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.
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.
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...
The use of microfluidics in chemical synthesis is topical due to the potential to improve reproducibility and the ability promptly interrogate a wide range of reaction parameters, the latter of which is necessary for the training of artificial intelligence (AI) algorithms. Applying microfluidic techniques to semiconductor nanocrystals, or quantum dots (QDs), is challenging due to the need for a high-temperature nucleation event followed by particle growth at lower temperatures. Such a high-temperature gradient can be realized using complex, segmented microfluidic reactor designs, which represents an engineering approach. Here, an alternative chemical approach is demonstrated using the cluster seed method of nanoparticle synthesis in a simple microfluidic reactor system. This enables quantum dot nucleation at lower temperatures due to the presence of molecular organometallic compounds (NMe4)4[Cd10Se4(SPh)16] and (NMe4)4[Zn10Se4(SPh)16]. This integration of cluster seeding with microfluidics affords a new mechanism to tailor the reaction conditions for optimizing yields and tuning product properties.
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