Fundamental Limit of the Emission Linewidths of Quantum Dots: An Ab Initio Study of CdSe Nanocrystals

摘要： The emission linewidth of a semiconducting nanocrystal (NC) significantly affects the performance in light-emitting applications but its fundamental limit is still elusive. Herein we analyze exciton-phonon coupling (EPC) from Huang-Rhys (HR) factors using ab initio calculations, and compute emission line shapes of CdSe NCs. When surface traps are absent, acoustic modes are found to dominate EPC. The computed linewidths are mainly determined by the size of NCs, being largely insensitive to the shape and crystal structure. Linewidths obtained in this work are much smaller than most measurements on the homogeneous linewidth, but they are consistent with a CdSe/CdxZn1?xSe (core/shell) NC [Park et al. Nat. Mater. 2019, 18, 249-255]. Based on this comparison, it is concluded that the large linewidths in most experiments originated from internal fields by surface (or interface) traps or quasi-type Ⅱ band alignment that amplify EPC. Thus, the present results on NCs with ideal passivation provide the fundamental minimum of homogeneous linewidths, indicating that only the CdSe/CdxZn1?xSe NC has achieved this limit through well-controlled synthesis of the shell structure. To further verify the role of internal fields, we model NCs with charged surface defects. We find that the internal field significantly increases HR factors and linewidths, in reasonable agreements with experiments on single cores. By revealing the fundamental limit of emission linewidths of quantum dots, this work will pave the way to engineering quantum dots with ultrasharp spectrum.