Reaction chemistry and ligand exchange at cadmium selenide nanocrystal surfaces
Chemical modification of nanocrystal surfaces is fundamentally important to their assembly, their implementation in biology and medicine, and greatly impacts their electrical and optical properties. However, it remains a major challenge owing to a lack of analytical tools to directly determine nanoparticle surface structure. Early nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) studies of CdSe nanocrystals prepared in tri-n-octylphosphine oxide (1) and tri-n-octylphosphine (2), suggested these coordinating solvents are datively bound to the particle surface. However, assigning the broad NMR resonances of surface-bound ligands is complicated by significant concentrations of phosphorus-containing impurities in commercial sources of 1, and XPS provides only limited information about the nature of the phosphorus containing molecules in the sample. More recent reports have shown the surface ligands of CdSe nanocrystals prepared in technical grade 1, and in the presence of alkylphosphonic acids, include phosphonic and phosphinic acids. These studies do not, however, distinguish whether these ligands are bound datively, as neutral, L-type ligands, or by X-type interaction of an anionic phosphonate/phosphinate moiety with a surface Cd{sup 2+} ion. Answering this question would help clarify why ligand exchange with such particles does not proceed generally as expected based on a L-type ligand model. By using reagents with reactive silicon-chalcogen and silicon-chlorine bonds to cleave the ligands from the nanocrystal surface, we show that our CdSe and CdSe/ZnS core-shell nanocrystal surfaces are likely terminated by X-type binding of alkylphosphonate ligands to a layer of Cd{sup 2+}/Zn{sup 2+} ions, rather than by dative interactions. Further, we provide spectroscopic evidence that 1 and 2 are not coordinated to our purified nanocrystals.
- Research Organization:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Organization:
- Materials Sciences Division
- DOE Contract Number:
- DE-AC02-05CH11231
- OSTI ID:
- 944434
- Report Number(s):
- LBNL-1259E; JACSAT; TRN: US200902%%754
- Journal Information:
- Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
36 MATERIALS SCIENCE
77 NANOSCIENCE AND NANOTECHNOLOGY
BIOLOGY
CADMIUM SELENIDES
CHEMISTRY
IMPLEMENTATION
IMPURITIES
ION EXCHANGE
LIGANDS
MEDICINE
MODIFICATIONS
NUCLEAR MAGNETIC RESONANCE
OPTICAL PROPERTIES
OXIDES
PHOSPHINIC ACIDS
PHOSPHORUS
SOLVENTS
X-RAY PHOTOELECTRON SPECTROSCOPY
surface chemistry
nanocrystal
ligand exchange