Publication date: 15th May 2025
This work describes our recent efforts to unravel the ligand exchange dynamics of phosphonic and phosphinic acid ligands on the surfaces of atomically precise “magic-sized” semiconducting nanocrystals (MSNCs) via isothermal titration calorimetry (ITC) and nuclear magnetic resonance (NMR) spectroscopy. Being highly precise in their structure, MSNC-based semiconducting compounds are increasingly sought as nucleating scaffolds and single source precursors for synthesizing highly uniform nanocrystals (NCs). Their extreme surface-area-to-volume ratio makes understanding and characterizing their surface chemistry crucial for engineering them for specific uses, while also allowing for predictive modeling of the behavior of larger or less precisely-controlled NCs. Historically, strongly coordinating phosphorus-based acids are very crucial in making anisotropic NCs. Hence, understanding the binding thermodynamics of phosphorus-based ligands to the NC surface plays a vital role in advancing control of the resulting NC shape as well as their photophysical properties. In this study, the surface chemistry of a series of non-stoichiometric zinc blende CdSe MSNCs are investigated by measuring the displacement of native oleate ligands with more strongly binding alkyl phosphonic acids and phosphinic acids. A combination of 1H NMR and ITC elucidates the exchange reaction mechanisms, while also highlighting insights from the systematic structural variation of the phosphonic and phosphinic acid ligands. The findings from this fundamental study advance the understanding of CdSe MSNC surface chemistry and provide strategies for studying site-specific interactions on nanocrystals.
This work is supported by the US National Science Foundation under grant CHE-MSN, 1613388, 2109064, 2404405. M.M.I. was additionally supported by DURIG Travel Award offered by College of Arts and Science of the University of South Carolina. We are especially grateful for assistance from Dr. Perry Pellechia.
nanoGe is a prestigious brand of successful science conferences that are developed along the year in different areas of the world since 2009. Our worldwide conferences cover cutting-edge materials topics like perovskite solar cells, photovoltaics, optoelectronics, solar fuel conversion, surface science, catalysis and two-dimensional materials, among many others.
Previously nanoGe Spring Meeting (NSM) and nanoGe Fall Meeting (NFM), MATSUS is a multiple symposia conference focused on a broad set of topics of advanced materials preparation, their fundamental properties, and their applications, in fields such as renewable energy, photovoltaics, lighting, semiconductor quantum dots, 2-D materials synthesis, charge carriers dynamics, microscopy and spectroscopy semiconductors fundamentals, etc.
International Conference on Hybrid and Organic Photovoltaics
International Conference on Hybrid and Organic Photovoltaics (HOPV) is celebrated yearly in May. The main topics are the development, function and modeling of materials and devices for hybrid and organic solar cells. The field is now dominated by perovskite solar cells but also other hybrid technologies, as organic solar cells, quantum dot solar cells, and dye-sensitized solar cells and their integration into devices for photoelectrochemical solar fuel production.
Asia-Pacific International Conference on Perovskite, Organic Photovoltaics and Optoelectronics
The main topics of the Asia-Pacific International Conference on Perovskite, Organic Photovoltaics and Optoelectronics (IPEROP) are discussed every year in Asia-Pacific for gathering the recent advances in the fields of material preparation, modeling and fabrication of perovskite and hybrid and organic materials. Photovoltaic devices are analyzed from fundamental physics and materials properties to a broad set of applications. The conference also covers the developments of perovskite optoelectronics, including light-emitting diodes, lasers, optical devices, nanophotonics, nonlinear optical properties, colloidal nanostructures, photophysics and light-matter coupling.
The International Conference on Perovskite Thin Film Photovoltaics Perovskite Photonics and Optoelectronics (NIPHO) is the best place to hear the latest developments in perovskite solar cells as well as on recent advances in the fields of perovskite light-emitting diodes, lasers, optical devices, nanophotonics, nonlinear optical properties, colloidal nanostructures, photophysics and light-matter coupling.