Friday, July 28, 2006

Phys. Chem. Chem. Phys., 2006, 8, 3510 - 3519

Solid state NMR studies of photoluminescent cadmium chalcogenide nanoparticles

Christopher I. Ratcliffe, Kui Yu, John A. Ripmeester, Md. Badruz Zaman, Cristina Badarau and Shanti Singh

Solid state 113Cd, 77Se, 13C and 31P NMR have been used to study a number of Cd chalcogenide nanoparticles synthesized in tri-n-octyl-phosphine (TOP) with different compositions and architectures. The pure CdSe and CdTe nanoparticles show a dramatic, size-sensitive broadening of the 113Cd NMR line, which can be explained in terms of a chemical shift distribution arising from multiple Cd environments. From 13C NMR, it has been discovered that TOP, or its derivatives such as TOPO (trioctylphosphine oxide), is rapidly moving about the surface of the nanoparticles, indicating that it is relatively weakly bound as compared to other materials used as surface ligands, such as hexadecylamine. 31P NMR of the nanoparticles shows at least five species arising from coordination of the ligands to different surface sites. 113Cd NMR of CdSeTe alloy and layered nanoparticles has provided crucial information which, in conjunction with results from other techniques (especially optical characterization), has made it possible to develop a detailed picture of the composition and structure of these materials: (i) a true CdSeTe homogeneous alloy nanoparticle, (ii) a nanoparticle segregated into an alloy core region rich in Te, with a CdSeTe (close to 1 : 1 Se : Te) alloy shell and (iii) a CdSe/CdTe/CdSe layered nanoparticle in which the CdTe layer contains a small amount of Se and which forms a Quantum Dot Quantum Well (QDQW) system. The results demonstrate that solid state NMR is a vital tool in the arsenal of characterisation techniques available for nanomaterials.

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