Due to its abundance, silicon is the preferred solar-cell material despite the fact that current silicon materials have indirect band gaps. Although the band gap properties of silicon have been studied intensively, until now, no direct band gap silicon-based material has been found or suggested. We report here the discovery of direct band gap silicon crystals. By using conformational space annealing, we optimize various crystal structures containing multiple (10 to 20) silicon atoms per unit cell so that their electronic structures become direct band gap. Through first-principles calculations, we identify many direct and quasidirect band gap crystal structures, which exhibit excellent photovoltaic efficiency.

Diamond Si is a semiconductor with an indirect band gap that is the basis of modern semiconductor technology. Although many metastable forms of Si were observed using diamond anvil cells for compression and chemical precursors for synthesis, no metallic phase at ambient conditions has been reported thus far. Here we report the prediction of pure metallic Si allotropes with open channels at ambient pressure, unlike a cubic diamond structure in covalent bonding networks. The metallic phase termed $P6/m\text{−}{\mathrm{Si}}_6$ can be obtained by removing Na after pressure release from a novel Na-Si clathrate called $P6/m\text{−}{\mathrm{NaSi}}_6$, which is predicted through first-principles study at high pressure. We identify that both $P6/m\text{−}{\mathrm{NaSi}}_6$ and $P6/m\text{−}{\mathrm{Si}}_6$ are stable and superconducting with the critical temperatures of about 13 and 12 K at ambient pressure, respectively. The prediction of new Na-Si and Si clathrate structures presents the possibility of exploring new exotic allotropes useful for Si-based devices.

Silicon is the most popular material used in electronic devices. However, its poor optical properties owing to its indirect band gap nature limit its usage in optoelectronic devices. Here we present the discovery of super-stable pure-silicon superlattice structures that can serve as promising materials for solar cell applications and can lead to the realization of pure Si-based optoelectronic devices. The structures are almost identical to that of bulk Si except that defective layers are intercalated in the diamond lattice. The superlattices exhibit dipole-allowed direct band gaps as well as indirect band gaps, providing ideal conditions for the investigation of a direct-to-indirect band gap transition. The fact that almost all structural portions of the superlattices originate from bulk Si warrants their stability and good lattice matching with bulk Si. Through first-principles molecular dynamics simulations, we confirmed their thermal stability and propose a possible method to synthesize the defective layer through wafer bonding.

Global searching for reaction pathways is a long-standing challenge in computational chemistry and biology. Most existing approaches perform only local searches due to computational complexity. Here we present a computational approach, Action-CSA, to find multiple diverse reaction pathways connecting fixed initial and final states through global optimization of the Onsager–Machlup action using the conformational space annealing (CSA) method. Action-CSA successfully overcomes large energy barriers via crossovers and mutations of pathways and finds all possible pathways of small systems without initial guesses on pathways. The rank order and the transition time distribution of multiple pathways are in good agreement with those of long Langevin dynamics simulations. The lowest action folding pathway of FSD-1 is consistent with recent experiments. The results show that Action-CSA is an efficient and robust computational approach to study the multiple pathways of complex reactions and large-scale conformational changes.