Surface engineering in Cu(In,Ga)Se2 solar cells

Surface modifications of three‐stage co‐evaporated Cu(In,Ga)Se₂ (CIGS) thin films are investigated by finishing the evaporation with gallium‐free (CuInSe₂, CIS) stages of various lengths. Secondary‐ion mass spectrometry shows substantial interdiffusion of indium and gallium, smearing out the Ga/(Ga + In) profile so that the addition of a CIS layer merely lowers the gallium content at the surface. For the thinnest top layer, equivalent to 20 nm of pure CIS, X‐ray photoelectron spectroscopy does not detect any compositional difference compared with the reference device. The modifications are evaluated electrically both by temperature‐dependent characterisation of actual solar‐cell devices and by modelling, using the latest version of scaps‐1d (Electronics and Information Systems, Ghent University, Belgium). The best solar‐cell device from this series is obtained for the 20 nm top layer, with an efficiency of 16.6% after antireflective coating. However, we observe a trend of decreasing open‐circuit voltage for increasingly thick top layers, and we do not find direct evidence that the lowering of the gallium concentration at the CIGS surface should generally be expected to improve the device performance. A simulated device with reduced bulk and interface defect levels achieves nearly 20% efficiency, but the trends concerning the CIS top layer remain the same. Copyright © 2011 John Wiley & Sons, Ltd.     

Model for electronic transport in Cu(In,Ga)Se2 solar cells

Temperature-dependent measurements of the current–voltage characteristics and of the junction admittance of ZnO/CdS/Cu(In,Ga)Se₂ heterojunction solar cells are presented, together with numerical modelling of these experimental results. We explain the cross-over between dark and illuminated current–voltage characteristics currently observed for this type of device by the impact of the defect chalcopyrite layer at the surface of the Cu(In,Ga)Se₂ absorber. Our model assumes an illumination-dependent voltage drop across a defect layer with a thickness of 15 nm to explain the cross-over. The voltage drop results from the electrical dipole made up of donor-like states at the interface between the defect layer and CdS and deep acceptor states in the defect layer itself. The illumination dependence of this voltage drop is explained by photogenerated holes trapped by the deep acceptor states in the defect layer. Numerical simulations have been carried out using the program SCAPS-1D in order to verify our model assumptions. From our model, indirect conclusions are derived concerning the maximum conduction band offsets between CdS and the defect layer and between CdS and ZnO. Copyright © 1998 John Wiley & Sons, Ltd.     

Cu(In,Ga)Se2 superstrate solar cells: prospects and limitations

Superstrate solar cells were prepared by thermal evaporation of Cu(In,Ga)Se2 onto ZnO coated glass substrates. For the first time, photo‐conversion efficiencies above 11% were reached without the necessity of additional light soaking or forward biasing of the solar cell. This was achieved by modifying the deposition process as well as the sodium doping. Limitations of the superstrate device configuration and possible ways to overcome these were investigated by analyzing the hetero‐interface with electron microscopy and X‐ray photoemission spectroscopy measurements, combined with capacitance spectroscopy and device simulations. A device model was derived that explains how on the one hand the GaO_x, which forms at the CIGSe/ZnO interface, reduces the interface recombination. On the other hand how it limits the efficiency by acting as an electron barrier at the hetero‐interface presumably because of a high density of negatively charged acceptor states like Cu_Ga. The addition of sodium enhances the p‐type doping of the absorber but also increases the net doping within the GaO_x. Hence, a trade‐off between these two effects is required. The conversion efficiency was found to decrease over time, which can be explained in our model by field‐induced diffusion of sodium cations out from the GaO_x layer. The proposed device model is able to explain various effects frequently observed upon light soaking and forward biasing of superstrate devices. Copyright © 2014 John Wiley & Sons, Ltd.     

Flexible Cu(In,Ga)Se2 solar cells with reduced absorber thickness

Reduction of the absorber thickness combined with deposition on a flexible substrate is a technically viable strategy to allow lower cost manufacturing of Cu(In,Ga)Se₂ solar modules. Flexible plastic substrates, however, require a low‐temperature deposition process and appropriate control of the band gap grading for achieving high efficiencies. In this work, we developed solar cells on polyimide films using evaporated Cu(In,Ga)Se₂ absorbers with thickness of 0.8–1.3 µm. The double Ga‐grading profile across the absorber thickness was modified by varying the maximum Cu excess at the end of the second stage or by adapting the In and Ga evaporation flux profiles during the growth process. By minimizing the Cu excess during the intermediate stage of the growth process, no loss in open circuit voltage and fill factor is observed compared with a device having a thicker absorber. Efficiency of 16.3% was achieved for cells with an absorber thickness of 1.25 µm. Insufficient absorption of photons in the long wavelength region is mainly responsible for current loss. By changing the In and Ga evaporation profiles, the shape and position of the Ga notch were effectively modified, but it did not lead to a higher device performance. Modifications of the Ga compositional profile could not help to significantly reduce absorption losses or increase charge carrier collection in absorbers with thickness below 1 µm. Changes of open circuit voltage and fill factor are mostly related to differences in the net acceptor density or the reverse saturation current rather than changes of the double Ga grading. Copyright © 2013 John Wiley & Sons, Ltd.     

Spray‐ILGAR indium sulfide buffers for Cu(In,Ga)(S,Se)2 solar cells

Thin‐film indium sulfide buffer layers have been prepared using the Spray‐ILGAR technique for use in chalcopyrite solar cells. Buffers deposited on commercially grown Cu(In,Ga)(S,Se)₂ absorbers have produced cells reaching a certified efficiency of 14·7% and average efficiencies matching the reference solar cells prepared with a conventional cadmium sulfide buffer layer. The process parameters have been optimized and the resulting cells have been studied using current–voltage and temperature–illumination‐dependent current–voltage analysis as well as quantum efficiency measurements. Copyright © 2005 John Wiley & Sons, Ltd.     

Failure analysis of Cu(In,Ga)Se2 photovoltaic modules: degradation mechanism of Cu(In,Ga)Se2 solar cells under harsh environmental conditions

High‐temperature‐induced and humidity‐induced degradation behaviors were investigated through the failure analysis of encapsulated Cu(In,Ga)Se₂ (CIGS) modules and non‐encapsulated CIGS cells. After being exposed to high temperature (85 °C) for 1000 h, the efficiency loss of CIGS modules and the resistivities of the aluminum‐doped zinc oxide (AZO) layer, CIGS layer, and Mo layer were slightly increased. After damp heat (DH) testing (85 °C/85% RH), the efficiency of some modules decreased significantly accompanied by discoloration, and in these areas, the resistivity of the AZO layers increased markedly. The causes of degradation of CIGS cells after high temperature and DH tests were suggested through X‐ray photoelectron spectroscopy analysis. The high‐temperature‐induced degradation behaviors were revealed to be increases in series resistance of the CIGS cells, due to the adsorption of oxygen on the AZO, CIGS, and Mo layers. The degradation behavior after DH (85 °C/85% RH) exposure was caused by the adsorption of oxygen, as well as the generation of Zn(OH)₂ due to water molecules. In particular, the humidity‐induced degradation behavior in discolored CIGS modules was ascribed to the generation of Zn(OH)₂ and carboxylic acids in the AZO layer, due to a chemical reaction between the AZO, ethylene‐vinyl acetate copolymer, and water. Copyright © 2014 John Wiley & Sons, Ltd.     

Bandgap optimization of submicron‐thick Cu(In,Ga)Se2 solar cells

Reducing Cu(In,Ga)Se₂ (CIGS) absorber thickness into submicron regime provides an opportunity for reducing CIGS solar cell manufacturing time and cost. However, CIGS with submicron‐thick absorber would suffer strong absorption loss in the long‐wavelength region. In this paper, we report a new fabrication route for CIGS solar cells on soda‐lime glass substrates with different Ga content (0.3 < [Ga]/([Ga] + [In]) < 0.6), all with absorber thicknesses around 0.9 µm. Efficiency of 17.52% has been achieved for cells with high Ga content of [Ga]/([Ga] + [In]) = 41%, which is currently the best reported efficiency for submicron‐thick CIGS solar cells. Unlike the normal‐thickness absorber (2–3 µm) that has an optimal [Ga]/([Ga] + [In]) of ~32%, the increased value of optimal [Ga]/([Ga] + [In]) in submicron‐thick absorber greatly enhances the open‐circuit voltage, by nearly 15% compared with that of samples with Ga content optimized at normal absorber thickness. This large gain in V_OC well compensates the absorption loss in the long‐wavelength region and contributes to the enhancement of final solar cell efficiency. Copyright © 2014 John Wiley & Sons, Ltd.     

Gallium gradients in Cu(In,Ga)Se2 thin‐film solar cells

The gallium gradient in Cu(In,Ga)Se₂ (CIGS) layers, which forms during the two industrially relevant deposition routes, the sequential and co‐evaporation processes, plays a key role in the device performance of CIGS thin‐film modules. In this contribution, we present a comprehensive study on the formation, nature, and consequences of gallium gradients in CIGS solar cells. The formation of gallium gradients is analyzed in real time during a rapid selenization process by in situ X‐ray measurements. In addition, the gallium grading of a CIGS layer grown with an in‐line co‐evaporation process is analyzed by means of depth profiling with mass spectrometry. This gallium gradient of a real solar cell served as input data for device simulations. Depth‐dependent occurrence of lateral inhomogeneities on the µm scale in CIGS deposited by the co‐evaporation process was investigated by highly spatially resolved luminescence measurements on etched CIGS samples, which revealed a dependence of the optical bandgap, the quasi‐Fermi level splitting, transition levels, and the vertical gallium gradient. Transmission electron microscopy analyses of CIGS cross‐sections point to a difference in gallium content in the near surface region of neighboring grains. Migration barriers for a copper‐vacancy‐mediated indium and gallium diffusion in CuInSe₂ and CuGaSe₂ were calculated using density functional theory. The migration barrier for the In_Cu antisite in CuGaSe₂ is significantly lower compared with the Ga_Cu antisite in CuInSe₂, which is in accordance with the experimentally observed Ga gradients in CIGS layers grown by co‐evaporation and selenization processes. Copyright © 2014 John Wiley & Sons, Ltd.     

Photosensitivity of thin-film ZnO/CdS/Cu(In, Ga)Se2 solar cells

The photoelectric properties of thin-film ZnO/CdS/Cu(In,Ga)Se₂ solar cells were studied by polarization photoactive absorption spectroscopy. It was shown that the thin-film solar cells have a high efficiency relative to the intensity of unpolarized radiation in the photon energy range from 1.2 to 2.5 eV. The induced photopleochroism coefficient P _I increases with the angle of incidence of the incident radiation as P _I ∼θ ² and at 70° it reaches 17–20% with photon energy 1.3 eV. Oscillations of the photopleochroism were also observed. These results are discussed taking into account the antireflection effect. The results obtained by us make it possible to use such solar cells as wide-band photosensors for linearly polarized radiation and for monitoring the production of high-efficiency, thin-film solar cells based on ternary semiconductors. Fiz. Tekh. Poluprovodn. 31, 806–810 (July 1997)     

Wide bandgap Cu(In,Ga)Se2 solar cells with improved energy conversion efficiency

We report on improvements to the energy conversion efficiency of wide bandgap (E_g > 1.2 eV) solar cells on the basis of CuIn_1−xGa_xSe₂. Historically, attaining high efficiency (>16%) from these types of compound semiconductor thin films has been difficult. Nevertheless, by using (a) the alkaline‐containing high‐temperature EtaMax glass substrates from Schott AG, (b) elevated substrate temperatures of 600–650 °C, and (c) high vacuum evaporation from elemental sources following National Renewable Energy Laboratory's three‐stage process, we have been able to improve the performance of wider bandgap solar cells with 1.2 < E_g < 1.45 eV. The current density–voltage (J–V) data we present includes efficiencies >18% for absorber bandgaps of ~1.30 eV and efficiencies of ~16% for bandgaps up to ~1.45 eV. In comparing J–V parameters in similar materials, we establish gains in the open‐circuit voltage and, to a lesser degree, the fill factor value, as the reason for the improved performance. The higher voltages seen in these wide gap materials grown at high substrate temperatures are due to reduced recombination. We establish the existence of random and discrete grains within the CIGS absorbers that yield limited or no generation/collection of minority carriers. We also show that interfacial recombination is the main mechanism limiting additional enhancements to open‐circuit voltage and therefore performance. Solar cell results, absorber materials characterization, and experimental details and discussion are presented. Copyright © 2012 John Wiley & Sons, Ltd.     

Polarization photosensitivity of ZnO/CdS/Cu(In,Ga)Se2 solar cells

Results of the application of polarization spectroscopy of the photosensitivity of ZnO/CdS/Cu(In,Ga)Se₂ thin-film solar cells with different thicknesses of the CdS (50 and 100 nm) and ZnO (500 and 1000 nm) layers are considered. It is established that the induced photopleochroism coefficient is lowered while the quantum efficiency of photoconversion of the solar cells is raised by increasing the thickness of the front layer. The experimental conditions and spectral dependence of the induced photopleochroism are linked with the antireflection properties of the ZnO front layers. It is concluded that photosensitivity polarization spectroscopy can be used for rapid diagnostics of finished solar cells and to optimize their fabrication technology. Fiz. Tekh. Poluprovodn. 33, 484–487 (April 1999)     

MOCVD as a dry deposition method of ZnSe buffers for Cu(In,Ga)(S,Se)2 solar cells

ZnSe prepared by metal organic chemical vapor deposition is used as a buffer layer in Cu(In,Ga)(S,Se)₂ solar cells without any utilization of wet chemistry. Cell efficiencies are as good as cells with the conventional CdS buffer. Stability of unencapsulated cells under damp heat conditions is somewhat lower for the alternative buffer. The first stages of photoassisted growth are studied. X‐ray photoemission spectroscopy shows that a continuous layer is formed. Copyright © 2004 John Wiley & Sons, Ltd.     

Compositional engineering of chemical bath deposited (Zn,Cd)S buffer layers for electrodeposited CuIn(S,Se)2 and coevaporated Cu(In,Ga)Se2 solar cells

A comparative study of chemical bath deposition (CBD) of ZnS, CdS, and a mixture of (Cd,Zn)S buffer layers has been carried out on electrodeposited CuIn(S,Se)₂ (CISSe) and coevaporated Cu(In,Ga)Se₂ (CIGS) absorbers. For an optimal bath composition with the ratio of [Zn]/[Cd] = 25, efficiencies higher than those obtained with CdS and ZnS recipes, both on co‐evaporated CIGS and electrodeposited CISSe, have been obtained independent of the absorber used. In order to better understand the (Cd,Zn)S system and its impact on the increased efficiency of cells, predictions from the solubility diagrams of CdS and ZnS in aqueous medium were made. This analysis was completed by in situ growth studies with varying bath composition by quartz crystal microbalance (QCM). The morphology and composition of the films were studied using scanning electron microscopy (SEM) and X‐ray photoelectron spectra (XPS) techniques. Preliminary XPS studies showed that films are composed of a mixture of CdS and Zn(O,OH) phases and not a pure ternary Cd_{1 − x}Zn_xS compound. The effect of the [Zn]/[Cd] molar ratio on properties of the corresponding CISSe and CIGS solar cells was investigated by current voltage [J(V)] and capacitance voltage [C(V)] characterizations. The origin of optimal results is discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

The Zn(S,O,OH)/ZnMgO buffer in thin film Cu(In,Ga)(S,Se)2‐based solar cells part I: Fast chemical bath deposition of Zn(S,O,OH) buffer layers for industrial application on Co‐evaporated Cu(In,Ga)Se2 and electrodeposited CuIn(S,Se)2 solar cells

This paper is focused on the basic study and optimization of short time (<10 min) Chemical Bath Deposition (CBD) of Zn(S,O,OH) buffer layers in co‐evaporated Cu(In,Ga)Se₂ (CIGSe) and electrodeposited CuIn(S,Se)₂ ((ED)‐CIS) solar cells for industrial applications. First, the influence of the deposition temperature is studied from theoretical solution chemistry considerations by constructing solubility diagrams of ZnS, ZnO, and Zn(OH)₂ as a function of temperature. In order to reduce the deposition time under 10 min, experimental growth deposition studies are then carried out by the in situ quartz crystal microgravimetry (QCM) technique. An optimized process is performed and compared to the classical Zn(S,O,OH) deposition. The morphology and composition of Zn(S,O,OH) films are determined using SEM and XPS techniques. The optimized process is tested on electrodeposited‐CIS and co‐evaporated‐CIGSe absorbers and cells are completed with (Zn,Mg)O/ZnO:Al windows layers. Efficiencies similar or even better than CBD CdS/i‐ZnO reference buffer layers are obtained (15·7% for CIGSe and 8·1% for (ED)‐CIS). Copyright © 2009 John Wiley & Sons, Ltd.     

Quantitative luminescence mapping of Cu(In,Ga)Se2 thin‐film solar cells

We investigate photoluminescence and electroluminescence (PL and EL) emission images from Cu(In,Ga)Se₂‐based solar cells by means of a Hyperspectral Imager. Using the generalized Planck's law, maps of the effective quasi‐Fermi level splitting Δμ_eff in absolute values are obtained. A good agreement is found between the spatially averaged splitting in PL and the global open‐circuit voltage. However, from a local carrier transport discussion, we conclude that the equality does not hold locally. The spatial variations are rather attributed to local depth variations of the quasi‐Fermi level splitting due to material properties spatial fluctuations. By comparing PL and EL emissions, we discuss qualitatively the local effective lifetimes and collection efficiencies. Copyright © 2014 John Wiley & Sons, Ltd.     

Electronic structure of the Zn(O,S)/Cu(In,Ga)Se2 thin‐film solar cell interface

The electronic band alignment of the Zn(O,S)/Cu(In,Ga)Se₂ interface in high‐efficiency thin‐film solar cells was derived using X‐ray photoelectron spectroscopy, ultra‐violet photoelectron spectroscopy, and inverse photoemission spectroscopy. Similar to the CdS/Cu(In,Ga)Se₂ system, we find an essentially flat (small‐spike) conduction band alignment (here: a conduction band offset of (0.09 ± 0.20) eV), allowing for largely unimpeded electron transfer and forming a likely basis for the success of high‐efficiency Zn(O,S)‐based chalcopyrite devices. Furthermore, we find evidence for multiple bonding environments of Zn and O in the Zn(O,S) film, including ZnO, ZnS, Zn(OH)₂, and possibly ZnSe. Copyright © 2016 John Wiley & Sons, Ltd.     

ZnO nanorod arrays as an antireflective coating for Cu(In,Ga)Se2 thin film solar cells

A ZnO nanorod antireflective coating has been prepared on Cu(In,Ga)Se₂ thin film solar cells. This coating leads to a decrease of the weighted global reflectance of the solar cells from 8.6 to 3.5%. It boosts the solar cells short‐circuit current up to 5.7% without significant effect on their open‐circuit voltage and fill factor (FF), which is comparable to a conventional optimized single layer MgF₂ antireflective coating. The ZnO nanorod antireflective coating was electrochemically prepared from an aqueous solution at 80°C. The antireflective capability of ZnO nanorod arrays (ZNAs) may be further improved by optimization of growth conditions and their geometry. Copyright © 2010 John Wiley & Sons, Ltd.     

Monolithically interconnected lamellar Cu(In,Ga)Se2 micro solar cells under full white light concentration

Thin film solar cells already benefit from significant material and energy savings. By using photon management, the conversion efficiency and the power density can be enhanced further, including a reduction of material costs. In this work, micrometer‐sized Cu(In,Ga)Se₂ (CIGS) thin film solar cells were investigated under concentrated white light illumination (1–50×). The cell design is based on industrially standardized, lamellar shaped solar cells with monolithic interconnects (P‐scribe). In order to characterize the shunt and serial resistance profiles and their impact on the device performance the cell width was reduced stepwise from 1900 to 200 µm and the P1‐scribe thickness was varied between 45 and 320 µm. The results are compared to macroscopic solar cells in standard geometry and dot‐shaped microcells with ring contacts. Under concentrated white light, the maximal conversion efficiency could be increased by more than 3.8% absolute for the lamellar microcells and more than 4.8% absolute in case of dot‐shaped microcells compared to their initial values at 1 sun illumination. The power density could be raised by a factor of 51 and 70, respectively. But apparently, the optimum concentration level and the improvement in performance strongly depend on the chosen cell geometry, the used contact method and the electrical material properties. It turns out, that the widely used industrial thin film solar cell design pattern cannot simply be adapted to prepare micro‐concentrator CIGS solar modules, without significant optimization. Based on the experimental and simulated results, modifications for the cell design are proposed. Copyright © 2015 John Wiley & Sons, Ltd.     

Influence of high growth rates on evaporated Cu(In,Ga)Se2 layers and solar cells

Thin film solar cells based on polycrystalline Cu(In,Ga)Se₂ were prepared by elemental co‐evaporation using modified three‐stage processes on soda lime glass substrates at a low substrate temperature of 450°C intended for application on polyimide foils. The growth rates in the different stages of the growth process were varied, and it was observed that the final composition profile and structural quality of the film are mainly determined by the growth rate in the third stage. Application of high growth rates in the second stage was found to have no significant impact on layer morphology and gallium grading profile, which was confirmed by scanning electron microscopy, secondary ion mass spectroscopy, and x‐ray diffraction measurements. On the other hand, scanning electron microscopy cross sections revealed that high growth rates in the third stage lead to a fine‐grained structure toward the surface as well as smaller grains toward the back contact. Secondary ion mass spectroscopy and x‐ray diffraction measurements of such layers revealed a pronounced gallium grading profile, while Raman spectroscopy showed strong occurrence of group III‐rich phases in the near‐surface region. The final device performance was found to deteriorate by about 10% relative to the baseline process efficiency when growth rates of up to 500 nm min⁻¹ were applied in the second stage or 600 nm min⁻¹ in the third stage. Copyright © 2011 John Wiley & Sons, Ltd.