II3 V2 semiconductors have become increasingly popular for a variety of applications including solar light harvesting, near-IR imaging, and low energy light detection. The bulk physical and electronic structure of these materials is highlighted, followed by an in-depth survey on progress in synthesizing these semiconductors as colloidal nanocrystals. Interestingly, no universal synthetic approach has yet been developed to access all compounds within this family. A discussion on how the complex crystal structure of these materials translates to small domain sizes will highlight current challenges in the characterization of II3 V2 nanocrystals. Finally, potential avenues for further research will be proposed as a way to advance this field towards greater utilization in light harvesting applications.
The synthesis and characterization of crystalline colloidal zinc phosphide quantum dots with observable excitonic transitions ranging between 424-535 nm (2.3-2.9 eV) are reported. A ternary combination of ZnEt2, Zn(O2CR)2, and P(SiMe3)3, forms a pentanuclear zinc cluster on mixing followed by conversion to (Et2Zn)P(ZnO2CR)2(SiMe3) in a rate-determining step prior to quantum dot formation.
Divalent nickel (Ni(2+)), Cu(II)EDTA, methyl orange, and dichromate were used to investigate diffusion from hydrated silica sol-gel monoliths. The objective was to examine diffusion of compounds on a size regime relevant to supporting biological components encapsulated within silica gel prepared in a biologically compatible process space with no post-gelation treatments. With an initial sample set, gels prepared from tetraethoxysilane were explored in a factorial design with Ni(2+) as the tracer, varying water content during hydrolysis, acid catalyst present during hydrolysis, and the final concentration of silica. A second sample set explored diffusion of all four tracers in gels prepared with aqueous silica precursors and a variety of organically modified siloxanes. Excluding six outliers which displayed significant syneresis, the mean diffusion constant (D(gel)) across the entire process space of sample set 1 was 2.42×10(-10) m(2) s(-1); approximately 24% of the diffusion coefficient of Ni(2+) in unconfined aqueous solution. In sample set 2, the tracer size and not gel hydrophobicity was the primary determinant of changes in diffusion rates. A strong linear inverse correlation was found between tracer size and the magnitude of D(gel). Based on correlation with the tracers used in this investigation, the characteristic 1-h diffusion distance for carbonate species relevant to supporting active phototrophic organisms was approximately 1.5mm. These results support the notion that silica sol-gel formulations may be optimized for a given biological entity of interest with manageable impact to the diffusion of small ions and molecules.
Gels/chemistry , Silicon Dioxide/chemistry , Diffusion , Silanes/chemistry , Siloxanes/chemistry
