Characterization of Band Gaps of Silicon Quantum Dots Synthesized by Etching Silicon Nanopowder with Aqueous Hydrofluoric Acid and Nitric Acid

Silicon quantum dots (Si QDs) were synthesized by etching silicon nanopowder with aqueous hydrofluoric acid (HF) and nitric acid ($HNO_3$). Then, the hydride-terminated Si QDs (H-Si QDs) were functionalized by 1- octadecene (ODE). By only controlling the etching time, the maximum luminescence peak of octadecylterminated Si QDs (ODE-Si QDs) was tuned from 404 nm to 507 nm. The average optical gap was increased from 2.60 eV (ODE-Si QDs-5 min) for 5 min of etching to 3.20 eV (ODE-Si QDs-15 min) for 15 min of etching, and to 3.40 eV (ODE-Si QDs-30 min) for 30 min of etching. The electron affinities (EA), ionization potentials (IP), and quasi-particle gap (${\varepsilon}^{qp}_{gap}$) of the Si QDs were determined by cyclic voltammetry (CV). The quasi-particle gaps obtained from the CV were in good agreement with the average optical gap values from UV-vis absorption. In the case of the ODE-Si QDs-30 min sample, the difference between the quasi-particle gap and the average optical gap gives the electron-hole Coulombic interaction energy. The additional electronic levels of the ODE-Si QDs-30 min and ODE-Si QDs-15 min samples determined by the CV results are interpreted to have originated from the Si=O bond terminating Si QD.