Thin film solar cells with the structure sodalimeglass∕Mo∕Cu(In,Ga)Se2∕Zn(O,S)∕ZnO∕ZnO:Al are studied for varying thickness and sulfur content of the Zn(O,S) buffer layer. These Zn(O,S) layers were deposited by atomic layer deposition (ALD) at 120°C. Devices with no or small concentrations of sulfur in the buffer layer show low open-circuit voltages. This is explained by the cliff, or negative conduction-band offset (CBO), of −0.2eV measured by photoelectron spectroscopy (PES) and optical methods for the Cu(In,Ga)Se2 (CIGS)∕ZnO interface. Devices with ZnS buffer layers exhibit very low photocurrent. This is expected from the large positive CBO (spike) of 1.2eV measured for the CIGS∕ZnS interface. For devices with Zn(O,S) buffer layers, two different deposition recipes were found to yield devices with efficiencies equal to or above reference devices in which standard CdS buffer layers were used; ultrathin Zn(O,S) layers with S∕Zn ratios of 0.8–0.9, and Zn(O,S) layers of around 30nm with average S∕Zn ratios of 0.3. The sulfur concentration increases towards the CIGS interface as revealed by transmission electron microscopy and in vacuo PES measurements. The occurrence of this sulfur gradient in ALD-Zn(O,S) is explained by longer incubation time for ZnO growth compared to ZnS growth. For the Zn(O,S) film with high sulfur content, the CBO is large which causes blocking of the photocurrent unless the film is ultrathin. For the Zn(O,S) film with lower sulfur content, a CBO of 0.2eV is obtained which is close to ideal, according to simulations. Efficiencies of up to 16.4% are obtained for devices with this buffer layer.

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.

This contribution concerns the effect of the Ag content in wide‐gap AgwCu1‐wIn1‐xGaxSe2 (ACIGS) absorber films and its impact on solar cell performance. First‐principles calculations are conducted, predicting trends in absorber band gap energy (Eg) and band structure across the entire compositional range (w and x). It is revealed that a detrimental negative conduction band offset (CBO) with a CdS buffer can be avoided for all possible absorber band gap values (Eg = 1.0–1.8 eV) by adjusting the Ag alloying level. This opens a new path to reduce interface recombination in wide‐gap chalcopyrite solar cells. Indeed, corresponding samples show a clear increase in open‐circuit voltage (VOC) if a positive CBO is created by sufficient Ag addition. A further extension of the beneficial compositional range (positive CBO at buffer/ACIGS interface) is possible when exchanging CdS with Zn1‐ySnyOz, because of its lower electron affinity (χ). Nevertheless, the experimental results strongly suggest that at present, residual interface recombination still limits the performance of solar cells with optimized CBO, which show an efficiency of up to 15.1% for an absorber band gap of Eg = 1.45 eV.

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An important milestone in the development of photovoltaic thin-film solar cells is the achievement of 15% conversion efficiency. This letter describes the highest efficiency single junction thin-film cell reported to date. An active area efficiency of 14.8% is obtained with the cell structure n-ZnO/n-CdS/p-CuInSe2 deposited on a soda-lime glass substrate. The current achievements are due to improved properties of the CuInSe2 layer and the heterojunctions compared to previously reported results. The rate and substrate temperature profiles used during the coevaporation process yield a relatively large-grained material with very strong 〈112〉 orientation and low porosity. This results in reduced recombination rates, hence higher open circuit voltage and fill factor.