Ultrashallow thermal donor formation in silicon by annealing in ambient oxygen

Abstract

Czochralski-grown silicon wafers doped with phosphorus (∼1014 cm−3) have been annealed in nitrogen, wet nitrogen, oxygen, argon, and vacuum ambients at 470 °C for times up to 500 h. Sample characterization was made using predominantly electrical techniques such as admittance spectroscopy and thermally stimulated capacitance measurements but also secondary ion mass spectrometry (SIMS) and Fourier transform infrared spectroscopy were employed. In all samples, an increasing concentration of free carrier electrons is observed with increasing annealing time, reaching a maximum of ∼1016 cm−3 at 100 h. For durations in excess of 100 h gradual decrease of the free electron concentration takes place except for the samples treated in wet nitrogen and oxygen atmospheres, which display donors stable even after 200 h. These stable centers are found to have shallower donor level positions in the energy band gap (∼25 meV below the conduction band edge Ec) than those of the centers formed in vacuum, argon, and nitrogen atmospheres (∼35 meV below Ec). The latter centers are associated with the well-established shallow thermal donors (STDs) while the origin of the former ones, which are labeled ultrashallow thermal donors (USTDs) is less known. However, on the basis of a wealth of experimental results we show that the USTDs are most likely perturbated STDs modified through interaction with fast-in diffusing oxygen species, possibly oxygen dimers. Further, comparison between the electrical data and the SIMS measurements reveals unambiguously that neither the STD nor the USTD centers involve nitrogen, in contrast to recent suggestions in the literature.