We can therefore divide the NPs into two separate populations: those which are in contact with oxygen (represented in Figure 3) and those which are not. We write the proportion of NPs which do not have adsorbed oxygen molecules and which do not currently contain an exciton as n 0; excitons are created in these in one of the three triplet exciton states (index i = 1…3) with equal pumping rates P/3 to generate
fractional populations u i . The photoexcited NPs can de-populate only by radiative emission with rates r 0,r 1 for m j = 0, m j = ±1, respectively (note that, here, we set these equal; we will consider the consequences of these being different in a future work), spin-lattice relaxation to spin states lower in energy (γ ij ), or thermal excitation to spin states higher in energy by Δ ij (γ ij = γ exp(-Δ ij /k T)). Note that Δ ij is see more dependent on the magnetic field since it arises from the Zeeman splitting of the exciton states; this leads to a magnetic field dependence of γ ij . Non-radiative relaxation processes may also contribute to the triplet exciton relaxation at low temperatures [11] but would enter into our model in the same way as the radiative decay rates and so are not included explicitly. Under these assumptions, the steady state solution of the rate equations for the fractional populations u i ,n 0 yields the following result (Equation 1): (1) where F is the total fraction
of NPs with adsorbed oxygen. Silicon nanoparticles with oxygen We now consider the second population of NPs, those which are in contact with oxygen. We write the proportions of NPs which do not contain an exciton as n j , where GW-572016 purchase j runs over the three possible oxygen triplet states. As above, excitons are created in these NPs in one of the three triplet exciton states
(index i = 1…3) with equal pumping rates P/3 to generate fractional coupled exciton-oxygen populations n ij . The exciton radiative recombination oxyclozanide and spin-lattice relaxation terms are as above, and we introduce a spin-lattice relaxation and thermal excitation term between the oxygen triplet states analogous to γ ij (β ij ). Note, again, that β ij is in general a buy PCI-34051 function of magnetic field and depends on both zero-field and Zeeman terms (shown in Figure 4). We must also account for NPs in which the oxygen is in the singlet state and no exciton is present (the condition of an NP after energy transfer and before relaxation of the oxygen, with population n e ) and NPs in which an exciton has been excited whilst the oxygen is still in the singlet state (populations w j ). Figure 4 Energy level diagram for the energy transfer from photoexcited silicon nanoparticles to oxygen molecules. Left: the triplet (bottom) and singlet (top) levels of molecular oxygen in a magnetic field, showing the zero-field splitting between the m J = 0 and the m J = ±1 levels; right: the ground state (bottom) and triplet exciton (top) states of a silicon nanoparticle in a magnetic field.