This paper presents optimization studies on the formation of indium sulfide buffer layers for high-efficiency copper indium gallium diselenide (CIGS) thin-film solar cells with atomic layer chemical vapour deposition (ALCVD) from separate pulses of indium acetylacetonate and hydrogen sulfide. A parametric study of the effect of deposition temperature between 160° and 260°C and thickness (15–30 nm) shows an optimal value at about 220°C for a layer thickness of 30 nm, leading to an efficiency of 16·4%. Analysis of the device shows that indium sulfide layers are characterised by an improvement of the blue response of the cells compared with a standard CdS-processed cell, due to a high apparent band gap (2·7–2·8 eV), higher open-circuit voltages (up to 665 mV) and fill factor (78%). This denotes high interface quality. Atomic diffusion processes of sodium and copper in the buffer layer are demonstrated. Copyright © 2003 John Wiley & Sons, Ltd.