The kinetics of donor-acceptor pair transitions with strong phonon coupling in GaP

Donor-acceptor pair luminescence in GaP was studied by time-resolved spectroscopy, by measuring and analysing the integral band decay over many decades of intensity and time and by measuring and analysing the temperature dependence of the luminescence intensity. We report here the results obtained with some or all of these techniques for pairs involving deep as well as shallow centres. Those with a deep centre are: S_P-Si_P and Si_Ga-Si_P, in which the acceptor is the deep centre, and O_P-C_P and O_P-Zn_Ga, in which the donor is the deep centre. These pairs all have a broad, phonon-dominated luminescence band. The pairs involving shallow centres include Si_Ga-C_P, S_P-C_P and Te_P-C_P. Due to the different way of momentum conservation in these pairs, those involving a donor on a Ga-site have strong phonon co-operation and weak zero-phonon (ZP) transitions, whereas those with a donor on a P-site have strong ZP transitions.With time-resolved spectroscopy, well-resolved structure, due to a ZP pair band and its phonon replicas, is obtained for nearly all pairs. A comparison is made with the structure obtained by measuring in the stationary state at very low excitation densities. Some trends in the strength of phonon co-operation are noted. In the case of Si_Ga-C_P pairs, sharp replicas of ZP pair lines with a momentum-conserving phonon are also resolved.Using the integral band decay technique and results from time-resolved spectroscopy we have determined the transition probabilities for the total luminescence band as well as for the ZP band for nearly all pairs mentioned. The influence of incomplete saturation of the pairs during excitation with a focussed beam of an argon-ion laser is discussed and approximately corrected for. Extrapolated to zero pair separation, the total transition probability ranges from ∽ 10⁵s^-1 for Si_Ga-C_P pairs to ∽ 15 × 10⁵s^-1 for O_P-C_P and O_P-Zn_Ga pairs. The ZP probability ranges from ∽ 4 × 10³s^-1 for Si_Ga-C_P and Si_Ga-Si_P pairs to ∽ 4 × 10⁵s^-1 for S_P-C_P pairs. The transition probability for pairs in GaP is discussed in relation to the site occupied by the donor and the depth of the centres involved. The relatively high dope concentrations used in some cases, ∽ 1 to 2 × 10¹⁸cm^-3, are discussed briefly in relation to “concentration quenching”.The temperature dependence of the luminescence intensity of S_P-Si_P pairs is satisfactorily analysed with a simple linear model. The same model is applied to similar literature data on the S_P-C_P pair luminescence. Using in addition data on the average pair transition probability, trapping rate constants for hole capture by the Si_P and C_P acceptors were calculated to be ∽ 10^-9 cm³s^-1. Evidence is presented that the trapping rate constant for holes by the Zn_Ga-O_P complex is about 2 × 10^-9 cm³s^-1.