RESUMO
The kinetics for Schottky defect (Tl and Br vacancy pair) formation and annihilation in ionically conducting TlBr are characterized through a temperature induced conductivity relaxation technique. Near room temperature, defect generation-annihilation was found to take on the order of hours before equilibrium was reached after a step change in temperature, and that mechanical damage imparted on the sample rapidly increases this rate. The rate limiting step to Schottky defect formation-annihilation is identified as being the migration of lower mobility Tl (versus Br), with an estimate for source-sink density derived from calculated diffusion lengths. This study represents one of the first investigations of Schottky defect generation-annihilation kinetics and demonstrates its utility in quantifying detrimental mechanical damage in radiation detector materials.
RESUMO
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.
