ELECTRICAL AND CRYSTALLOGRAPHIC PROPIERTIES OF THE SPINEL TYPE ZnCr2-2x In2XS4
C. Vargas-Hernándeza
, b, B. Acevedo-Fríasb, F. Serranob a Departamento de Física, Centro de Investigación y de Estudios Avanzados del I. P. N. Apdo. Postal 14-740. 07000, México, D. F. México.b Facultad de Ciencias, Universidad Nacional de Colombia. Sede Manizales-Colombia.The spinels type ZnCr2-2xIn2xS4 are compounds with structure of face centered cubic, these are normal spinels for x=0 and crystallize in the space group Fd3m-Oh7. These structures possess tetrahedral (A) and octahedral (B) sites, Zinc and Chromium or Indium occupy these sites, respectively. When this happens, the spinel is said normal. In other case is inverse. The system ZnCr2-2xIn2xS4 is of considerable experimental and theoretical interest. Thus, electrical and crystallographic properties, such as structure map and cation distributions, with regard to the tetrahedral and octahedral sites and behaviour in term of bonding, ionicity and free carrier contribution have been studied thoroughly in the last four decades. In this work, we report the electrical resistivity and lattice constants of the system ZnCr2-2xIn2xS4 as a function of temperature and Indium molar substitution, at concentrations from x = 0.0 to x = 0.30, and temperatures between 73 and 300 ēK. The samples were prepared by heating a mixture of the elements Zn, Cr, In and S in an evacuated silica tube as describe by Vargas-Hernández1. Depending on the In concentration the room temperature resistivity and lattice constant varied in the ranges from10-7 to 10-11 W -cm and 9.978 a 10.024 Å, respectively. We observed that after x = 0.25 the lattice constant did not change. This was attributed to the competition between In (In+3 =0.81Å) and Cr (Cr+3 = 0.64Å) to occupy octahedral sites. Additionally, this produce that some Cr atoms occupy zinc ( Zn+2 = 0.74Å) tetrahedral sites. These sites are formed by S ions (S-2 = 1.84Å). These results are in agreement with EPR2 (Electronic Resonance Paramagnetic) experiments, where, the spinels for x
0.25 have an inverse behaviour type. The activation energy increases when we replace Cr by In because the size of octahedral sites increases, but at the same time the size of tetrahedral sites decreases. The electrical conductivity also decreases, which indicates that there are not direct overlaps of the 3d orbitals of the Cr+3 ions.