We investigate the synthesis of kesterite Cu 2 ZnSnS 4 (CZTS) polycrystalline thin films using cosputtering from binary sulfide targets followed by annealing in sulfur vapor at 500°C to 650°C. The films are the kesterite CZTS phase as indicated by x-ray diffraction, Raman scattering, and optical absorption measurements. The films exhibit (112) fiber texture and preferred low-angle and R3 grain boundary populations which have been demonstrated to reduce recombination in Cu(In,Ga)Se 2 and CdTe films. The grain growth kinetics are investigated as functions of temperature and the addition of Na. Significantly, lateral grain sizes above 1 lm are demonstrated for samples grown on Na-free glass, demonstrating the feasibility for CZTS growth on substrates other than soda lime glass.

CuInSe2 (CISe) is a prototype material for the I–III–VI chalcopyrites such as Cu(In,Ga)(S,Se)2 (CIGSSe) used as absorber layers in thin film photovoltaic cells. These thin film photovoltaic absorber layers are primarily synthesized by vacuum-based techniques in manufacturing. In this work, we investigate non-vacuum film synthesis by electrochemical deposition of CISe from a single bath followed by continuous wave laser annealing (CWLA) using a 1064 nm laser. We find that parameters exist for near-infrared CWLA which result in structural changes without melting and dewetting of the films. While Cu-poor samples show only about 40% reduction in the full width at half maximum (FWHM) of the respective x-ray diffraction (XRD) peaks, identically treated Cu-rich samples indicate a FWHM reduction of more than 70% in the XRD and Raman scattering data for irradiation at 50 W/cm2. This study demonstrates that an entirely solid-phase annealing path driven by intense illumination exists for chalopyrite phase formation and crystallization from electrodeposited CISe thin films.

Cu(In,Ga)Se2 (CIGSe) is a polycrystalline absorber layer in thin film solar cells with solar conversion efficiencies exceeding 20%. High temperature annealing for periods of minutes to hours is currently required to convert amorphous or nanocrystalline precursor material into high quality Cu(In,Ga)Se2 absorber layers. In this work, we perform the critical annealing step, using a 1064 nm laser, on electrodeposited precursor layers containing Cu, In, and Se, for times of 0.3–60 s thus synthesizing CuInSe2 absorber layers. An annealing time of 1 s is found to be sufficient to remove elemental concentration gradients in the bulk of the layer and to increase the average implied crystallite size (crystal coherence length, as determined by X-ray diffraction, XRD). Therefore the rate-determining step in producing higher quality layers with short annealing times is the rate of grain growth and not atomic diffusion. Optoelectronic analysis of the absorber layers revealed p-type doping with improved radiative recombination compared to the precursors. Laser annealed CuInSe2 layers did not produce working photovoltaic devices. This is first attributed to a loss of Se that occurs during laser annealing, resulting in detrimental substoichiometric quantities of Se in the absorber. Second, the likely presence of a thick surface layer of the CuIn3Se5 phase is expected to detrimentally impact device performance. These findings must be addressed if annealing times of the CuInSe2 absorber layer are to be reduced to seconds.

Rapid laser annealing converts CuInSe2 precursors into working semiconductors only when the precursor has suitable optical and microstructural properties.