Analysis of temporal evolution of quantum dot surface chemistry by surface-enhanced Raman scattering.

Temporal evolution of surface chemistry during oxidation of silicon quantum dot (Si-QD) surfaces were probed using surface-enhanced Raman scattering (SERS). A monolayer of hydrogen and chlorine terminated plasma-synthesized Si-QDs were spin-coated on silver oxide thin films. A clearly enhanced signal of surface modes, including Si-Clx and Si-Hx modes were observed from as-synthesized Si-QDs as a result of the plasmonic enhancement of the Raman signal at Si-QD/silver oxide interface. Upon oxidation, a gradual decrease of Si-Clx and Si-Hx modes, and an emergence of Si-Ox and Si-O-Hx modes have been observed. In addition, first, second and third transverse optical modes of Si-QDs were also observed in the SERS spectra, revealing information on the crystalline morphology of Si-QDs. An absence of any of the abovementioned spectral features, but only the first transverse optical mode of Si-QDs from thick Si-QD films validated that the spectral features observed from Si-QDs on silver oxide thin films are originated from the SERS effect. These results indicate that real-time SERS is a powerful diagnostic tool and a novel approach to probe the dynamic surface/interface chemistry of quantum dots, especially when they involve in oxidative, catalytic, and electrochemical surface/interface reactions.

Controlled doping of silicon nanocrystals investigated by solution-processed field effect transistors.

The doping of semiconductor nanocrystals (NCs), which is vital for the optimization of NC-based devices, remains a significant challenge. While gas-phase plasma approaches have been successful in incorporating dopant atoms into NCs, little is known about their electronic activation. Here, we investigate the electronic properties of doped silicon NC thin films cast from solution by field effect transistor analysis. We find that, analogous to bulk silicon, boron and phosphorus electronically dope Si NC thin films; however, the dopant activation efficiency is only ∼10(-2)-10(-4). We also show that surface doping of Si NCs is an effective way to alter the carrier concentrations in Si NC films.

Optical extinction spectra of silicon nanocrystals: size dependence upon the lowest direct transition.

We investigate the size-dependent optical extinction properties of colloidal silicon nanocrystals (Si NCs) from the near infrared (NIR) to the ultraviolet (UV). Experimental results are compared to the Mie solution to Maxwell's equations using the same refractive index as bulk Si to evaluate the deviation from bulk properties. We find that the energy for the lowest direct transition (E(1)) continuously blueshifts from near bulk-like at ~3.4 eV in large NCs (16 nm) to ~3.6 eV for small NCs (3.9 nm), contrary to the Mie solution. The extinction cross-section of NCs on a per atom basis was found to be independent of the NC size, within our experimental resolution. The results suggest that quantum confinement effects strongly influence excitons associated with the E(1) transition.

Synthesis and oxidation of luminescent silicon nanocrystals from silicon tetrachloride by very high frequency nonthermal plasma.

Silicon nanocrystals have recently attracted significant attention for applications in electronics, optoelectronics, and biological imaging due to their size-dependent optical and electronic properties. Here a method for synthesizing luminescent silicon nanocrystals from silicon tetrachloride with a nonthermal plasma is described. Silicon nanocrystals with mean diameters of 3-15 nm are synthesized and have a narrow size distribution with the standard deviation being less than 20% of the mean size. Control over crystallinity is achieved for plasma pressures of 1-12 Torr and hydrogen gas concentrations of 5-70% through adjustment of the plasma power. The size of nanocrystals, and resulting optical properties, is mainly dependent on the gas residence time in the plasma region. Additionally the surface of the nanocrystals is covered by both hydrogen and chlorine. Oxidation of the nanocrystals, which is found to follow the Cabrera-Mott mechanism under ambient conditions, is significantly faster than hydrogen terminated silicon due to partial termination of the nanocrystal surface by chlorine.

Combined plasma gas-phase synthesis and colloidal processing of InP/ZnS core/shell nanocrystals.

Indium phosphide nanocrystals (InP NCs) with diameters ranging from 2 to 5 nm were synthesized with a scalable, flow-through, nonthermal plasma process at a rate ranging from 10 to 40 mg/h. The NC size is controlled through the plasma operating parameters, with the residence time of the gas in the plasma region strongly influencing the NC size. The NC size distribution is narrow with the standard deviation being less than 20% of the mean NC size. Zinc sulfide (ZnS) shells were grown around the plasma-synthesized InP NCs in a liquid phase reaction. Photoluminescence with quantum yields as high as 15% were observed for the InP/ZnS core-shell NCs.

Universal size-dependent trend in auger recombination in direct-gap and indirect-gap semiconductor nanocrystals.

We report the first experimental observation of a striking convergence of Auger recombination rates in nanocrystals of both direct- (InAs, PbSe, CdSe) and indirect-gap (Ge) semiconductors, which is in contrast to a dramatic difference (by up to 4-5 orders of magnitude) in the Auger decay rates in respective bulk solids. To rationalize this finding, we invoke the effect of confinement-induced mixing between states with different translational momenta, which diminishes the impact of the bulk-semiconductor band structure on multiexciton interactions in nanocrystalline materials.