We demonstrate a method which can hyperpolarize both the electron and nuclear spins of 31 P donors in Si at low field, where both would be essentially unpolarized in equilibrium. It is based on the selective ionization of donors in a specific hyperfine state by optically pumping donor bound exciton hyperfine transitions, which can be spectrally resolved in 28 Si. Electron and nuclear polarizations of 90% and 76%, respectively, are obtained in less than a second, providing an initialization mechanism for qubits based on these spins, and enabling further ESR and NMR studies on dilute 31 P in 28 Si.Enriched 28 Si is the material of choice for silicon-based quantum computing schemes involving electron or nuclear spins [1,2,3,4,5], since the removal of the 29 Si nuclear spin results in very long coherence times [4,6,7,8]. Several methods for achieving quantum logic with spin states of the shallow neutral donor (D 0 ) 31 P in 28 Si have been proposed [1,2,3] and the manipulation of electron and nuclear spin coherences have been demonstrated [4], but unsolved challenges include the measurement of single spins and the initialization, or polarization, of these spins. Fortuitously, the isotopic enrichment of 28 Si has another dramatic effect: the linewidths of many optical transitions are drastically reduced [9,10,11,12,13], including those involving 31 P. These narrow transitions have been proposed both for measurement of single spins [12,13,14] and for preferentially populating specific spin states [12,13].Electron and nuclear spin polarization in silicon has been studied for decades [15,16,17,18,19,20,21,22,23,24], but the nuclear polarization obtained to date has typically been less than a few percent, and requires thousands of seconds to establish. Very recently, a 31 P nuclear polarization of 68% has been reported [24] in a high magnetic field, using a variation of a mechanism first proposed in 1959 [17], and demonstrated in InSb in 1963 [18], but the time constant was still a relatively long 150 s. The method demonstrated here works at low magnetic field, and can simultaneously hyperpolarize both the electron and nuclear spins of 31 P in less than a second.Preliminary attempts to demonstrate this mechanism yielded relatively small electron and nuclear polarizations [25], due to the fact that until now all samples of 28 Si with sufficiently high enrichment to resolve the donor bound exciton (D 0 X) hyperfine transitions were p-type, with residual boron acceptor concentrations typically ten times the 31 P concentration. At low temperature all donors were therefore ionized (D + ), precluding the observation of D 0 → D 0 X transitions, unless abovegap excitation provided photoneutralization. This need for above-gap excitation has a strong negative effect on the achievable electron and nuclear polarizations, since it acts to equalize the populations in the four D 0 hyperfine states.The results presented here were made possible by a newly grown crystal of 28 Si purposely doped with 31 P. This n-type sample allowed us to ...