Although gold is the subject of one of the most ancient themes of investigation in science, its renaissance now leads to an exponentially increasing number of publications, especially in the context of emerging nanoscience and nanotechnology with nanoparticles and self-assembled monolayers (SAMs). We will limit the present review to gold nanoparticles (AuNPs), also called gold colloids. AuNPs are the most stable metal nanoparticles, and they present fascinating aspects such as their assembly of multiple types involving materials science, the behavior of the individual particles, size-related electronic, magnetic and optical properties (quantum size effect), and their applications to catalysis and biology. Their promises are in these fields as well as in the bottom-up approach of nanotechnology, and they will be key materials and building block in the 21st century. Whereas the extraction of gold started in the 5th millennium B.C. near Varna (Bulgaria) and reached 10 tons per year in Egypt around 1200-1300 B.C. when the marvelous statue of Touthankamon was constructed, it is probable that “soluble” gold appeared around the 5th or 4th century B.C. in Egypt and China. In antiquity, materials were used in an ecological sense for both aesthetic and curative purposes. Colloidal gold was used to make ruby glass 293 Chem. Rev. 2004, 104, 293−346

Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology.

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Self-assembled monolayers of thiolates on metals as a form of nanotechnology.

The interest in nanoscale materials stems from the fact that new properties are acquired at this length scale and, equally important, that these properties * To whom correspondence should be addressed. Phone, 404-8940292; fax, 404-894-0294; e-mail, mostafa.el-sayed@ chemistry.gatech.edu. † Case Western Reserve UniversitysMillis 2258. ‡ Phone, 216-368-5918; fax, 216-368-3006; e-mail, burda@case.edu. § Georgia Institute of Technology. 1025 Chem. Rev. 2005, 105, 1025−1102

Chemistry and properties of nanocrystals of different shapes.

Synthesis of monodisperse iron-platinum (FePt) nanoparticles by reduction of platinum acetylacetonate and decomposition of iron pentacarbonyl in the presence of oleic acid and oleyl amine stabilizers is reported. The FePt particle composition is readily controlled, and the size is tunable from 3- to 10-nanometer diameter with a standard deviation of less than 5%. These nanoparticles self-assemble into three-dimensional superlattices. Thermal annealing converts the internal particle structure from a chemically disordered face-centered cubic phase to the chemically ordered face-centered tetragonal phase and transforms the nanoparticle superlattices into ferromagnetic nanocrystal assemblies. These assemblies are chemically and mechanically robust and can support high-density magnetization reversal transitions.

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Monodisperse FePt Nanoparticles and Ferromagnetic FePt Nanocrystal Superlattices

▪ Abstract Solution phase syntheses and size-selective separation methods to prepare semiconductor and metal nanocrystals, tunable in size from ∼1 to 20 nm and monodisperse to ≤5%, are presented. Preparation of monodisperse samples enables systematic characterization of the structural, electronic, and optical properties of materials as they evolve from molecular to bulk in the nanometer size range. Sample uniformity makes it possible to manipulate nanocrystals into close-packed, glassy, and ordered nanocrystal assemblies (superlattices, colloidal crystals, supercrystals). Rigorous structural characterization is critical to understanding the electronic and optical properties of both nanocrystals and their assemblies. At inter-particle separations 5–100 A, dipole-dipole interactions lead to energy transfer between neighboring nanocrystals, and electronic tunneling between proximal nanocrystals gives rise to dark and photoconductivity. At separations <5 A, exchange interactions cause otherwise insulating ass...

Synthesis and Characterization of Monodisperse Nanocrystals and Close-Packed Nanocrystal Assemblies

Close-packed planar arrays of nanometer-diameter metal clusters that are covalently linked to each other by rigid, double-ended organic molecules have been self-assembled. Gold nanocrystals, each encapsulated by a monolayer of alkyl thiol molecules, were cast froma colloidal solution onto a flat substrate to form a close-packed cluster monolayer. Organic interconnects (aryl dithiols or aryl di-isonitriles) displaced the alkyl thiol molecules and covalently linked adjacent clusters in the monolayer to form a two-dimensional superlattice of metal quantum dots coupled by uniform tunnel junctions. Electrical conductance through such a superlattice of 3.7-nanometer-diameter gold clusters, deposited on a SiO2 substrate in the gap between two gold contacts and linked by an aryl di-isonitrile [1,4-di(4-isocyanophenylethynyl)-2-ethylbenzene], exhibited nonlinear Coulomb charging behavior.

https://science.sciencemag.org/content/sci/273/5282/1690.full.pdf

Self-Assembly of a Two-Dimensional Superlattice of Molecularly Linked Metal Clusters

Double-ended aryl dithiols [α,α′-xylyldithiol (XYL) and 4,4′-biphenyldithiol] formed self-assembled monolayers (SAMs) on gold(111) substrates and were used to tether nanometer-sized gold clusters deposited from a cluster beam. An ultrahigh-vacuum scanning tunneling microscope was used to image these nanostructures and to measure their current-voltage characteristics as a function of the separation between the probe tip and the metal cluster. At room temperature, when the tip was positioned over a cluster bonded to the XYL SAM, the current-voltage data showed “Coulomb staircase” behavior. These data are in good agreement with semiclassical predictions for correlated single-electron tunneling and permit estimation of the electrical resistance of a single XYL molecule (∼18 ± 12 megohms).

https://science.sciencemag.org/content/sci/272/5266/1323.full.pdf

"Coulomb Staircase" at Room Temperature in a Self-Assembled Molecular Nanostructure

This paper presents a comparison of the theoretical and experimental current-voltage (I-V) characteristics of a self-assembled monolayer of $\ensuremath{\alpha},{\ensuremath{\alpha}}^{\ensuremath{'}}\ensuremath{-}\mathrm{x}\mathrm{y}\mathrm{l}\mathrm{y}\mathrm{l}$ dithiol molecules on a gold substrate measured with a scanning tunneling microscope probe. Good quantitative agreement is obtained with the tip-molecule distance as the only ``fitting parameter.'' Several other thiol-coupled molecules that we have studied also show similar agreement. The conceptual picture presented in this paper could be useful for the interpretation of I-V measurements on molecular monolayers in general.

Current-Voltage Characteristics of Self-Assembled Monolayers by Scanning Tunneling Microscopy

A relatively simple and straightforward procedure for characterizing molecular wires is to measure the conductance spectrum by forming a self-assembled ordered monolayer (SAM) on a metallic surface and using a high scanning-tunneling microscope resolution (STM) tip as the other contact. We find that the conductance spectrum (dI/dV vs. V) can be understood fairly well in terms of a relatively simple model, provided the spatial profile of the electrostatic potential under bias is properly accounted for. The effect of the potential profile is particularly striking and can convert a symmetric conductor into a rectifier and vice versa. The purpose of this paper is to (1) describe the theoretical model in detail, (2) identify the important parameters that influence the spectra and show how these parameters can be deduced directly from the conductance spectrum, and (3) compare the theoretical prediction with experimentally measured conductance spectra for xylyl dithiol and phenyl dithiol.

Conductance spectra of molecular wires

In this paper, we present a method for computing the resistance of molecular wires and illustrate it with a systematic theoretical study of a particular class of organic molecules. These molecules consist of one or more benzene rings with a thiol(-SH) group at the ends. This end group can attach readily to metallic surfaces, thus allowing the molecule to function as a nanoelectronic interconnect. The conduction through these molecules at low bias occurs by tunneling, leading to resistances that are typically several tens of megaohms. The resistance goes up exponentially with the number of rings and is sensitive to the relative orientation of the rings and the bonding between them. The Green-function-based method presented here provides a powerful tool for accurate modeling of the semi-infinite contacts that are used to measure molecular resistance.

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Jason I. Henderson

Papers

Self-Assembly of a Two-Dimensional Superlattice of Molecularly Linked Metal Clusters

"Coulomb Staircase" at Room Temperature in a Self-Assembled Molecular Nanostructure

Current-Voltage Characteristics of Self-Assembled Monolayers by Scanning Tunneling Microscopy

Conductance spectra of molecular wires

Electronic conduction through organic molecules