Enhanced semiconductor nanocrystal conductance via solution grown contacts.

We report a 100000-fold increase in the conductance of individual CdSe nanorods when they are electrically contacted via direct solution phase growth of Au tips on the nanorod ends. Ensemble UV-vis and X-ray photoelectron spectroscopies indicate this enhancement does not result from alloying of the nanorod. Rather, low temperature tunneling and high temperature (250-400 K) thermionic emission across the junction at the Au contact reveal a 75% lower interface barrier to conduction compared to a control sample. We correlate this barrier lowering with the electronic structure at the Au-CdSe interface. Our results emphasize the importance of a nanocrystal surface structure for robust device performance and the advantage of this contact method.

Reaction chemistry and ligand exchange at cadmium-selenide nanocrystal surfaces.

The surface chemistry of cadmium selenide nanocrystals, prepared from tri-n-octylphosphine selenide and cadmium octadecylphosphonate in tri-n-octylphosphine oxide, was studied with 1H and {1H}31P NMR spectroscopy as well as ESI-MS and XPS. The identity of the surface ligands was inferred from reaction of nanocrystals with Me3Si-X (X = -S-SiMe3, -Se-SiMe3, -Cl and -S-(CH2CH2O)4OCH3)) and unambiguous assignment of the organic byproducts, O,O'-bis(trimethylsilyl)octadecylphosphonic acid ester and O,O'-bis(trimethylsilyl)ocatdecylphosphonic acid anhydride ester. Nanocrystals isolated from these reactions have undergone exchange of the octadecylphosphonate ligands for -X as was shown by 1H NMR (X = -S-(CH2CH2O)4OCH3) and XPS (X = -Cl). Addition of free thiols to as prepared nanocrystals results in binding of the thiol to the particle surface and quenching of the nanocrystal fluorescence. Isolation of the thiol-ligated nanocrystals shows this chemisorption proceeds without displacement of the octadecylphosphonate ligands, suggesting the presence of unoccupied Lewis-acidic sites on the particle surface. In the presence of added triethylamine, however, the octadecylphosphonate ligands are readily displaced from the particle surface as was shown with 1H and {1H}31P NMR. These results, in conjunction with previous literature reports, indicate that as-prepared nanocrystal surfaces are terminated by X-type binding of octadecylphosphonate moieties to a layer of excess cadmium ions.

Electrical contacts to individual colloidal semiconductor nanorods.

We report the results of charge transport studies on single CdTe nanocrystals contacted via evaporated Pd electrodes. Device charging energy, E c, monitored as a function of electrode separation drops suddenly at separations below approximately 55 nm. This drop can be explained by chemical changes induced by the metal electrodes. This explanation is corroborated by ensemble X-ray photoelectron spectroscopy studies of CdTe films as well as single particle measurements by transmission electron microscopy and energy dispersive X-rays. Similar to robust optical behavior obtained when nanocrystals are coated with a protective shell, we find that a protective SiO 2 layer deposited between the nanocrystal and the electrode prevents interface reactions and an associated drop in E c,max. This observation of interface reactivity and its effect on electrical properties has important implications for the integration of nanocrystals into conventional fabrication techniques and may enable novel nanomaterials.

Metal to insulator transition in films of molecularly linked gold nanoparticles.

We report a metal to insulator transition (MIT) in disordered films of molecularly linked gold nanoparticles (NPs). As the number of carbons (n) of alkanedithiol linker molecules (C(n)S2) is varied, resistance (R) at low temperature (T = 2 K) and at 200 K, as well as trends in R vs T data at intermediate temperatures, all point to an MIT occurring at n = 5. We describe these results in a context of a Mott-Hubbard MIT. We find that all insulating samples (n > or = 5) exhibit a universal scaling behavior R approximately exp[(T0/T)nu] with nu = 0.65, and all metallic samples (n < or = 5) exhibit weaker R-T dependencies than bulk gold. We discuss these observations in terms of competitive thermally activated processes and strong, T-independent elastic scattering, respectively.

Influence of linker molecules on charge transport through self-assembled single-nanoparticle devices.

We investigate electrical characteristics of single-electron electrode/nanoisland/electrode devices formed by alkanedithiol assisted self-assembly. Contrary to predictions of the orthodox model for double tunnel junction devices, we find a significant ( approximately fivefold) discrepancy in single-electron charging energies determined by Coulomb blockade (CB) voltage thresholds in current-voltage measurements versus those determined by an Arrhenius analysis of conductance in the CB region. The energies do, however, scale with particle sizes, consistent with single-electron charging phenomena. We propose that the discrepancy is caused by a multibarrier junction potential that leads to a voltage divider effect. Temperature and voltage dependent conductance measurements performed outside the blockade region are consistent with this picture. We simulated our data using a suitably modified orthodox model.