Cu(In,Ga)Se2 thin films annealed using a continuous wave Nd:YAG laser (λ0 = 532 nm): Effects of laser-annealing time

Abstract

Preparation of Cu(In,Ga)Se2 (CIGS) thin films has continued to face problems related to the selenization of sputtered Cu-In-Ga precursors when using H2Se vapor in that the materials are highly toxic and the facilities extremely costly. Another obstacle facing the production of CIGS thin films has been the required annealing temperature, as it relates to the decomposition temperature of a typical flexible polymer substrate. A novel laser-annealing process for CIGS thin films, which does not involve the selenization process and which can be performed at a lower temperature, has been proposed. Following sputtering with a Cu0.9In0.7Ga0.3Se2 target, the laser-annealing of the CIGS thin film was performed using a continuous 532-nm Nd:YAG laser with an annealing time of 200 - 1000 s at a laser optical power of 2.75 W. CIGS chalcopyrite (112), (220/204), and (312/116) phases, with some weak diffraction peaks corresponding to the Cu-Se- or the In-Se-related phases, were successfully obtained for all the CIGS thin films that had been laser-annealed at 2.75 W. The lattice parameters, the d-spacing, the tetragonal distortion parameter, and the strain led to the crystallinity being worse and grain size being smaller at 600 s while better crystallinity was obtained at 200 and 800 s, which was closely related to the deviations from molecularity and stoichiometry, which were greatest at 600 s while the values exhibited near-stoichiometric compositions at 200 and 800 s. The band gaps of the laser-annealed CIGS thin films were within a range of 1.765 - 1.977 eV and depended on the internal stress. The mean absorbance of the laser-annealed CIGS thin films was within a range of 1.598 - 1.900, suggesting that approximately 97.47 - 98.74% of the incident photons in the visible spectral region were absorbed by this 400-nm film. The conductivity types exhibited the same deviations (Δm > 0 and Δs < 0) in all the laser-annealed CIGS thin films. After laser-annealing, the resistivity fell abruptly to a range of 3.551 × 10 −2 - 1.022 × 10 −1 Ω·cm. The carrier concentration was on the order of 1019 - 1021 cm −3, and the carrier mobility was 5.7 × 10 −2 - 5.7 × 100 cm2/V·s.