrogen (STH) efficiencies using both acidic and alkaline approaches and are validated with a smaller lab scale prototype. The results show that the lower power delivered by all the PV technologies under low irradiation is balanced by the lower demand for overpotentials for all the electrolysis approaches at these currents, with more or less retained STH efficiency over the full year if the catalyst area is the same as the PV area for the alkaline approach. The total yield of hydrogen, however, follows the irradiance, where a yearly hydrogen production of over 35 kg can be achieved for a 10 m(2) integrated PV-electrolysis system for several of the PV and electrolyser combinations that also allow a significant (100-fold) reduction in necessary electrolyser area for the acidic approach. Measuring the catalyst systems under intermittent and ramping conditions with different temperatures, a 5% lowering of the yearly hydrogen yield is extracted for some of the catalyst systems while the Pt-Ni foam-based alkaline system showed unaffected or even slightly increased yearly yield under the same conditions.

Amorphous tin-gallium oxide (a-SGO) grown with atomic layer deposition was evaluated as a buffer layer in (Ag,Cu)(In,Ga)Se2 thin-film solar cells in search for a new material that is compatible with a variety of absorber band gaps. Hard and soft X-ray photoelectron spectroscopy on absorber/a-SGO stacks combined with J–V characterization of solar cells that were fabricated, showed that the conduction band alignment at the absorber/a-SGO interface can be tuned by varying the cation composition and/or growth temperature. Here, the surface band gap was 1.1 eV for the absorber. However, optical band gap data for a-SGO indicate that a suitable conduction band alignment can most likely be achieved even for wider absorber band gaps relevant for tandem top cells. A best efficiency of 17.0% was achieved for (Ag,Cu)(In,Ga)Se2/a-SGO devices, compared to η = 18.6% for the best corresponding CdS reference. Lower fill factor and open-circuit voltage values were responsible for lower cell efficiencies. The reduced fill factor is explained by a larger series resistance, seemingly related to interface properties, which are yet to be optimized. Some layer constellations resulted in degradation in fill factor during light soaking as well. This may partly be explained by light-induced changes in the electrical properties of a-SGO, according to analysis of Al/SGO/n-Si metal-oxide-semiconductor capacitors that were fabricated and characterized with J–V and C–V. Moreover, the introduction of a 1 nm thick Ga2O3 interlayer between the absorber and a-SGO improved the open-circuit voltage, which further indicates that the absorber/a-SGO interface can be improved.

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Herein, sulfurization of CuInSe(2)and CuGaSe2(CGSe) absorber layers is compared to improve the understanding of sulfur incorporation into Cu(In,Ga)Se(2)films by annealing in a sulfur atmosphere. It is found for Cu-poor CuInSe(2)that for an annealing temperature of 430 degrees C, sulfur is incorporated into the surface of the absorber and forms an inhomogeneous CuIn(S,Se)(2)layer. In addition, at 530 degrees C, a surface layer of CuInS(2)is formed. In contrast, for Cu-poor CuGaSe(2)samples, S can only be introduced at 530 degrees C, mainly forming an alloy of CuGa(S,Se)(2), where no closed CuGaS(2)layer is found. In Cu-rich CuGaSe(2)samples, however, selenium is substituted by S already at 330 degrees C, which can be explained by a rapid phase transformation of Cu2 - xSe into Cu2 - x(S,Se). This transformation facilitates S in-diffusion and catalyzes CuGa(S,Se)(2)formation, likewise that previously reported to occur in CuInSe2. Finally, the Cu-poor CuInSe(2)solar cell performance is improved by the sulfurization step at 430 degrees C, whereas for the 530 degrees C sample, a decreasing fill factor and short-circuit current density are observed, indicating lower diffusion length accompanied by possible formation of an electron transport barrier. In contrast, the electrical characteristics deteriorate for all sulfurized Cu-poor CuGaSe(2)cells.

This contribution evaluates the effect of absorber off‐stoichiometry in wide‐gap (Ag,Cu)(In,Ga)Se2 (ACIGS) solar cells. It is found that ACIGS films show an increased tendency to form ordered vacancy compounds (OVCs) with increasing Ga and Ag contents. Very little tolerance to off‐stoichiometry is detected for absorber compositions giving the desired properties of 1) an optimum bandgap (EG) for a top cell in tandem devices (EG = 1.6–1.7 eV) and at the same time 2) a favorable band alignment with a CdS buffer layer. Herein, massive formation of either In‐ or Ga‐enriched OVC patches is found for group I‐poor ACIGS. As a consequence, carrier transport and charge collection are significantly impeded in corresponding solar cells. The transport barrier appears to be increasing with storage time, questioning the long‐term stability of wide‐gap ACIGS solar cells. Furthermore, the efficiency of samples with very high Ga and Ag contents depends on the voltage sweep direction. It is proposed that the hysteresis behavior is caused by a redistribution of mobile Na ions in the 1:1:2 absorber lattice upon voltage bias. Finally, a broader perspective on OVC formation in the ACIGS system is provided and fundamental limitations for wide‐gap ACIGS solar cells are discussed.

In this study, we assessed the potential of KF-post deposition treatment (PDT) performed on a silver-alloyed Cu (In,Ga)Se-2 (ACIGS) solar absorber. ACIGS absorbers with Ag/Ag + Cu ratio (Ag/I) clos ...

We investigate the possibility to combine Zn(O,S) buffer layers grown by atomic layer deposition (ALD) with KF post-deposition treated Cu(In,Ga)Se-2 (CIGS-KF) in solar cells. It is shown that the b ...

This work concerns the interpretation of defect spectroscopy signals in CuInSe2-and Cu(In,Ga)Se2-based Schottky junctions and thin films, which are investigated using capacitance- and current-based techniques. Two common signals are distinguished. It is shown here that the activation energies and consequently the emission rates vary between the samples and are strongly correlated with the hole concentration in the material. Models that can account for these changes are discussed. Based on deep-level transient spectroscopy and conductivity measurements, we present arguments for the validity of the existing models and discuss the hypothesis that the observable signals may originate from extended defects in Cu(In,Ga)Se2.

Hydrogen‐doped In2O3 (IOH) films are used as a transparent back contact in bifacial Cu(In,Ga)Se2 (CIGS) solar cells. The effect of the IOH thickness and the impact of the sodium incorporation techn ...

This study evaluates the potential of hydrogen‐doped In2O3 (IOH) as a transparent back contact material in (Agy,Cu1‐y)(In1‐x,Gax)Se2 solar cells. It is found that the presence of Na promotes the cr ...

In this contribution, we show that silver substitution for copper in Cu(In,Ga)Se2 (CIGS) to form (Ag,Cu)(In,Ga)Se2 (ACIGS) leads to a reduction of the voltage loss expressed as Eg/q – V oc. This, in turn, leads to higher device efficiencies as compared to similar CIGS devices without Ag. We report $V_{{\rm{oc}}}$ at 814 mV at a conversion efficiency of 21% for our best ACIGS device with 20% of the group I element consisting of silver. Comparing ACIGS and CIGS devices with the same Ga/(Ga + In) ratio, the ACIGS devices exhibit about 0.05 eV higher bandgap. Alkali postdeposition treatment with KF leads to improvements in efficiency both for CIGS and ACIGS, but we find that the dose of KF needed for optimum device for ACIGS is 10–20% of the dose used for CIGS.

The effect of absorber stoichiometry in (Ag,Cu)(In,Ga)Se2(ACIGS) solar cells withbandgaps (Eg) > 1.40 eV is studied on a large sample set. It is conrmed thatmoving away in composition from ternary AgGaSe2by simultaneous reduction inGa and Ag content widens the chalcopyrite single-phase region and therebyreduces the amount of ordered vacancy compounds (OVCs). As a consequence, adistortion in currentvoltage characteristics, ascribed to OVCs at the back contact,can be successfully avoided. A clear anticorrelation between open-circuit voltage(VOC) and short-circuit current density (JSC) is detected with varying absorberstoichiometry, showing decreasingVOCand increasingJSCvalues for [I]/[III] > 0.9.Capacitance proling reveals that the absorber doping gradually decreases towardstoichiometric composition, eventually leading to complete depletion. It isobserved that only such fully depleted samples exhibit perfect carrier collection,evidencing a very low diffusion length in wide-gap ACIGS lms. The results indicatethat OVCs at the surface play a minor or passive role for device performance.Finally, a solar cell withVOC¼ 0.916 V atEg¼ 1.46 eV is measured, which is, to thebest of our knowledge, the highest value reported for this bandgap to date.

This contribution evaluates a sequential post‐deposition treatment of Cu(In,Ga)Se2 (CIGS) films, consisting of 1) a post‐sulfurization in elemental S‐atmosphere and 2) a subsequent treatment by heavy alkali fluorides (Alk‐PDT). First, the effect of the sulfurization step on the corresponding solar cell performance is investigated and optimum process parameters, leading to an efficiency improvement, are identified. Losses in carrier collection observed after S‐incorporation are attributed to an increased grain boundary (GB) recombination. It is found that the corresponding reduction in short‐circuit current density can be mitigated by a RbF‐ or KF‐PDT, supposedly by depleting GBs in Cu. However, in strong contrast to non‐sulfurized CIGS, the Alk‐PDT results in a lower open‐circuit voltage and distortions in the current–voltage (I –V ) characteristics for sulfurized absorbers. Possible explanations are the absence of a wide‐gap surface phase and/or air exposure between the post‐treatment steps. It is further proposed that a back contact barrier may be responsible for the distortions in I–V.

Perovskite solar cells, as a newly emerged solar energy conversion technology, have attracted tremendous attention in the solar cell community by demonstrating impressive enhancement in power conversion efficiencies. However, the high temperature and manually processed TiO2 underlayer prepared by spray pyrolysis has significantly limited the large-scale application and device reproducibility of the perovskite solar cells. Here, we for the first time utilize low-temperature atomic layer deposition (ALD) to prepare a compact Al2O3 underlayer for perovskite solar cells. The thickness of the Al2O3 layer can be controlled well by adjusting the deposition cycles during the ALD process. An optimal Al2O3 layer can effectively block the electron recombination at the perovskite/FTO interface as well as sufficiently transport the electrons via tunneling. Perovskite solar cells fabricated with an Al2O3 layer demonstrated the highest efficiency of 16.2% for 50 cycles of ALD (~5 nm), which is a significant improvement over the underlayer free PSCs which have an efficiency of 11.0%. Detailed characterization confirms that the thickness of the Al2O3 underlayer significantly influences the charge transfer resistance and electron recombination process in the devices. Furthermore, this work successfully shows the feasibility of using a high-bandgap semiconductor like Al2O3 as the underlayer in perovskite solar cells and opens up pathways to use ALD Al2O3 underlayers for flexible solar cells.

The compatibility of atomic layer deposition directly onto the mixed halide perovskite formamidinium lead iodide:methylammonium lead bromide (CH(NH2)2, CH3NH3)Pb(I,Br)3 (FAPbI3:MAPbBr3) perovskite films is investigated by exposing the perovskite films to the full or partial atomic layer deposition processes for the electron selective layer candidates ZnO and SnOx. Exposing the samples to the heat, the vacuum, and even the counter reactant of H2O of the atomic layer deposition processes does not appear to alter the perovskite films in terms of crystallinity, but the choice of metal precursor is found to be critical. The Zn precursor Zn(C2H5)2 either by itself or in combination with H2O during the ZnO atomic layer deposition (ALD) process is found to enhance the decomposition of the bulk of the perovskite film into PbI2 without even forming ZnO. In contrast, the Sn precursor Sn(N(CH3)2)4 does not seem to degrade the bulk of the perovskite film, and conformal SnOx films can successfully be grown on top of it...