Driven by the emergence of colloidal semiconductor quantum dots (QDs) of tunable emission wavelengths, characteristic of exciton absorption peaks, outstanding photostability and solution processability in device fabrication have become a key tool in the development of nanomedicine and optoelectronics. Diamond cubic crystalline silicon (Si) QDs, with a diameter larger than 2 nm, terminated with hydrogen atoms are known to exhibit bulk-inherited spin and valley properties. Herein, we demonstrate a newly discovered size region of Si QDs, in which a fast radiative recombination on the order of hundreds of picoseconds is responsible for photoluminescence (PL). Despite retaining a crystallographic structure like the bulk, controlling their diameters in the 1.1-1.7 nm range realizes the strong PL with continuous spectral tunability in the 530-580 nm window, the narrow spectral line widths without emission tails, and the fast relaxation of photogenerated carriers. In contrast, QDs with diameters greater than 1.8 nm display the decay times on the microsecond order as well as the previous Si QDs. In addition to the five-orders-of-magnitude variation in the PL decay time, a systematic study on the temperature dependence of PL properties suggests that the energy structure of the smaller QDs does not retain an indirect band gap character. It is discussed that a 1.7 nm diameter is critical to undergo changes in energy structure from bulky to molecular configurations.
Keywords: Decay dynamics; Photoluminescence; Quantum dot; Silicon; Size matters.