Introducing Impurity

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Prof. David Cahen and team. doping molecular materials
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
The world runs on impurity. Impurities in the colorless mineral beryl turn it to emerald. A bit of carbon tossed into pure iron hardens it into steel. And the ubiquitous silicon chips that form the basis of everything from our computers and electronic devices to musical birthday cards must contain impurities to work. In a process called doping, small amounts of other materials are introduced into pure silicon, and these impurities are what enable electricity to flow through the semiconductor and allow designers to control the electronic properties of the material.
 
Dr. Hagai Cohen. impurities to order
 
Scientists at the Weizmann Institute are working on substitutes for the silicon that most of the electronics industry relies on today. Molecular electronics is based on single organic (carbon-based) molecules or thin layers the thickness of a single molecule. Semiconductors based on organic molecules might be inexpensive, biodegradable, versatile and easy to manipulate, and the wide variety of these molecules might open up all sorts of possibilities for new applications. But, like today's silicon semiconductors, organic monolayers would need to be doped to work efficiently.
 
The question facing scientists working in the field is whether such molecular systems, which tend to be delicate and hard to manipulate, can be properly doped. That is, can these materials first be purified and then impurities added to order? Prof. David Cahen and postdoctoral fellow Dr. Oliver Seitz of the Weizmann Institute's Materials and Interfaces Department, together with Drs. Ayelet Vilan and Hagai Cohen of Chemical Research Support, all of the Faculty of Chemistry of the Weizmann Institute, and Prof. Antoine Kahn, from Princeton University (a regular visitor to the Institute), showed for the first time that such doping of molecular electronic systems is, indeed, possible.

 

First they succeeded in purifying the molecular layer to such an extent that the remaining impurities did not affect the system's electrical behavior. The scientists then doped the clean monolayers by irradiating the surface with UV light or weak electron beams. In this case, the impurities were not a second kind of molecule but a change in the chemical bonds between the carbon atoms that make up the molecular layer. These bonds ultimately influenced electronic transport through the molecules.
 
This achievement was recently described in the Journal of the American Chemical Society (JACS). The researchers foresee that this method may enable scientists and electronics engineers to substantially broaden the use of organic monolayers in the field of nano-electronics. Cahen: "After establishing an ideal system (a uniform layer of 'pure' molecules), we can dope it, introducing impurities that will allow us to control electron transport properties according to specific needs." Seitz: "If I am permitted to dream a little, it could be that this method will allow us to create types of electronics that are different, and maybe even more environmentally friendly, than the standard ones that are available today."
 
Prof. David Cahen's research is supported by the Nancy and Stephen Grand Research Center for Sensors and Security; the Philip M. Klutznick Fund for Research; Mr. Yehuda Bronicki, Israel; and Mr. and Mrs. Yossie Hollander, Israel. Prof. Cahen is the incumbent of the Rowland and Sylvia Schaefer Professorial Chair in Energy Research.
 
(l-r) Prof. Antoine Kahn, Dr. Oliver Seitz, Prof. David Cahen and Dr. Ayelet Vilan. Changing chemical bonds
Chemistry
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Transistor Genetics

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Take a few tiny spoonfuls of phosphates, sugars and nucleotides to create several types of DNA, add a pinch of carbon nanotubes, sprinkle in a few grains of gold, mix well on a clean silicon surface -and what do you have? A transistor, according to research conducted by Prof. Ron Naaman of the Weizmann Institute's Chemical Physics Department.
 

Several unique strands of DNA were created and programmed to form different types of attachments. One tiny set of DNA strands was designed to connect to minuscule electrical contacts made of gold that were anchored to the silicon surface, while a second type of DNA strand was designed to fasten to the carbon nanotubes – extra-strong hollow tubes a mere 10 hydrogen atoms in diameter. The end result was a sort of carbon nanotube “bridge” spanning the silicon surface between two gold contacts.
 
Similar nanobridges may one day form the basis of tiny nanotransistors that will be used to build fast, efficient, miniaturized electronic circuits. This “recipe for success” appeared in Applied Physics Letters.  

 
Prof. Ron Naaman’s research is supported by the Fritz Haber Center for Physical Chemistry; the Ilse Katz Institute for Material Sciences and Magnetic Resonance Research; the Wolfson Advanced Research Center; the Philip M. Klutznick Fund for Research; and Dr. Pamela Scholl, Northbrook, IL. Prof. Naaman is the incumbent of the Aryeh and Mintze Katzman Professorial Chair.
 

DNA/nanotube bridge

 

 

A carbon nanotube (shown in brown) forms a bridge between two segments of DNA supported by gold contacts (yellow) attached to a silicon surface (green)
Chemistry
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Nanotubes Stay in Step

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Carbon nanotube on sapphire substrate

 

Sometimes a rough start makes for a smooth finish. Carbon nanotubes are excellent candidates for components of tiny nanoelectronic circuits, but their organization into ordered arrays on surfaces remains a major obstacle.

 

 

 

In an effort to manipulate their growth, the research group of Dr. Ernesto Joselevich of the Institute’s Materials and Interfaces Department experimented with the application of electrical fields to control the direction of nanotube formation on various surfaces. When a sapphire surface was chosen, the group was surprised to observe a beautiful parallel arrangement of nanotubes formed in an orientation completely independent of the electrical field. Closer examination of the sapphire revealed that it had not been cut precisely along the crystal plane, so the surface consisted of a series of terraces separated by steps of atomic dimensions. The iron nanoparticles used as a catalyst to produce nanotubes proved to be a lazy partner that didn't like to “climb stairs” but instead preferred to “glide” along the edge of the step. In its wake lay an organized trail of nanotubes formed snugly along this edge.  The nanotubes even followed kinks in the steps caused by defects in the crystal. This resulted in either straight or zigzag-shaped tubes, which are expected to have particularly interesting electronic properties.
 
“The direction and shape of the atomic steps can be controlled simply by the cut of the crystal,” says Joselevich. “This could lead to intriguing nanotube architectures.” Exploiting these small steps could mean a big step toward large-scale nano-fabrication to produce different nanowire arrangements in a controlled fashion.
 
Full details of the study appear in the cover story of the prestigious journal Angewandte Chemie
 
Dr. Ernesto Joselevich’s research is supported by the Ilse Katz Institute for Material Sciences and Magnetic Resonance Research; the Asher and Jeannette Alhadeff Research Award; Sir Harry A.S. Djanogly, CBE, UK; the Philip M. Klutznick Fund for Research; and Sylvia and Henry Legrain, Spain. Dr. Joselevich is the incumbent of the Dr. Victor L. Ehrlich Career Develop-ment Chair.
Nanotube formation along atomic steps
Chemistry
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Tubes with a Twist

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Prof. Israel Rubinstein and his team. Tubes in a template

In a discovery filled with surprises, Institute scientists have created a new type of nanotube made of gold, silver and other metals. Made at room temperature - a first time achievement - the tubes exhibit unique electrical and optical properties, and may lead to a variety of applications in medicine, industry and security systems.


Nanotubes are among the most promising materials of nanoscience, a rapidly growing field aimed at creating novel materials and structures by manipulating matter on the tiniest of scales - atom by atom, molecule by molecule. (Nanos, the Greek for dwarf, is one billionth, so a nano-meter is one billionth of a meter - or roughly one hundred-thousandth the width of a human hair.)


The first nanotubes, discovered in 1991, were made of carbon and captured the attention of scientists worldwide when, despite their incredibly small dimensions, they proved to be the strongest material ever made (see box).


The new nanotube created at the Institute lacks the mechanical strength of carbon nanotubes. Its advantages lie instead in its use of nanoparticles made of gold, silver and other metals as building blocks. This makes it possible to tailor the tube’s properties to diverse functions according to the nature of the nanoparticles chosen. These nanoparticles can also serve as a scaffold for various add-ons, such as semiconducting or polymeric materials, thus further expanding the tubes’ available properties.


The study, published in Angewandte Chemie, was performed by Prof. Israel Rubinstein, Dr. Alexander Vaskevich, post-doctoral associate Dr. Michal Lahav and Ph.D. student Tali Sehayek - all of the Institute’s Materials and Interfaces Department.


The scientists had started out with a totally different target - to create nanosized templates for studying how biological molecules pass through different membranes. “We were amazed when we discovered the beautifully formed nanotubes,” says Rubinstein. “The construction of nanotubes out of nanoparticles is unprecedented, and,” he adds smiling, “the twist is that we’re not yet sure how this happens, which, of course, is one of the fun things about science.”


What is clear is the specific scheme that led to the tubes’ formation. The team started out with an aluminum oxide template with nanosized pores, which they modified chemically to make it readily connect to gold or silver nanoparticles. When a solution containing the nanoparticles was poured through (each only 14 nanometers in diameter), the particles bonded to both the template and to one another, creating multi-layered nanotubes in the template pores. In the final step, the template can be dissolved, leaving an assembly of free-standing, solid nanotubes. “We expected the nanoparticles to bind to the template - that had been done before; but we did not expect them to bind to one another, creating the tubes,” says Rubinstein.


The resulting tubes are porous and have a high surface area, distinct optical properties and electrical conductivity. Collectively, the tubes’ unusual properties may enable the design of new catalysts as well as sensors capable of detecting diverse substances present in minuscule amounts. A key feature of their success would be the ability, due to the tube’s room-temperature production, to add on biological molecules that would otherwise be destroyed by high production temperatures. These would then perform their natural function of recognizing other molecules in nature, in a key-fits-lock manner. Other tube applications might include lab-on-a-chip systems used in biotechnology, such as DNA chips that detect genetic mutations or evaluate drug performance. Yeda, the Institute’s technology transfer arm, has filed a patent application for the tubes.

 

A close look shows hollow gold/palladium tubes

Tough stuff

While major hurdles remain, scientists believe that the products of nanoscience might change our future. Carbon nanotubes, for instance, are already a favorite with researchers worldwide. Researchers estimate that a fiber about the width of a human hair made of these carbon tubes could support around 2 tons. The first experiment demonstrating the strength of carbon nanotubes was performed here at the Institute by Prof. Daniel Wagner. The tubes’ phenomenal strength (over 100 times stronger than steel) has triggered research targeting applications that run the gamut from classic engineering quests, such as longer bridges and taller buildings, to science-fiction- like missions, including nanotube cables that would tether a satellite in orbit or even make possible “space elevators” carrying people or equipment into outer space.

Different dimensions

Look for Rubinstein and his team outside of the lab and you might be surprised. Rubinstein, for instance, has a black belt in karate, having picked up the sport at age 45; Vaskevich (Sasha) spends his downtime trekking through mountains and art museums; for Michal Lahav, currently pursuing a postdoc at Harvard University, time-off is best spent deep-water diving in the Red Sea’s world-famous reefs; and roaming through the jungles of Peru or the temples of Thailand is how Ph.D. student Tali Sehayek chooses to relax.

Prof. Rubinstein’s research is supported by the Clore Center for Biological Physics; the Fritz Haber Center for Physical Chemistry; the Angel Faivovich Foundation for Ecological Studies; the Philip M. Klutznick Fund for Research; the Edward D. and Anna Mitchell Family Foundation; and Minerva Stiftung Gesellschaft fuer die Forschung m.b.H.

Prof. Wagner is the incumbent of the Livio Norzi Professorial Chair.

(l-r) Dr. Alexander Vaskevich, Prof. Israel Rubinstein and Ph.D. student Tali Sehayek. Tube tales
Chemistry
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Shaping the Future

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Frydman, Maoz, Sagiv and Cohen. Nano-building techniques

History repeats itself. However, can the history of "big things" be deliberately duplicated when developing "the small stuff"? Can massive be made into diminutive? Most importantly, can the process be revealed ­ and then restructured? And what does all of this have to do with cavemen?

Using the history of man-made architecture as an example, is it replicable when designing, manufacturing, and building electronic apparatus ­ when its size is only one-millionth of a millimeter?

Sounding the philosopher-architect in addition to the materials scientist, Prof. Jacob Sagiv of the Materials and Interfaces Department at the Institute is asking these questions, and he believes this is exactly the direction tomorrow's technology will take.

"Our ancestors," says Prof. Sagiv, "lived in the caves that nature provided. Later, they learned how to carve out the rock and to extend their caves. In this way, for example, ancient water cisterns were crafted. Thus, the city of Petra was carved out of the red rock in the southern part of the Kingdom of Jordan.

"Early man showed that with rock carving, one can produce some very impressive achievements. But at a certain stage this technology reaches the limit of its possibilities; those with the determination to progress must abandon it and find a more advanced replacement. This is exactly what the ancients did. Instead of continuing to carve out living accommodation from the existing natural rock, they began to chisel away at smaller stones, so that they could be used as building blocks to fabricate various structures with them: water cisterns, walls, and housing.

"Using the technique of building blocks, it was possible to reach a level of sophistication and complexity that surpasses previous, ancient methods. It cannot be compared with the products that were made using the technique of carving out natural rock. For example, today's building methods, to which various strengthening techniques were added, allow for the construction of the most complicated skyscrapers built by man. And he's still testing the limits.

"A similar development is also likely to take place in the field of constructing small electronic devices. Presently, integrated electronic circuits are being manufactured using methods based on 'digging,' by etching the crystals of semiconductors. The trend toward miniaturization of integrated circuits, to whatever extent possible, demands chemical 'carving' to a very delicate degree. But what level of delicacy can be reached? What are the boundaries of complexity of the structures that we can create in this way?

"As it's clear that we're approaching these limits, if we're going to continue to advance, we have to imitate the ancient architects. We've got to abandon the technique of carving out existing materials and start building structures and apparatus from the tiniest of building blocks available: molecules and atoms."

Prof. Sagiv, Dr. Rivka Maoz and research student Eli Frydman of the Institute's Materials and Interfaces Department, together with Dr. Sidney Cohen of the Institute's Chemical Services Unit, have recently taken some first steps in this direction; they've succeeded in building planned, simple three-dimensional structures out of molecules.

In the first stage, the researchers manufactured a base layer, one molecule thick, which was attached in a well-defined manner to the outer surface of a selected solid material, in this case, silicon. To do this, they used molecules that on one side are hydrophilic (i.e., water "loving") and on the other side, hydrophobic (i.e., water "hating"). When a plate of glass or a silicon chip is immersed in a solution containing such molecules, their hydrophilic sides attach themselves to the plate (as its properties are similar to those of water), while the hydrophobic sides face outwards.

Then they were ready for the building stage. This is how it works.

To mark the foundations of the molecular building, the researchers used an atomic force microscope. This is a lensless instrument that works by blindly groping about the face of the surface of the material using a needle with a fine tip which "feels out" the atoms and the molecules protruding from the top of the surface. The needle sends "sensations" to the computerized system which translates the "feelings" into pictures on a computer screen.

The distance between the sensing tip and the material's surface must be less than one nanometer (one-millionth of a millimeter). Following an idea suggested by Dr. Maoz, the Weizmann Institute team discovered that when a small electric current flows down the fine sensing tip, it can induce a localized chemical reaction which changes the properties of the molecules located directly beneath it, on the surface of the material being treated. In this way, the researchers were able to change the properties of the surface molecules in a specified area. Only "the chosen" will be adapted for additional connections to other selected molecules.

Using the needle of the atomic force microscope, the scientists could deliberately change the chemical properties of the hydrophobic, outwards-facing side of the molecules attached to the silicon chip, so that at any point where the tip "draws" lines of such chemical changes, new molecules can attach themselves to those first attached to the surface. In this way the "walls" of the molecular building are constructed.

In one experiment, for example, the members of the research team made a two-story molecular building in the shape of a tiny Star of David whose sides had a width of one-thousandth the width of a human hair.

These first steps in the architecture of molecular buildings are likely to bring about the development of tiny devices and other products which cannot be constructed using existing miniaturization technologies. The devices will be designed for high efficiency and, by their nature, will offer maximum space saving.

New and unconventional properties are likely to be derived both from their minuscule dimensions andfrom the purpose-designed spatial organization of their molecular components.

Prof. Sagiv and Dr. Maoz dream of giving new meaning to "Small is beautiful." While most of us are still struggling with "Think big," it's apparent that creative living solutions are literally right under our noses, in miniature.

From big to small

 
Chemistry
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Of Magnets, Molecules, and Memory

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Reducing switch size. Prof. Reshef Tenne

Toast 'em, roast 'em, shape 'em, salt 'em: Chip consumption has reached an all-time high. The consumer can't get enough of them, as the market clamors for the bigger, better and more perfect chip. There's another chip to add to the pile: computer chips. And make that with an extra dose of memory, please.

It all has to do with the law of supply and demand. The constant, urgent need for increased computer memory best exemplifies this theory.

While most computer users may not be aware of it, scientists and entrepreneurs worldwide are working nonstop to develop ways of creating more efficient and smaller-sized computer memory, as the demand for more minute and efficient memory continues to increase. But computer chip memory isn't just mixed in a test kitchen before hitting the shelves. This "recipe" calls for finetuning ­ of molecules and molecular structure. Computer memory is built from a large number of "switches" capable of being in one of two positions that can be called "on" or "off."

The switches in most computer memories are built of blocks of magnetic material, where a change in its magnetic polarity determines whether they change from on or off (or vice versa, as the instruments' developers determine).

In order to increase, as much as possible, the amounts of data that can be stored in any given physical space, scientists are being asked to constantly reduce the size of each switch. To what extent is this possible? Until every switch is based on only one molecule of material.

In various places around the world, and notably, at the Weizmann Institute of Science, different types of molecular switches have already been created. That's the good news. The bad news: The experiments for applying them to the construction of multiswitch computer memory have run into new obstacles. The ideal magnetic switch must be characterized by the low power of its magnetism (which allowsits magnetic polarity to be changed easily), and its stability (which allows the data to be stored reliably over long periods of time).

In other words, scientists trying to develop the molecular magnetic switches are searching for a material that is well-defined chemically, i.e., a pure substance, which contains only one type of molecule with no impurities, organized into a defined multimolecular spatial structure characterized by defined magnetic properties. At the same time it must also be resistant, as much as possible, to environmental effects: electrical fields, temperature changes, etc.

Unfortunately, demanding that all these properties exist together involves a catch. When single molecules comprising molecular switches are located very close to one another, any change in the magnetic polarity of one (for example, as a result of a temperature change), is liable to bring about a change in the magnetic polarity of its neighboring molecular switch. This effectively damages the ability of the medium to be used as a computer memory store or for it to reliably store data over the long term.

One proposal to solve this situation was recently made by Prof. Reshef Tenne of the Materials and Interfaces Department of the Weizmann Institute of Science. With colleagues Dr. Enrique Grunbaum of Weizmann and Drs. Jeremy Sloan and John Hutchinson of the University of Oxford, Prof. Tenne and his research student, Yaron Rosenfeld Hacohen, succeeded in creating a single molecular layer in a spherical shape, like a soccer ball, made from nickel-chloride molecules. The molecules are expected to have defined magnetic properties on one hand, and relative resistance to changing environmental conditions on the other. In effect, these are molecules capable of serving as magnetic memory switches with a high degree of reliability. Their findings are now being published in the prestigious international journal Nature.

Prof. Tenne and Rosenfeld Hacohen have also succeeded in creating tiny molecular "pipes" from nickel-chloride molecules. Tenne was the first to show that it's possible to build the molecular nanotubes from inorganic materials. Observation was done on a very small number of objects of this kind. In order to characterize and measure their properties, millions of such structures must first be synthesized. While research is in its earliest stages, it's hoped the nanotubes might one day serve a relatively large number of industrial applications, including their use as tools for "writing" magnetic data onto computer disks, and also for "reading" the data stored on such disks. The unique properties of nickel-chloride are likely to make it possible to read and write magnetic data, both optical and electrical, as one.
 
Another possible application of the new molecular tubes is to control the manufacture of computer chips. Additional uses? That's part of the thrill of the scientific process. It's probable that the greatest and most important employment of the first inorganic molecular tubes is yet to come.
 
Chemistry
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Size Counts...

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Prof. Israel Rubenstein and Dr. Gary Hodes. Smaller and higher

 
 
When it comes to size, Dr. Gary Hodes and Prof. Israel Rubinstein of the Materials and Interfaces Department are getting everything under control.

Their research is focusing on controlling the property and size of quantum particles (less than one-millionth of a millimeter) of semiconductors. Semiconductors are the basis of the transistor, which is the fundamental unit in radio, TV, computers, communications and other equipment. Their studies are an important step toward developing a single electron transistor, much smaller than present transistors.

As a result of their research, it emerges that when individual quantum particles are electro-deposited on a metal surface, the surface can act as a kind of template which determines both the direction and size of the particles.

Size is of the essence when it comes to quantum-sized semiconductors. It determines the amount of energy separating the conduction band and the valence band which electrons may occupy, known as the bandgap. Hodes and Rubinstein, in collaboration with Dr. Sidney Cohen of the Chemical Services Unit, and graduate student Boaz Alperson, developed a method to measure the dependence of the bandgap on the size of the quantum particle. The smaller a quantum particle, the wider its bandgap. This property may have great importance for the development of future electroopticaldevices.

How did they do it? Hodes' and Rubinstein's work involves the use of an atomic force microscope; they improved its measuring capability by covering its tip with an electricity-conducting metal.

Using the enhanced atomic microscope, they've succeeded in measuring the width of the bandgap in sing le quantum particles of the semiconductors they deposited. In these measurements, the first of their kind to be carried out at room temperature, the researchers also succeeded in monitoring the transfer of individual electrons into the semiconducting quantum particles.


...and Height Counts, Too


Prof. Israel Rubinstein of the Materials and Interfaces Department, and Prof. Abraham Shanzer of the Organic Chemistry Department, have developed a new technique for building ordered molecular structures. The structures are made from layers of organic molecules arranged in an orderly manner on the top of metal surfaces, and what's holding them together is a metal ion "cement."

The scientists can choose what kind of "building blocks" to use according to their expected chemical reactions. They can mix two or more types of building blocks, which respond differently to chemical reactants.

In this collaborative effort, Rubinstein and Shanzer are also working with Dr. Hagai Cohen of the Chemical Services Unit, and graduate students Anat Hatzor and Tamar Moav. When doing their "construction work," the scientists have already encoded the shape that will emerge after a specific chemical reaction. Therefore, by putting the whole building through a chosen chemical reaction, they're able to break up certain connections in a controlled way.

Using this technique, it's possible to build a complex molecular-scale building whose various wings reach different heights and different shapes, based on the architectural information which has been encoded in the building during its construction process.
 
Chemistry
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Tiniest Switches Promise Ultracompact Computer Memories

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A unique organic molecule that my pave the way toward the design of incredibly compact digital storage devices or computer memories has been developed by Weizmann Institute scientists.

The researchers -- a team or organic chemists including graduate student Lior Zelikovich, senior staff scientist Dr. Jacqueline Libman, and group leader Prof. Abraham Shanzer -- have synthesized novel, triple-stranded complexes of iron that my serve as the basis for switches the size of a small molecule.

Adapting these molecular-sized switches for use as ultracompact electronic devices -- whose digital circuitry would contain tens of million of "on"-"off" elements -- will require the solution of several inherent problems. There are no known methods for turning individual molecular switches "on" and "off" (the so-called "addressing" problem), or for detecting whether a particular molecular switch is "on" or "off" (the "reading" problem), or for "wiring" individual molecules to the external world. Improved switching complexes that operate much more rapidly will also be needed.

"There is no way to predict when molecular switches will become integrated into functional devices," says Shanzer. "But because of the importance of further miniaturization of electronic components, research into the ultimate level of miniaturization -- the use of molecular components -- is now attracting increasing scientific interest. When this technology comes of age, it could result in digital storage elements and memories millions of times more compact than now available, and in novel devices with capabilities far beyond anything possible today."

Building on their experience in synthesizing metal-binding organic compounds for medical, industrial and agricultural applications, the Shanzer-Libman team turned to the design of similar complexes with switch-like properties. In this work, they engineered an organic molecule with two sites, each of which binds iron in differently charged states. Using simple chemical techniques, the charge on the iron can be raised or lowered, causing it to jump between the two molecular sites. This jump causes the complex to change its color from yellow-brown to purple, a change that is easily seen in the test tube.

The Shanzer-Libman team is now working on other molecules that may have a potential to be "switched," as well as on molecular structures that may be applicable for use as conductors or diodes. They are also examining ways of turning their molecular switches "on" and "off" by electrochemical and photochemical means, approaches that are closer to real-life, solid-state conditions than reaction chemistry in a test tube.

This research, which was undertaken at the Institute's Department of Organic Chemistry, was supported by the Israel Science Foundation (which is administered by the Israel Academy of Sciences and Humanities) and by the Consortium of German Chemical Companies.

Prof. Shanzer is the incumbent of the Siegfried and Irma Ullmann Professorial Chair.
Chemistry
English

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