Phosphorescence and Donor-Acceptor Pair Recombination in Laboratory-Grown Diamonds

Intense "blue-green" phosphorescence is commonly observed in near colourless lab-grown high-pressure high-temperature (HPHT) diamonds following optical excitation at or above the indirect bandgap. We have employed a holistic combination of optically-excited time-resolved techniques (in addition to standard spectroscopic characterisation techniques) to study the physics of this long-lived phosphorescence and understand luminescence-related charge transfer processes. It is shown that the properties of the broad "blue-green" luminescence and phosphorescence band can be fully explained by emission from neutral substitutional nitrogen-boron donor-acceptor pairs ($\text{N}_\text{S}^0$...$\text{B}_\text{S}^0$) , once the configurational change between charge states is considered, and both tunneling between defects and thermal ionization of donors and acceptors is considered. Significant concentrations of metastable $\text{N}_\text{S}^-$, are identified after optical excitation at or above the indirect bandgap. $\text{N}_\text{S}^-$ is much shallower ($\sim$0.2 eV) than previously thought and plays a key role in resetting the $\text{N}_\text{S}^0$...$\text{B}_\text{S}^0$ donor-acceptor pairs.