Electronic and optical properties of 4H Si from first principles

Abstract: The cubic polytype of silicon (Si) is the most commercialized semiconductor material and finds applications in numerous electronic and optoelectronic devices such as solar cells. However, recent reports on the synthesis of the hexagonal 4H Si polytype have attracted the attention of the scientific community to understand its functional properties. Here we report the electronic, vibrational, and optical properties of the 4H Si polytype obtained with predictive first-principles calculations. We find that, compared to the cubic polytype, 4H Si shows a slightly narrower indirect gap by $\sim$ 0.05 eV. By calculating its direct and phonon-assisted optical spectra, we show that 4H Si exhibits a stronger absorption coefficient than cubic Si across the visible and IR spectral regions. We further evaluate the short-circuit current density of textured thin-films, and we demonstrate that 4H Si can achieve the same short-circuit current density for a five times thinner film compared to the cubic polytype. Our work demonstrates the advantages of 4H Si for thin-film silicon-based solar-cell applications.