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Dopants in silicon have been studied for many decades using optical andelectron spin resonance (ESR) spectroscopy. Recently, new features have beenobserved in the spectra of dopants in isotopically enriched 28Si since thereduced inhomogeneous linewidth in this material improves spectral resolution.With this in mind, we measured ESR on exchange coupled phosphorus dimers in28Si and report two results. First, a new fine structure is observed in the ESRspectrum arising from state mixing by the hyperfine coupling to the 31P nuclei,which is enhanced when the exchange energy is comparable to the Zeeman energy.This fine structure enables us to spectroscopically address two separate dimersub-ensembles, the first with exchange (J) coupling ranging from 2 to 7 GHz andthe second with J ranging from 6 to 60 GHz. Next, the average spin relaxationtimes, T1 and T2 of both dimer sub-ensembles were measured using pulsed ESR at0.35 T. Both T1 and T2 for transitions between triplet states of the dimerswere found to be identical to the relaxation times of isolated phosphorusdonors in 28Si, with T2 = 4 ms at 1.7 K limited by spectral diffusion due todipolar interactions with neighboring donor electron spins. This result,consistent with theoretical predictions, implies that an exchange coupling of 2- 60 GHz does not limit the dimer T1 and T2 in bulk Si at the 10 ms timescale.

ESR measurements of phosphorus dimers in isotopically enriched 28Si silicon