Solution-state NMR studies of the surface structure and dynamics of semiconductor nanocrystals

H-1 and C-13 nuclear magnetic resonance (NMR) relaxation studies of thiophenol-capped CdS nanocrystals are presented. The transverse and longitudinal relaxation times were investigated as a function of nanocrystal radius, and the transverse relaxation time was also studied as a function of temperature. Both proton and carbon T-2 values were found to increase with nanocrystal radius, contrary to initial expectations. This effect is explained in terms of motion of the thiophenol with respect to the nanocrystalline surface. Theoretical expressions for relaxation due to anisotropic motion are developed based on both bridging and terminal bonding configurations of the thiophenol ligands, and the data are fit to these models. The data are found to be consistent with thiophenol ligands bound in a terminal fashion to a single Cd atom. The temperature dependence of the proton T-2 value is also suprising. T-2 is found to decrease with increasing temperature, and the size of this change scales with the nanocrystal radius. This is explained in terms of an extra component of relaxation due to thermally excited electrons.


Published in:
JOURNAL OF PHYSICAL CHEMISTRY B, 102, 50, 10117-10128
Year:
1998
Publisher:
AMER CHEMICAL SOC
ISSN:
1089-5647
Laboratories:




 Record created 2015-01-08, last modified 2018-03-17


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