Issue 0, 1969

Charge transfer in mixed-valence solids. Part V. Semiconductivity of hexachloroantimonates(III,V)

Abstract

Two-probe D.C. conductivity measurements are reported for the three series of hexachloroantimonates(III,V) whose optical properties were examined in the preceding paper: A2ISbxSn1-xCl6(AI= NH4+, Cs+), Cs2lnIII½ySbIIIy SbV½Cl6. For values of x and y greater than about 0·1, the compounds behave as ohmic semiconductors. The specific conductivities at room temperature are proportional to x2 and y respectively, while the activation energies are independent of the antimony concentration. Seebeck coefficients, determined at room temperature, indicate that for x and y > 0·1 the majority carriers are holes, but below 0·1, electrons. It is suggested that the conductivity of the compounds containing sufficient antimony to form a continuous path through the lattice is electronic while that of the dilute materials and single-valence host lattices is ionic. In the former, the magnitude of the conductivity is consistent with a diffusion mechanism in which carrier formation by electron transfer between SbCl63– and SbCl6 is followed by migration of the resulting SbCl62– among the SbCl63–. The charge-carrier formation step is the adiabatic analogue of the Franck–Condon intermolecular charge transfer process studied in the preceding paper. Relaxation frequencies calculated from the observed conductivity by use of the diffusion model are in the range of Sb–Cl vibrations. The relation between the semiconductor activation energy and the optical chargetransfer energy is discussed.

Article information

Article type
Paper

J. Chem. Soc. A, 1969, 2432-2436

Charge transfer in mixed-valence solids. Part V. Semiconductivity of hexachloroantimonates(III,V)

L. Atkinson and P. Day, J. Chem. Soc. A, 1969, 2432 DOI: 10.1039/J19690002432

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Spotlight

Advertisements