Thin-film photovoltaic devices based on chalcopyrite Cu(In,Ga)Se2 (CIGS) absorber layers show excellent light-to-power conversion efficiencies exceeding 20%. This high performance level requires a small amount of alkaline metals incorporated into the CIGS layer, naturally provided by soda lime glass substrates used for processing of champion devices. The use of flexible substrates requires distinct incorporation of the alkaline metals, and so far mainly Na was believed to be the most favourable element, whereas other alkaline metals have resulted in significantly inferior device performance. Here we present a new sequential post-deposition treatment of the CIGS layer with sodium and potassium fluoride that enables fabrication of flexible photovoltaic devices with a remarkable conversion efficiency due to modified interface properties and mitigation of optical losses in the CdS buffer layer. The described treatment leads to a significant depletion of Cu and Ga concentrations in the CIGS near-surface region and enables a significant thickness reduction of the CdS buffer layer without the commonly observed losses in photovoltaic parameters. Ion exchange processes, well known in other research areas, are proposed as underlying mechanisms responsible for the changes in chemical composition of the deposited CIGS layer and interface properties of the heterojunction.

Solar cells based on polycrystalline Cu(In,Ga)Se(2) absorber layers have yielded the highest conversion efficiency among all thin-film technologies, and the use of flexible polymer films as substrates offers several advantages in lowering manufacturing costs. However, given that conversion efficiency is crucial for cost-competitiveness, it is necessary to develop devices on flexible substrates that perform as well as those obtained on rigid substrates. Such comparable performance has not previously been achieved, primarily because polymer films require much lower substrate temperatures during absorber deposition, generally resulting in much lower efficiencies. Here we identify a strong composition gradient in the absorber layer as the main reason for inferior performance and show that, by adjusting it appropriately, very high efficiencies can be obtained. This implies that future manufacturing of highly efficient flexible solar cells could lower the cost of solar electricity and thus become a significant branch of the photovoltaic industry.

Thin film solar cells with a Cu(In,Ga)Se2 (CIGS) absorber layer achieved efficiencies above 20%. In order to achieve such high performance the absorber layer of the device has to be doped with alkaline material. One possibility to incorporate alkaline material is a post deposition treatment (PDT), where a thin layer of NaF and/or KF is deposited onto the completely grown CIGS layer. In this paper we discuss the effects of PDT with different alkaline elements (Na and K) on the electronic properties of CIGS solar cells. We demonstrate that whereas Na is more effective in increasing the hole concentration in CIGS, K significantly improves the pn-junction quality. The beneficial role of K in improving the PV performance is attributed to reduced recombination at the CdS/CIGS interface, as revealed by temperature dependent J-V measurements, due to a stronger electronically inverted CIGS surface region. Computer simulations with the software SCAPS are used to verify this model. Furthermore, we show that PDT with either KF or NaF has also a distinct influence on other electronic properties of the device such as the position of the N1 signal in admittance spectroscopy and the roll-over of the J-V curve at low temperature. In view of the presented results we conclude that a model based on a secondary diode at the CIGS/Mo interface can best explain these features.

Roll-to-roll manufacturing of CdTe solar cells on flexible metal foil substrates is one of the most attractive options for low-cost photovoltaic module production. However, various efforts to grow CdTe solar cells on metal foil have resulted in low efficiencies. This is caused by the fact that the conventional device structure must be inverted, which imposes severe restrictions on device processing and consequently limits the electronic quality of the CdTe layer. Here we introduce an innovative concept for the controlled doping of the CdTe layer in the inverted device structure by means of evaporation of sub-monolayer amounts of Cu and subsequent annealing, which enables breakthrough efficiencies up to 13.6%. For the first time, CdTe solar cells on metal foil exceed the 10% efficiency threshold for industrialization. The controlled doping of CdTe with Cu leads to increased hole density, enhanced carrier lifetime and improved carrier collection in the solar cell. Our results offer new research directions for solving persistent challenges of CdTe photovoltaics.

Doping the Cu(In,Ga)Se 2 (CIGS) absorber layer with alkaline metals is necessary to process high efficiency solar cells. When growth of CIGS solar cells is performed on soda-lime glass (SLG), the alkaline elements naturally diffuse from the substrate into the absorber layer. On the other hand, when CIGS is grown on alkaline free substrates, the alkaline metals have to be added from another source. In the past, Na was believed to be the most important dopant of the alkaline elements, even though K was also observed to diffuse into CIGS from the SLG. Recently, the beneficial effect of a post deposition treatment with KF was pointed out and enabled the production of a 20.4% CIGS solar cell grown at low substrate temperature (<500 C). However, possible negative effects of the presence or addition of the alkaline impurities during the low temperature growth process were observed for Na, but were not investigated for K so far. In this study, we investigate in detail the role of K on the defect formation in CIGS layers deposited at low temperature on alkaline free polyimide with intentional addition of K during selected time intervals of the CIGS layer growth. By means of admittance spectroscopy and deep level transient spectroscopy, we identify a deep minority carrier trap at around 280 meV below the conduction band E C in CIGS layers grown with K. Its influence on recombination and minority carrier lifetime in the absorber layer is investigated with external quantum efficiency measurements and time-resolved photoluminescence. Furthermore, to support the experimental findings device simulations were performed using the software SCAPS. V

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Non‐vacuum methods for Cu(In,Ga)Se2 (CIGS) absorber deposition have gained wide interest because of their inherent cost and energy saving potential. Here, a solution‐based processing route for CIGS absorber layers is presented that employs binder‐free solutions of metal salts in non‐toxic, alcohol solvents. Despite the low‐boiling‐point nature of the employed solvents, a residual carbon‐rich layer is observed between the CIGS and metal back contact. Based on comprehensive investigations by scanning electron microscopy, energy‐/wavelength dispersive X‐ray spectroscopy, X‐ray fluorescence, X‐ray diffraction, thermogravimetric analysis, differential thermal analysis, and extended X‐ray absorption fine structure spectroscopy, a formation reaction mechanism through intermediate metal–organic complexes is proposed. In this route, the CIGS layer is formed in selenium atmosphere via a gradual decomposition of the carbon‐rich layer comprising carboxylic chelate complexes of metals. A compositional gradient occurs in the CIGS absorber, whereas a significant amount of metals remains in the carbon‐rich layer. The incorporation of Ga into CIGS is affected by the initial salt concentration and the selenization temperature. Fabricated solar cells exhibit active area efficiencies of up to 7.7% on 0.3 cm2 area without anti‐reflection coating, which is among the highest reported efficiencies for solar cells from a solution process with non‐explosive gases or solvents. Copyright © 2012 John Wiley & Sons, Ltd.

Thin-film solar cells based on the chalcopyrite Cu(In,Ga)Se 2 (CIGS) absorber material show high potential for further cost reduction in photovoltaics. Compared with polycrystalline silicon (p-Si) wafer technology, thin-film technology has inherent advantages due to lower energy and material consumption during production but has typically shown lower conversion efficiency. However, in the past two years, new scientific insights have enabled the processing of CIGS solar cells with efficiencies up to 21%, surpassing the p-Si wafer value of 20.4% efficiency for the first time. Now several research groups report record cell efficiency values above 20% using different deposition processes and buffer layers. The presence of potassium was observed in many CIGS devices over the years, but it is only very recently that differences with Na have started being taken into full consideration for device processing and that K was added intentionally to the absorber. In this study, previous reports showing the presence of potassium are reviewed and discussed in more detail. Furthermore, on a scale-up perspective, additional progress has also taken place with CIGS minimodules achieving efficiency up to almost 19% and where further increase can be expected in the near future with the improvements induced by the use of potassium. This shows that the CIGS technology is continuously progressing not only on scientific level but on technological level as well.