In this study, Si-doped Cu<sub>2</sub>ZnSnS<sub>4</sub> compounds (Cu<sub>2</sub>ZnSn<sub>1-x</sub>Si<sub>x</sub>S<sub>4</sub>, 0 ≤ x ≤ 1) were...In this study, Si-doped Cu<sub>2</sub>ZnSnS<sub>4</sub> compounds (Cu<sub>2</sub>ZnSn<sub>1-x</sub>Si<sub>x</sub>S<sub>4</sub>, 0 ≤ x ≤ 1) were prepared by solid state reaction method for use of materials for photovoltaic cells. The structural and spectroscopic properties of the as-prepared compounds were studied by X-ray diffraction (XRD), <sup>119</sup>Sn, <sup>29</sup>Si and <sup>65</sup>Cu Magic Angle Spinning nuclear magnetic resonance (MAS NMR) and Raman spectroscopy. The Si-substitution in the Sn-site induces three different types of XRD patterns which depend largely on the Si content in the compound. For 0 ≤ x ≤ 0.5, XRD analysis reveals the presence of a pure tetragonal phase of solid solution with I-42m as a space group. Mixed tetragonal and orthorhombic phases were observed for 0.5 < x < 0.8, followed by a pure orthorhombic structure with a space group Pmn2<sub>1</sub> at high content of Si (x ≥ 0.8). <sup>119</sup>Sn MAS NMR spectra show the presence of Sn/Si disorder as a function of the Si content. The <sup>65</sup>Cu MAS NMR spectra of the quadratic solid solution confirm the presence of the two copper sites (Cu-2a and Cu-2c) at 780 ppm while in the case of the orthorhombic solid solution samples, a very broad band is observed. The optical properties were investigated of all compounds by UV-Vis diffuse reflectance and the obtained optical band gap values (1.31 to 2.43 eV) confirm a semiconductor character.展开更多
文摘In this study, Si-doped Cu<sub>2</sub>ZnSnS<sub>4</sub> compounds (Cu<sub>2</sub>ZnSn<sub>1-x</sub>Si<sub>x</sub>S<sub>4</sub>, 0 ≤ x ≤ 1) were prepared by solid state reaction method for use of materials for photovoltaic cells. The structural and spectroscopic properties of the as-prepared compounds were studied by X-ray diffraction (XRD), <sup>119</sup>Sn, <sup>29</sup>Si and <sup>65</sup>Cu Magic Angle Spinning nuclear magnetic resonance (MAS NMR) and Raman spectroscopy. The Si-substitution in the Sn-site induces three different types of XRD patterns which depend largely on the Si content in the compound. For 0 ≤ x ≤ 0.5, XRD analysis reveals the presence of a pure tetragonal phase of solid solution with I-42m as a space group. Mixed tetragonal and orthorhombic phases were observed for 0.5 < x < 0.8, followed by a pure orthorhombic structure with a space group Pmn2<sub>1</sub> at high content of Si (x ≥ 0.8). <sup>119</sup>Sn MAS NMR spectra show the presence of Sn/Si disorder as a function of the Si content. The <sup>65</sup>Cu MAS NMR spectra of the quadratic solid solution confirm the presence of the two copper sites (Cu-2a and Cu-2c) at 780 ppm while in the case of the orthorhombic solid solution samples, a very broad band is observed. The optical properties were investigated of all compounds by UV-Vis diffuse reflectance and the obtained optical band gap values (1.31 to 2.43 eV) confirm a semiconductor character.
