Understanding of sub-band gap absorption of femtosecond-laser sulfur hyperdoped siliconusing synchrotron-based techniques

摘要

The correlation between sub-band gap absorption and the chemical states and electronic and atomic structures of S-hyperdoped Si have been extensively studied, using synchrotron-based x-ray photoelectron spectroscopy (XPS), x-ray absorption near-edge spectroscopy (XANES), extended x-ray absorption fine structure (EXAFS), valence-band photoemission spectroscopy (VB-PES) and first-principles calculation. S 2p XPS spectra reveal that the S-hyperdoped Si with the greatest (~87%) sub-band gap absorption contains the highest concentration of S²⁻ (monosulfide) species. Annealing S-hyperdoped Si reduces the sub-band gap absorptance and the concentration of S²⁻ species, but significantly increases the concentration of larger S clusters [polysulfides (Sn²⁻, n > 2)]. The Si K-edge XANES spectra show that S hyperdoping in Si increases (decreased) the occupied (unoccupied) electronic density of states at/above the conduction-band-minimum. VB-PES spectra evidently reveal that the S-dopants not only form an impurity band deep within the band gap, giving rise to the sub-band gap absorption, but also cause the insulator-to-metaltransition in S-hyperdoped Si samples. Based on the experimental results and thecalculations by density functional theory, the chemical state of the S species andthe formation of the S-dopant states in the band gap of Si are critical indetermining the sub-band gap absorptance of hyperdoped Si samples.