Zn ( O , S ) buffer layers by atomic layer deposition in Cu(In,Ga)Se2 based thin film solar cells: Band alignment and sulfur gradient

Abstract

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.