Study of Cu(In,Al)Se2 thin films prepared by selenisation of sputtered metallic precursors for application in solar cells

Abstract

Cu-In, Cu-Al and Cu-In-Al metallic precursor layers were deposited using radio-frequency magnetron sputtering and selenised to produce thin films of CuInSe2 (CIS), CuAlSe2 (CAS) and CuIn1-xAlxSe2 (CIAS), respectively. The selenisation stage of this 2-stage process was carried out in a tube furnace (TF) or a rapid thermal processor (RTP) in the presence of elemental Se, either deposited on top of the precursor film or provided from an external source in the chamber, in order to fabricate the chalcopyrite material. The aim was to produce single phase, device quality CIS, CAS and CIAS for use as an absorber layer material in thin film photovoltaic solar cells. Profilometry performed on the as-deposited Cu-In-Al metallic precursors showed an important increase in surface roughness compared to the Cu-In and Cu-Al precursors. This was found to be due to the preferential formation of Cu9(In,Al)4, which stoichiometry led the excess In to form island-shaped In phases at the surface of the bulk, while only Cu2In and CuIn2 formed in Cu-In precursors. Regarding the selenisation, temperatures ranging from 250°C to 550°C were used, and the resulting samples were investigated using scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), secondary ion mass spectroscopy (SIMS) and glow-discharge optical emission spectroscopy (GD-OES). Thin films of single phase CIS and CAS were successfully produced with energy band gaps of 0.99 eV and 2.68 eV, respectively. However the incorporation of Al proved to be difficult. The results showed that no incorporation of the Al into the chalcopyrite lattice was achieved in the samples selenised in the RTP, which was believed to be due to the oxidation of the element Al into amorphous Al2O3. In the tube furnace, possibly due to lower levels of oxidation, incorporation occurred more readily but Al and In segregated towards the back and front of the layer, respectively. The causes of the segregation were studied and solutions to avoid it developed, resulting under certain conditions in successful production of CuIn1-xAlxSe2. Samples were tested in a photoelectrochemical cell and showed (apparent) external quantum efficiency values comparable to a CuInSe2 (CIS) sample used as a standard