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Unraveling the Mechanism Underlying Surface Ligand Passivation of Colloidal Semiconductor Nanocrystals: A Route for Preparing Advanced Hybrid Nanomaterials
journal contribution
posted on 2017-09-25, 00:00 authored by Meghan
B. Teunis, Thakshila Liyanage, Sukanta Dolai, Barry B. Muhoberac, Rajesh Sardar, Mangilal AgarwalOptically
bright colloidal semiconductor nanocrystals (CSNCs) are
important nanomaterials because of their potential applications such
as cellular imaging and solid-state lighting. The optoelectronic properties
of CSNCs are strongly controlled by the chemical nature of the surface
passivating ligands that are introduced during their synthesis. However,
the existing LaMer growth model does not provide a clear understanding
of the stage when ligands become attached onto the CSNC surface. Herein,
apart from the three stage formation mechanism of CSNCs (supersaturation,
nucleation, and growth), an entirely new stagesolely involving
surface ligand attachment onto fully grown CSNCsis now reported
that controls their photoluminescence properties. Furthermore, we
also demonstrate a fundamentally new surface modification approach
using partially passivated CSNCs to introduce a variety of functional
groups (azide, alkene, and siloxane), including photoisomerizable
molecular machines (e.g., azobenzene), without the use of “state-of-the
art” ligand exchange chemistry. Knowledge of the ligand adsorption
phenomena and resulting adsorption time dependence expands our fundamental
understanding of structure–property relationships while allowing
us to engineer novel hybrid functional nanomaterials with both previously
unknown optoelectronic properties and supermolecular assembly options
for various applications.
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LaMer growth modelCSNCColloidal Semiconductor Nanocrystalssurface passivating ligandsoptoelectronic propertiesligand adsorption phenomenasurface modification approachPreparing Advanced Hybrid Nanomaterials Opticallysupermolecular assembly optionssurface ligand attachmentstage formation mechanismadsorption time dependenceSurface Ligand Passivation
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