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.     

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.     

Dynamic radiative properties of the Cu(In,Ga)Se2 layer during the co‐evaporation process

A study of the wavelength‐integrated emissivity has been performed on the optical stack Cu_xSe/Cu(In,Ga)Se₂/Mo. The wavelength interval used in the study was 2–20 µm, which covers 95% of the radiated heat from a black body heated to 500°C. Substrate temperatures around 500°C are commonly used in production of Cu(In,Ga)Se₂ thin films for solar cells. The integrated emissivity was obtained from directional reflectivity measurements of experimental samples with different thicknesses of the Cu_xSe layers. It was subsequently compared to the emissivity from numerical simulations based on newly obtained values of the refractive index values for Cu(In,Ga)Se₂ and Cu_xSe at these wavelengths. Good agreement was found between the measured and simulated values. At a Cu(In,Ga)Se₂ thickness of 1.8 µm and a Mo thickness of 400 nm, a maximum in the integrated emissivity was found for a Cu_xSe thickness of 30 nm. The results are valuable input into understanding the dynamics of the change in emissivity between Cu‐rich Cu(In,Ga)Se₂ with segregated Cu_xSe and Cu‐poor single phase Cu(In,Ga)Se₂ at temperatures around 500°C. In co‐evaporation of Cu(In,Ga)Se₂, this emissivity change is often monitored and used as a process control (end‐point detection). Copyright © 2010 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.     

The effect of Zn1−xSnxOy buffer layer thickness in 18.0% efficient Cd‐free Cu(In,Ga)Se2 solar cells

The influence of the thickness of atomic layer deposited Zn_1−xSn_xO_y buffer layers and the presence of an intrinsic ZnO layer on the performance of Cu(In,Ga)Se₂ solar cells are investigated. The amorphous Zn_1−xSn_xO_y layer, with a [Sn]/([Sn] + [Zn]) composition of approximately 0.18, forms a conformal and in‐depth uniform layer with an optical band gap of 3.3 eV. The short circuit current for cells with a Zn_1−xSn_xO_y layer are found to be higher than the short circuit current for CdS buffer reference cells and thickness independent. On the contrary, both the open circuit voltage and the fill factor values obtained are lower than the references and are thickness dependent. A high conversion efficiency of 18.0%, which is comparable with CdS references, is attained for a cell with a Zn_1−xSn_xO_y layer thickness of approximately 13 nm and with an i‐ZnO layer. Copyright © 2012 John Wiley & Sons, Ltd.     

Minimizing metastabilities in Cu(In,Ga)Se2/(CBD)Zn(S,O,OH)/i‐ZnO‐based solar cells

Chemical bath deposited (CBD)Zn(S,O,OH) is among the alternatives to (CBD)CdS buffer layers in Cu(In,Ga)Se₂(CIGSe)‐based devices. Nevertheless, the performances reached by devices buffered with (CBD)Zn(S,O,OH) vary strongly from one sample to another and from one laboratory to another, indicating that parameters of minority impact with (CBD)CdS‐buffered devices have major influence when buffered with (CBD)Zn(S,O,OH). Moreover, the literature reports, but not systematically, the requirement of substituting the standard resistive intrinsic ZnO by (Zn,Mg)O and/or soaking the devices in ultraviolet‐containing light in order to reach optimal device operation. The present study investigates the impact of the three following parameters on the optoelectronic behavior of the Cu(In,Ga)Se₂/(CBD)Zn(S,O,OH)/i‐ZnO‐based solar cells: (i) CIGSe surface composition; (ii) (CBD)Zn(S,O,OH) layer thickness; and (iii) i‐ZnO layer resistivity. The first conclusion of this study is that all of these parameters are observed to influence the electrical metastabilities of the devices. The second conclusion is that the light soaking time needed to achieve optimal photovoltaic parameters is decreased by (i) using absorbers with Cu content close to stoichiometry, (ii) increasing the buffer layer thickness, and (iii) increasing the resistivity of i‐ZnO. By optimizing these trends, stable and highly efficient Zn(S,O,OH)‐buffered CIGSe solar cells have been fabricated. 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.     

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.     

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.     

Co‐optimization of SnS absorber and Zn(O,S) buffer materials for improved solar cells

Thin‐film solar cells consisting of earth‐abundant and non‐toxic materials were made from pulsed chemical vapor deposition (pulsed‐CVD) of SnS as the p‐type absorber layer and atomic layer deposition (ALD) of Zn(O,S) as the n‐type buffer layer. The effects of deposition temperature and annealing conditions of the SnS absorber layer were studied for solar cells with a structure of Mo/SnS/Zn(O,S)/ZnO/ITO. Solar cells were further optimized by varying the stoichiometry of Zn(O,S) and the annealing conditions of SnS. Post‐deposition annealing in pure hydrogen sulfide improved crystallinity and increased the carrier mobility by one order of magnitude, and a power conversion efficiency up to 2.9% was achieved. Copyright © 2014 John Wiley & Sons, Ltd.     

ILGAR In2S3 buffer layers for Cd‐free Cu(In,Ga)(S,Se)2 solar cells with certified efficiencies above 16%

In₂S₃ buffer layers have been prepared using the spray ion layer gas reaction deposition technique for chalcopyrite‐based thin‐film solar cells. These buffers deposited on commercially available Cu(In,Ga)(S,Se)₂ absorbers have resulted in solar cells with certified record efficiencies of 16.1%, clearly higher than the corresponding CdS‐buffered references. The deposition process has been optimized, and the resulting cells have been studied using current–voltage and quantum efficiency analysis and compared with previous record cells, cells with a thermally evaporated In₂S₃ buffer layer and CdS references. Copyright © 2012 John Wiley & Sons, Ltd.     

Investigation of Cu(In,Ga)Se2 thin‐film formation during the multi‐stage co‐evaporation process

In order to transfer the potential for the high efficiencies seen for Cu(In,Ga)Se₂ (CIGSe) thin films from co‐evaporation processes to cheaper large‐scale deposition techniques, a more intricate understanding of the CIGSe growth process for high‐quality material is required. Hence, the growth mechanism for chalcopyrite‐type thin films when varying the Cu content during a multi‐stage deposition process is studied. Break‐off experiments help to understand the intermediate growth stages of the thin‐film formation. The film structure and morphology are studied by X‐ray diffraction and scanning electron microscopy. The different phases at the film surface are identified by Raman spectroscopy. Depth‐resolved compositional analysis is carried out via glow discharge optical emission spectrometry. The experimental results imply an affinity of Na for material phases with a Cu‐poor composition, affirming a possible interaction of sodium with Cu vacancies mainly via In(Ga)_Cu antisite defects. An efficiency of 12.7% for vacancy compound‐based devices is obtained. Copyright © 2011 John Wiley & Sons, Ltd.     

The effect of Mo back contact ageing on Cu(In,Ga)Se2 thin‐film solar cells

In this work, we investigate the effect of ageing Mo‐coated substrates in a dry and N₂ flooded cabinet. The influence was studied by preparing Cu(In,Ga)Se₂ solar cells and by comparing the electrical performance with devices where the Mo layer was not aged. The measurements used for this study were current–voltage (J‐V), external quantum efficiency (EQE), secondary ion mass spectroscopy (SIMS) and capacitance–voltage (C‐V). It was concluded that devices prepared with the aged Mo layer have, in average, an increase of 0.8% in efficiency compared with devices that had a fresh Mo layer. Devices with aged Mo exhibited a nominal increase of 12.5 mV of open circuit voltage, a decrease of 1.1 mA/cm⁻² of short circuit current and a fill factor increase of 2.4%. Heat treatment of fresh Mo layers in oxygen atmosphere was also studied as an alternative to ageing and was shown to provide a similar effect to the aged device's performance. Copyright © 2013 John Wiley & Sons, Ltd.     

Thin‐film Cu(In,Ga)(Se,S)2‐based solar cell with (Cd,Zn)S buffer layer and Zn1−xMgxO window layer

(Cd,Zn)S buffer layer and Zn_1−x Mg_x O window layer were investigated to replace the traditional CdS buffer layer and ZnO window layer in Cu(In,Ga)(Se,S)₂ (CIGSSe)‐based solar cell. (Cd,Zn)S with band‐gap energy (E _g) of approximately 2.6 eV was prepared by chemical bath deposition, and Zn_1−x Mg_x O films with different [Mg]/([Mg] + [Zn]) ratios, x , were deposited by radio frequency magnetron co‐sputtering of ZnO and MgO. The estimated optical E _g of Zn_1−x Mg_x O films is linearly enhanced from 3.3 eV for pure ZnO (x  = 0) to 4.1 eV for Zn_0.6Mg_0.4O (x  = 0.4). The quality of the Zn_1−x Mg_x O films, implied by Urbach energy, is severely deteriorated when x is above 0.211. Moreover, the temperature‐dependent current density‐voltage characteristics of the CIGSSe solar cells were conducted for the investigation of the heterointerface recombination mechanism. The external quantum efficiency of the CIGSSe solar cell with the (Cd,Zn)S buffer layer/Zn_1−x Mg_x O window layer is improved in the wavelength range of 320–520 nm. Therefore, a gain in short‐circuit current density up to about 5.7% was obtained, which is higher conversion efficiency of up to around 5.4% relative as compared with the solar cell with the traditional CdS buffer layer/ZnO window layer. The peak efficiency of 19.6% was demonstrated in CIGSSe solar cell with (Cd,Zn)S buffer layer and Zn_1−x Mg_x O window layer, where x is optimized at 0.211. Copyright © 2017 John Wiley & Sons, Ltd.     

Improved fill factor and open circuit voltage by crystalline selenium at the Cu(In,Ga)Se2/buffer layer interface in thin film solar cells

A surface treatment by evaporated selenium on Cu(In,Ga)Se₂ (CIGS) is shown to improve open circuit voltage, V_oc, and in some cases fill factor, FF, in solar cells with CdS, (Zn,Mg)O or Zn(O,S) buffer layers. V_oc increases with increasing amount of crystalline Se, while FF improves only for small amounts. The improvements are counteracted by a decreasing short circuit current assigned to absorption in hexagonal Se. Improved efficiency is shown for device structures with (Zn,Mg)O and Zn(O,S) buffer layers by atomic layer deposition. Analysis by grazing incidence X‐ray diffraction and photoelectron spectroscopy show partial coverage of the CIGS surface by hexagonal selenium. The effects on device performance from replacing part of the CIGS/buffer interface area by a Se/buffer junction are discussed. Copyright © 2010 John Wiley & Sons, Ltd.     

Above 16% efficient sequentially grown Cu(In,Ga)(Se,S)2‐based solar cells with atomic layer deposited Zn(O,S) buffers

We report the development of Cd‐free buffers by atomic layer deposition for chalcopyrite‐based solar cells. Zn(O,S) buffer layers were prepared by atomic layer deposition on sequentially grown Cu(In,Ga)(Se,S)₂ absorbers from Bosch Solar CISTech GmbH. An externally certified efficiency of 16.1% together with an open circuit voltage of 612 mV were achieved on laboratory scale devices. Stability tests show that the behavior of the ALD‐Zn(O,S)‐buffered devices can be characterized as stable only showing a minor drift of the open circuit voltage and the fill factor. Copyright © 2015 John Wiley & Sons, Ltd.     

Influence of the Cu(In,Ga)Se2 thickness and Ga grading on solar cell performance

Thin‐film solar cells with Cu(In,Ga)Se₂ (CIGS) absorber layers ranging from 1.8 to 0.15 μm in thickness were fabricated by co‐evaporation, with both homogeneous and Ga/(Ga + In) graded composition. The absorption of the CIGS layers was determined and compared with corresponding QE measurements in order to obtain the optical related losses. The material characterization included XRD as well as cross‐sectional SEM analysis. Devices with CIGS layers of all thicknesses were fabricated, and down to 0.8–1 μm they showed a maintained high performance (η ∼ 15%). When the CIGS layer was further reduced in thickness the loss in performance increased. The main loss was observed for the short‐circuit current, although the loss was not only due to a reduced absorbance. The open‐circuit voltage was essentially not affected by the reduction of the CIGS thickness, while the fill factor showed a slight decrease. The fill factor loss was eliminated by introducing a Ga/(Ga+In) graded CIGS, which also resulted in an increased open‐circuit voltage of 20–30 mV for all CIGS thicknesses. Device results of 16.1% efficiency at 1.8 μm CIGS thickness, 15.0% at 1.0 μm and 12.1% at 0.6 μm (total area without anti‐reflective coating) were achieved. Copyright © 2002 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.     

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.     

Improving the photovoltaic performance of co‐evaporated Cu2ZnSnS4 thin‐film solar cells by incorporation of sodium from NaF layers

We have investigated the influence of sodium (Na) on the properties of co‐evaporated Cu₂ZnSnS₄ (CZTS) layer microstructures and solar cells. The photovoltaic performance and diode properties were improved by incorporating Na from NaF layers into the CZTS layers, while Na had a negligible effect on the microstructural properties of the layer. The best cell fabricated by using an optimal CZTS layer (Cu/(Zn + Sn) = 0.70, Zn/Sn = 1.8) yielded an active area efficiency of 5.23%. The analysis of device properties suggests that charge‐carrier recombination at CZTS/CdS interface is suppressed by intentional Na incorporation from NaF layers. Copyright © 2016 John Wiley & Sons, Ltd.