New Type of Nanotube Made of Gold or Silver Created

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Weizmann Institute scientists have created a new type of nanotube built of gold, silver and other nanoparticles. The tubes exhibit unique electrical, optical and other properties, depending on their components, and as such, may form the basis for future nanosensors, catalysts and chemistry-on-a-chip systems.
 
The study, published in Angewandte Chemie, was performed by Prof. Israel Rubinstein, Dr. Alexander Vaskevich, postdoctoral associate Dr. Michal Lahav and doctoral student Tali Sehayek, all of the Institute’s Department of Materials and Interfaces.
 
Nanotubes are tiny cylinder-shaped structures (a nanometer is one millionth of a millimeter). Discovered in 1991, the first nanotubes were made of carbon and captured the attention of scientists worldwide when they proved to be the strongest material ever made (100 times stronger than steel), as well as being excellent conductors of electricity and heat.
 
The new nanotube created at the WIS lacks the mechanical strength of carbon nanotubes. Its advantages lie instead in its use of nanoparticles as building blocks, which makes it possible to tailor the tube’s properties for diverse applications. The properties can be altered by choosing different types of nanoparticles or even a mixture, thus creating composite tubes. Moreover, the nanoparticle building blocks can serve as a scaffold for various add-ons, such as metallic, semiconducting or polymeric materials – thus further expanding the available properties.
 
The tubes are produced at room temperature – a first-time achievement – in a three-step process. The scientists start out with a nanoporous aluminum oxide template that they modify chemically to make it bind readily to gold or silver nanoparticles. When a solution containing the nanoparticles (each only 14 nanometers in diameter) is poured through, they bind both to the aluminum oxide membrane and to themselves, creating multi-layered nanotubes in the membrane pores. In step three, the aluminum oxide membrane is dissolved, leaving an assembly of free-standing, solid nanotubes.
 
“We were amazed when we discovered the beautifully formed tubes,” says Rubinstein. “The construction of nanotubes out of nanoparticles is unprecedented. We expected the nanoparticles to bind to the aluminum oxide template – that had been done before; but we did not expect them to bind to each other, creating the tubes.”
 
The discovery process held other surprises for the Institute team. They had set out to accomplish something else entirely – to create a nanoporous template for studying the passage of biological molecules through different membranes. Likewise, having employed annealing – a process that uses heat to bind structures – they found that annealing actually prevented tube formation. “Everything interesting, in fact, happened at room temperature,” says Rubinstein. “This exceptional process, of spontaneous room-temperature binding of nanoparticles to form tubes, is not yet fully understood and is currently being studied.”        
 
The resulting tube is porous and has a high surface area, distinct optical properties and electrical conductivity.  Collectively, the tube’s unusual properties may enable the design of future sensors and catalysts (both requiring high surface area), as well as microfluidic, chemistry-on-a-chip systems applied in biotechnology, such as DNA chips (used to detect genetic mutations and evaluate drug performance).
 
Applying their approach, the team has succeeded in creating various metal and composite nanotubes, including gold, silver, gold/palladium and copper-coated gold tubes. Yeda, the Institute’s technology transfer arm, has filed a patent application for the new tubes.
 
Prof. Israel Rubinstein’s research is supported by the Clore Center for Biological Physics, The Philip M. Klutznick Fund for Research, the Fritz Haber Center for Physical Chemistry, the Minerva Stiftung Gesellschaft fuer die Forschung m.b.H., and the Angel Faivovich Foundation for Ecological Studies.

 
There are 300 dpi JPEG files of the following images available upon request to news@weizmann.ac.il.
 
 
(1) Image of gold nanoparticle nanotubes obtained with a scanning electron microscope.

 

(2A) Image of composite gold/palladium (1:1) nanotubes.

 

(2B) Enlargement showing the arrangement of individual gold/palladium nanoparticles and the fact that the structure is multi-layered and hollow.
 
 
Chemistry
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How 'Micro' Can We Go?

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Microelectronics may be a growth industry, but the devices it produces are getting smaller every year. Just how "micro" can electronic devices go?

Weizmann Institute scientists have provided one of the answers to this question. Making simple and elegant use of a chemical theory of liquids, they developed a way to predict the minimal possible size of bipolar transistors, one of the major types of transistors commonly used in microelectronics. They then managed to manufacture such a tiny structure using the experimental semiconductor copper indium diselenide. With an inner core of just 20 nanometers (billionths of a meter) and total width of 50 nanometers - less than one-thousandth the width of a human hair - the device is five times smaller than today's smallest standard transistors of this type.

This research, reported recently in Applied Physics Letters, was performed by doctoral student Shachar Richter, working with Prof. David Cahen of the Materials and Interfaces Department, Dr. Yishay Manassen, formerly of Weizmann's Chemical Physics Department and now a professor of physics at Ben-Gurion University of the Negev, and Dr. Sidney Cohen, head of Weizmann's Surface Analysis Unit.

In his research, Richter used atomic force microscopy - a technique in which a phonograph-like stylus probes the surface of a material - to manipulate atoms in a semiconductor. Normally, such microscopes can only shift atoms on the surface of a material, but Richter, building on earlier research by Prof. Cahen, managed to move these atoms around inside the semiconductor.

Richter achieved his results by applying a voltage to the semiconductor and passing a current through the material. Aided by the slight heating produced by the current, the voltage caused atoms called dopants, which determine the material's conductivity, to be propelled in a particular direction. Even though only 100 to 200 dopants were moved in this manner, this sufficed to produce a tiny transistor. It consisted of a hemispherical layer of relatively high conductivity containing the redistributed dopants, flanked on both sides by material with different conductivity.

Next, Richter used the same microscope stylus - at low voltage - to map the conductivity of this miniature structure. Richter's new mapping method, called scanning spreading resistance, reveals the precise path that would be taken by an electric current flowing through a transistor of this type. This new type of measurement, developed independently by Belgian researchers around the time of Richter's study, promises to become an important tool for evaluating miniature electronic devices.

These findings don't necessarily mean that microelectronic devices will eventually get as small as Richter's transistor. His device, however, can serve as a valuable research tool for studying the limits of miniaturization.

Funding for this research was provided by the Israel Science Foundation and the Minerva Foundation, Munich, Germany.

The Weizmann Institute of Science is a major center of scientific research and graduate study located in Rehovot, Israel.
Chemistry
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A Mismatch Made in Heaven

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A perfect match may be a blessing in love or marriage, but in materials science a slight mismatch may sometimes help achieve the best results. Researchers at the Weizmann Institute have shown that by manipulating the mismatch between the spacing of atoms in two materials they can control the size of microscopic semiconductor crystals.

The finding holds a possible key to the development of tiny semiconductors with new optoelectronic properties for basic research and for tomorrow's optics and electronics industries. This is because the properties of crystals smaller than approximately 10 nanometers, or 10 millionths of a millimeter, can be altered by merely changing their dimensions.

This research was conducted by Dr. Gary Hodes, Prof. Israel Rubinstein and then doctoral student Yuval Golan, all of the Materials and Interfaces Department, and was described in a series of papers, the most recent two published in Advanced Materials .

Using a technique called electrodeposition, the scientists laid down crystals of the semiconductor cadmium selenide, each measuring four to five nanometers, onto a gold substrate. The crystals were found to be oriented in a uniform manner. This configuration is highly beneficial for controlling the semiconductor properties and it occurs because the atoms of the crystals tend to align themselves with the atoms in the surface layer of the substrate. Such alignment is attributed to the good match between the interatomic spacings of cadmium selenide crystals and of gold.

"We now run into what might at first glance seem to be a paradox," says Hodes. "On the one hand, attaining a close match is the important first step leading to crystal alignment. On the other hand, the match is not perfect - but this imperfection can also be made to work to our advantage. In fact," he says, "it is the small remaining mismatch that allows for precise control over crystal size."

The substrate "stretches" the growing crystal in an attempt to minimize the mismatch, creating a strain within the crystal that eventually causes it to stop growing altogether. Therefore, by fine-tuning the mismatch the scientists were able to determine when the crystal will stop growing, in other words, its size. They showed that the addition of small amounts of a material called tellurium to the semiconductor reduced the mismatch to a predictable degree.

This allowed them to produce uniformly oriented crystals of varying sizes. "Compared with alternative approaches, our method is much simpler and cheaper and makes it possible to control the size of smaller crystals," says Rubinstein.
 

The study by Prof. Rubinstein and Dr. Hodes was supported by the U.S. Office of Naval Research.

The Weizmann Institute of Science is a major center of scientific research and graduate study located in Rehovot, Israel.

 
Chemistry
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On the Surface of Things

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From pens to pans, from hard disks to compact discs, an increasing number of products are made of polymers, giant complex molecules with repeating structural units.

Different polymers are often mixed together in liquid form and then allowed to harden in order to impart the best properties of each to the final product. During the mixing, certain types of polymers are more likely than others to move to the surface, forming a coating that thickens with time.

It is important to know which constituent is more likely to move to the outside: for example, a polymer that excels in dirt-resistance or lubrication will be of greatest benefit if it settles closer to the surface. It is also important to know whether the polymer layer at the surface will have time to thicken sufficiently before the molten mixture hardens.

A series of Weizmann Institute studies -- the latest of which appears in a recent issue of Physical Review Letters -- helps to answer these questions and may lead to better polymer materials.

Prof. Jacob Klein and his student Ullrich Steiner of the Institute's Materials and Interfaces Department have determined that the more flexible polymer chains in a mixture -- the ones easier to bend -- will be found at the surface.

They also discovered that the rate of thickening is primarily controlled by the weak forces of attraction between neutral molecules, known as van der Waals forces. Due to the weakness of these forces, the thickening is extremely slow -- it proceeds in accordance with a mathematical formula involving approximately the power of 4. If, for example, a wetting layer grows to a certain thickness after one hour, then it will double its thickness after 16 hours (2 to the 4th power), and double once again after 256 hours (4 to the 4th power), and so on -- until the mixture hardens and this process stops.

These studies were carried out at the Weizmann Institute's 3 MV Van de Graaff particle accelerator, where the nuclei of polymers were bombarded by atoms propelled to high speeds. An analysis of the reactions occurring within these nuclei provides detailed data about the formation of the polymer surface coating and its properties.

These findings advance the basic understanding of processes taking place in polymer mixtures. They may also help optimize the surface properties of materials made up of different polymer components.



Prof. Klein's research was partially supported by the German-Israeli Foundation for Scientific Research and Development (GIF), the Minerva Foundation, the Commission of the European Union and Israel's Ministry of Science. Prof. Klein holds the Hermann Mark Chair of Polymer Physics. Ullrich Steiner now conducts research at the University of Konstanz in Germany.


The Weizmann Institute of Science is a major center of scientific research and graduate study located in Rehovot, Israel.
Chemistry
English

Tough Enough

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Being only one ten-thousandth the thickness of a human hair, yet displaying structural properties akin to those of diamonds, carbon nanotubes are heralded as the biggest of the little things that are set to revolutionize the world. These tiny hollow cylinders made from sheets of hexagonally-arranged carbon atoms could be ideal for use in applications including synthetic muscles, artificial nerve systems that may serve as smart sensors, high-performance car bodies and bridges, as well as novel electronic devices.

What makes them so appealing is that according to theoretical calculations, nanotubes should have incredible mechanical properties – close to the absolute best – rendering them the strongest, hardest, stiffest, toughest material ever to exist. So incorporating these nanotubes into other materials to make composites should greatly enhance those materials’ properties. “But their infinitesimal size makes it hard to prove this experimentally,” explains Prof. Daniel Wagner of the Weizmann Institute of Science’s Materials and Interfaces Department.
 
Together with his postdoctoral fellow Lu-Qi Liu from China, Wagner developed unique methods for creating nanocomposites and probing their mechanical properties. Their method, based on the so-called electrospinning technique, involves injecting the nanotubes into nanofibers in a parallel fashion and then twisting the strands of nanofibers into a microrope structure. They achieved this by attaching the nanofibers to a rotating motor that weaves the strands in a way similar to children dancing with ribbons around a maypole. The results, recently published in Advanced Materials, show that the nanocomposites turn out to be extremely tough. 
 
Prof. Daniel Wagner is the incumbent of the Livio Norzi Professorial Chair.
Chemistry
English