Nanocrystals (NCs) discussed in this Review are tiny crystals of metals, semiconductors, and magnetic material consisting of hundreds to a few thousand atoms each. Their size ranges from 2-3 to about 20 nm. What is special about this size regime that placed NCs among the hottest research topics of the last decades? The quantum mechanical coupling * To whom correspondence should be addressed. E-mail: dvtalapin@uchicago.edu. † The University of Chicago. ‡ Argonne National Lab. Chem. Rev. 2010, 110, 389–458 389

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Prospects of Colloidal Nanocrystals for Electronic and Optoelectronic Applications

Through the use of photoelectron spectroscopy in air (PESA), we investigate the size-dependent valence and conduction band-edge energies of CdSe, CdTe, PbS, and PbSe semiconductor quantum dots (QDs). The results are compared to those of previous studies, based on differing experimental methods, and to theoretical calculations based on k·p theory and state-of-the-art atomistic semiempirical pseudopotential modeling. To accurately map out the energy level landscapes of QDs as a function of size, the QDs must be passivated by comparable surface chemistries. This is highlighted by studying the effect of surface chemistry on the valence band-edge energy in an ensemble of 4.7 nm CdSe QDs. An energy level shift as large as 0.35 eV is observed for this system through modification of surface chemistry alone. This shift is significantly larger than the size-dependent valence band-edge shift that is observed when comparable surface chemistries are used.

Size-dependent valence and conduction band-edge energies of semiconductor nanocrystals.

A bottleneck limiting the widespread application of semiconductor nanocrystal solids is their poor conductivity. We report that the conductivity of thin films of n-type CdSe nanocrystals increases by many orders of magnitude as the occupation of the first two electronic shells, 1Se and 1Pe, increases, either by potassium or electrochemical doping. Around half-filling of the 1Se shell, a peak in the conductivity is observed, indicating shell-to-shell transport. Introducing conjugated ligands between nanocrystals increases the conductivities of these states to approximately 10(-2) siemens per centimeter.

https://science.sciencemag.org/content/sci/300/5623/1277.full.pdf

n-Type Conducting CdSe Nanocrystal Solids

Charge transport in nanoparticle assemblies.

The quintessence of the hot-injection method, a synthesis route for monodisperse, highly luminescent semiconductor nanocrystals, is reviewed. The separate stages of nucleation and growth of the nanocrystals are discussed in the framework of classical nucleation theory and an equilibrium model proposed by Debye. We also review the numerous adaptations of the original synthesis that currently provide colloidal nanocrystals with well-defined, size-dependent optical, electrical, and magnetic properties. The availability of these remarkable materials is one of the most promising developments in nanoscience and nanotechnology.

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Physicochemical evaluation of the hot-injection method, a synthesis route for monodisperse nanocrystals.

Transport properties of artificial solids composed of colloidal CdSe nanocrystals (NCs) are studied from 6 K to 250 K, before and after annealing. Annealing results in greatly enhanced dark and photocurrent in NC solids, while transmission electron microscopy (TEM) micrographs show that the inter-dot separation decreases. The increased current can be attributed to the enhancement of inter-dot tunneling caused by the decreased separation between NCs and by chemical changes in their organic cap. In addition, the absorption spectra of annealed solids are slightly red-shifted and broadened. These red-shifts may result from the change of the dielectric environment around the NCs. Our measurements also indicate that Coulomb interactions between charges on neighboring NCs play an important role in the tunneling current.

M. Vitasovic

Papers

Transport properties of annealed CdSe nanocrystal solids