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As surface ligands play a critical role in the colloidal stability and optoelectronic properties of semiconductor nanocrystals, we used solution NMR experiments to investigate the surface coordination chemistry of Ge nanocrystals synthesized by a microwave-assisted reduction of GeI 2 in oleylamine. The as-synthesized Ge nanocrystals are coordinated to a fraction of strongly bound oleylamide ligands (with covalent X-type Ge–NHR bonds) and a fraction of more weakly bound (or physisorbed) oleylamine, which readily exchanges with free oleylamine in solution. The fraction of strongly bound oleylamide ligands increases with increasing synthesis temperature, which also correlates with better colloidal stability. Thiol and carboxylic acid ligands bind to the Ge nanocrystal surface only upon heating, suggesting a high kinetic barrier to surface binding. These incoming ligands do not displace native oleylamide ligands but instead appear to coordinate to open surface sites, confirming that the as-prepared nanocrystals are not fully passivated. These findings will allow for a better understanding of the surface chemistry of main group nanocrystals and the conditions necessary for ligand exchange to ultimately maximize their functionality.
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Polysalt ligands achieve higher quantum yield and improved colloidal stability for CsPbBr 3 quantum dots
Colloidal lead halide perovskite quantum dots (PQDs) are relatively new semiconductor nanocrystals with great potential for use in optoelectronic applications. They also present a set of new scientifically challenging fundamental problems to investigate and understand. One of them is to address the rather poor colloidal and structural stability of these materials under solution phase processing and/or transfer between solvents. In this contribution, we detail the synthesis of a new family of multi-coordinating, bromide-based polysalt ligands and test their ability to stabilize CsPbBr 3 nanocrystals in polar solutions. The ligands present multiple salt groups involving quaternary cations, namely ammonium and imidazolium as anchors for coordination onto PQD surfaces, along with several alkyl chains with varying chain length to promote solubilization in various conditions. The ligands provide a few key benefits including the ability to repair damaged surface sites, allow rapid ligand exchange and phase transfer, and preserve the crystalline structure and morphology of the nanocrystals. The polysalt-coated PQDs exhibit near unity PLQY and significantly enhanced colloidal stability in ethanol and methanol.
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- PAR ID:
- 10327885
- Date Published:
- Journal Name:
- Nanoscale
- Volume:
- 13
- Issue:
- 39
- ISSN:
- 2040-3364
- Page Range / eLocation ID:
- 16705 to 16718
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d1nr04753a
