The defect and transport properties of acceptor doped TlBr: role of dopant exsolution and association

The role of acceptor dopants (S and Se) in controlling the ionic conductivity of single crystal TlBr, grown by the vertical Bridgman method, was examined as a function of temperature with the aid of impedance spectroscopy. Several features in the conductivity were identified and related to acceptor dopant-Br vacancy association, acceptor dopant exsolution, and Br vacancy mobility. The corresponding enthalpies for these processes were extracted from the data and were found to be equal to H(a) = 0.42 ± 0.07 eV, H(sol) = 1.55 ± 0.18 eV and H(m,Br) = 0.31 ± 0.02 eV respectively, the latter consistent with earlier studies on donor doped and undoped TlBr. A long term conductivity decay in the extrinsic region, attributed to S or Se exsolution, was observed. The time constant associated with exsolution was found to be thermally activated with an activation energy of 0.47 ± 0.1 eV. Estimates for Se solubility at different temperatures are provided.