Abstract

The improvement of low cost, efficient photovoltaic devices is a leading technological challenge in the recent decade. There is a need to develop scalable and high-throughput manufacturing techniques that could reduce costs and improve manufacturing of chalcogenide solar cells. Copper, indium, gallium, and selenium (CIGS) Thin films polycrystalline heterojunction solar cells appear to be most appropriate with to cost and ease of manufacture. Currently Cu (In,Ga) (Se, S)2 materials hold the highest record cell efficiency of 22.3% in laboratory scale for thin films solar cells and the efficiency still be boosted by improving the different layers of the photovoltaic devices. CIGS chalcogenide absorber layers has been a leading candidate material in photovoltaic devices for thin films solar cells and space applications due to its unique optical-electronic properties as well as its radiation resistance. In the present work, thin films of Cu (In, Ga) (Se, S)2 were deposited at room temperature on glass substrates coated with ITO and Mo by electrodeposition techniques. The obtained polycrystalline thin films were characterized by UV-Vis spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS) analysis. Thin films of Cu (In, Ga) (Se, S)2 grown by electrodeposition were subsequently processed into several sets of conditions including vacuum heat treatment, heat treatment in the presence of selenium or sulfur, heat treatment in nitrous gas atmosphere (N2H2) at different temperature and processing times. To improve the composition and the crystalline structure of the thin layers and to optimize the electro-optical properties a heat treatment of the thin films was developed in two stages after the electrodeposition. It was observed that the first annealing step (heating treatment at 450 °C in a selenium atmosphere 40 minutes) produced an appreciable improvement in the crystalline structure in the thin layer composition. In a second stage a sulfurization of the CuGaSe2 films was performed at 400 °C for 10 min in the presence of molecular sulfur and under the forming gas atmosphere. The effect of sulfurization was the complete conversion of selenium to sulfur and, therefore, the transformation of CuGaSe2 into CuGaS2. The formation of CuGaS2 thin films was evidenced by the by the displacement of the diffraction peaks of the CuGaSe2 towards higher angles to which makes the X-Ray diffraction 18 pattern which makes it coincide with the diffraction pattern of the CuGaSe2 films, and by the shift towards the blue (higher energies) of the optical gap. The optical gap found for the CuGaSe2 layer was 1.66 eV, while the optical gap for the CuGaS2 was raised up to 2.2 eV. CdS thin films have been widely used as buffer layer in CIGS solar cells. However, when alloyed with Zn, ZnCdS can still improve its performance as buffer layer. ZnCdS can be used as buffer and as window material in photoconductive devices and in heterojunction thin film solar cells due the possibility to tune the bandgap with the content of Zn. The band spacing of this ternary material can be from 2.42 to 3.50 eV, depending on the Cd/Zn ratio.

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