Parabolic Potential Surfaces Localize Charge Carriers in Nonblinking Long-Lifetime "Giant" Colloidal Quantum Dots.

Materials for studying biological interactions and for alternative energy applications are continuously under development. Semiconductor quantum dots are a major part of this landscape due to their tunable optoelectronic properties. Size-dependent quantum confinement effects have been utilized to create materials with tunable bandgaps and Auger recombination rates. Other mechanisms of electronic structural control are under investigation as not all of a material's characteristics are affected by quantum confinement. Demonstrated here is a new structure-property concept that imparts the ability to spatially localize electrons or holes within a core/shell heterostructure by tuning the charge carrier's kinetic energy on a parabolic potential energy surface. This charge carrier separation results in extended radiative lifetimes and in continuous emission at the single-nanoparticle level. These properties enable new applications for optics, facilitate novel approaches such as time-gated single-particle imaging, and create inroads for the development of other new advanced materials.

Charge carrier pairing can impart efficient reduction efficiency to core/shell quantum dots: applications for chemical sensing.

Semiconductor quantum dots (QDs) are bright fluorophores that have significant utility for imaging and sensing applications. Core QDs are often employed in chemosensing via redox processes that modulates their fluorescence in the presence of an analyte. However, such particles lack robust surface passivation and generally contain a sizable portion of nonfluorescent QDs, which is detrimental to the detection limit. We investigated an approach to "turn on" non-fluorescent core QDs by lightly overcoating them with a thin shell of a higher bandgap semiconductor. The shell augments the population of sensing chromophores and increases the emission lifetime; however, it simultaneously mollifies redox processes that are responsible for analyte sensitivity to begin with. This balancing act was successfully applied to enhance the sensitivity of CdZnS/ZnS QDs towards 2,4,6-trinitrotoluene (TNT). Unexpectedly, it was found that CdZnS/ZnS QDs with very thick shells retained substantial sensitivity to TNT. This observation may be due to close coupling of the reduced substrate with the QD hole that is enabled by the near-degeneracy of holes in the core CdZnS and ZnS shell. The ability of core/shell QDs to retain substantial reducing power may have implications for other applications that can benefit from the enhanced stability of robust core/shell nanomaterials.

Sterically Encumbered Tris(trialkylsilyl) Phosphine Precursors for Quantum Dot Synthesis.

The synthesis of nanomaterials with a narrow size distribution is challenging, especially for III-V semiconductor nanoparticles (also known as quantum dots). Concerning phosphides, this issue has been largely attributed the use of overly reactive precursors. The problem is exacerbated due to the narrow range of competent reagents for III-V semiconductor syntheses. We report the use of sterically encumbered tris(triethylsilyl) phosphine and tris(tributylsilyl) phosphine for InP quantum dot (QD) synthesis among others. The hypothesis was that these reagents are less reactive than the near-ubiquitous precursor tris(trimethylsilyl) phosphine and can be used to create more homogeneous materials. It was found that the InP products' quantum yields and emission color saturation (fwhm) were improved, but not to the levels realized in CdSe QDs. Regardless, these reagents have other positive attributes; they are less pyrophoric and can be applied toward the synthesis of II-V semiconductors and organophosphorus compounds. Concerning safe practices, we demonstrate that ammonium bifluoride is an effective replacement for highly toxic HF for the post-treatment of III-V semiconductor quantum dots.