X-ray diffraction analysis of stannite, wurtz-stannite and pseudo-cubic quaternary compounds by Rietveld method

M. Quintero^a,*, J. Marquina^b, E. Quintero^a, E. Moreno^a, S. Álvarez^a,b, C. Rincón^a, P. Grima^a, P. Bocaranda^a, D. Rivero^a, J. A. Henao^c, and M. A. Macías^c

^a Centro de Estudios de Semiconductores (CES), Departamento de Física, Facultad de Ciencias, Universidad de Los Andes, Mérida 5101, Venezuela. * e-mail: mquinterg@gmail.com; mquinter@ula.ve

^b Centro de Estudios Avanzados en Óptica (CEAO), Departamento de Física, Facultad de Ciencias, Universidad de los Andes 5101, Venezuela.

^c Grupo de Investigación en Química Estructural (GIQUE), Facultad de Ciencias, Escuela de Química, Universidad Industrial de Santander, Apartado aéreo 678, Bucaramanga, Colombia.

Received 6 November 2012.
Accepted 17 February 2014.

Abstract

Room temperature X-ray powder diffraction measurements were carried out on nine polycrystalline samples of the Cu₂B^II C^IVX₄ (B=Mn, or Fe, or Co; C=Si, or Ge, or Sn; X=S, or Se, or Te) magnetic semiconductor compounds. The diffraction patterns were used to show the equilibrium conditions and to derive crystalline parameter values. The results showed that four of these compounds have a tetragonal stannite structure with space group 142m(N° 121), two an orthorhombic wurtz-stannite structure with space group Pmn2₁(N° 31) and three of them an orthorhombic pseudo-cubic structure with space group F222 (N° 22). In each case, the structure was refined using the Rietveld method. When the obtained atomic parameter values for the tetragonal compounds were plotted as a function of molecular weight W, it was found that the values of the atomic positions, the cation-anion bond distances, tetragonal distortion and internal distortion of the compounds containing S and/or Se lay on different lines. Also, it was found that when the experimental points of the cation-anion bond distances d_Cu-VI, d_II-VI and d_IV-VI were plotted against the effective lattice parameter a_e = (V/N)^1/3, a linear variation of these distances with a_e was obtained. Values of the ionic energy gap C_i and homopolar energy gap E_h using the Phillips-Van Vechten scheme, with the present experimental crystallographic results as well as using the atomic data, were determined. It was found that the observed and predicted values of C_i and E_h lie on the same straight line.

Keywords: Magnetic semiconductors; crystal structure; X-ray powder diffraction; Rietveld refinement; crystal growth.

PACS: 61.05.cp; 61.50-f; 61.66.Fn; 75.50Pp

Acknowledgments

This work was partially supported by the CDCHT-ULA (Project No. C-1740-11-05-AA). E. Moreno would like to thank the Plan de Desarrollo de Talentos Humanos de Alto Nivel of FONACIT, through contract No. 200601411, Venezuela. S. Alvares would like to thank the Plan de Desarrollo de Talentos Humanos de Alto Nivel of FONACIT, through contract No. 200801535, Venezuela. P. Grima-Gallardo would like to thank to FONACIT, project PEII No 1697. M. A. Macías would to thank COLCIENCIAS (Colombia) for his doctoral fellowship. The authors would like to thank to the reviewer for its interest in this work and critical reading of the manuscript.

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