Chemical & Engineering News: Science & Technology - A Periodic Table Of Nanopartic...

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Science & Technology

August 21, 2006

Volume 84, Number 34
pp. 45-46

A Periodic Table Of Nanoparticles

Like chemical elements, nanoparticles of distinct types combine in definite proportions
Ivan Amato

Rest assured, the periodic table of elements' claim on front-and-center wall space in thousands of classrooms and
laboratories around the world is safe. But some enthusiasts in the nanoscience arena liken the minuscule particles they are
making—and mixing and matching like atoms—to the elements of a new periodic table: a periodic table of nanoparticles.
Even if this nascent nanoparticle table contains only a smidgen of the explanatory and predictive power of the traditional
table of elements, it could prove to be invaluable.

INTERACTIVE PHOTO GALLERY

Nanoparticle Show
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"When I look at all the structures these nanoparticles form, I think the nanoparticles must have some yet-to-be-discovered
purpose," says Stephen O'Brien of Columbia University, a supervising member of one of the more prolific nanoparticle
collaborations. The aim of his team's work, he says, is to identify and exploit the rules by which an enormous and growing
variety of easily made nanoscale particles can self-assemble into structures with what he and his coworkers describe in
one paper as "programmable physical and chemical properties" (Nature 2006, 439, 55).

"Our fundamental interest is to make as many new materials as we can," says O'Brien's colleague Elena V. Shevchenko of
the Molecular Foundry at Lawrence Berkeley National Laboratory in California. "We are taking nanoparticles of different
sizes and functionalities???you know, like atoms???and mixing them together."

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By mixing and matching pairs of semiconducting, metallic, and magnetic nanoparticles—with core diameters ranging
from about 3 to 13 nm but of uniform size for any given type of nanoparticle-the researchers have made many versions of
what they call "binary nanoparticle superlattices." Their theoretical analyses, modeling work, and experimental data
indicate that the factors that determine exactly what binary superlattice will form include relatively long-range
electrostatic forces between the nanoparticles, close-proximity effects such as dipole interactions and van der Waals
forces, size effects, and the relative concentrations of the paired nanoparticle ingredients. The scientists have made
superlattices with a range of nanoparticle stoichiometries—among them AB, AB2-6, and AB13—with tetragonal, cubic,
hexagonal, and orthorhombic crystal symmetries.

The research remains fundamental. No practical new semiconductor, catalyst, or optical filter has come of it yet, but the
simplicity of the process has made the researchers a bit giddy. "For me," Shevchenko says, "one of the most exciting
results is that it is possible to make so many structures and that it is so easy."

To make the nanoparticles, the researchers use ultrasonication to dissolve a metal salt or other metal-containing ingredient
in toluene or another nonpolar solvent. They also add a hydrocarbon coating agent important in the subsequent self-
assembly process that forms the superlattices. After a few more precipitation-inducing agents have been added, the
particles are harvested by centrifugation. The particles' size depends on the particular metal-containing ingredient used:
Silver nitrate yields 4.2-nm-diameter silver nanoparticles, whereas silver chloride gives 3.4-nm-diameter particles. Gold,
lead, iron oxide, lead selenide, lead sulfide, cobalt-platinum, and other nanoparticles can all be made with comparable
ease.

© Howard
Davis/GreatBuildings.com

Restraint Tilings in the Alhambra,

the famed 14th-century palace in
Granada, Spain, are reminiscent of
the superlattices into which some
nanoparticles self-assemble.

Making the superlattices is even less complicated. In almost all cases, the researchers simply place a surface-typically a
transparent silicon nitride chip or a silicon—based grid that can later double as the stage for transmission electron
microscope (TEM) imaging—in a jar. They then add a colloidal solution bearing the two nanoparticles that they decided
to pair up for self-assembly. When the solution is tilted at a drinking angle, placed inside a chamber at reduced pressure,
and then gently heated, the organic solvent evaporates. What's left behind is a binary nanoparticle superlattice.

The most instantly compelling component of the papers the researchers have written about their work are the TEM
images, including the scores of images in a 17-page chronicle of their research published earlier this year in the Journal of
the American Chemical Society (2006, 128, 3620) and in Nature. These images, some of which are reproduced on these

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Chemical & Engineering News: Science & Technology - A Periodic Table Of Nanopartic... Page 3 of 3

pages, reveal a plethora of patterned assemblies reminiscent of the geometric tessellations covering the walls and ceiling
of the Alhambra in Spain and other Moorish buildings.

"The pictures are nice," notes Irving P. Herman, head of Columbia University's Materials Research Science & Engineering
Center. "But they are nice because of the new synthetic control the researchers have. It will lead to whole new classes of
materials."

Chemical & Engineering News

ISSN 0009-2347
Copyright © 2010 American Chemical Society

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