Monday, January 24, 2011

Electron gas on insulator's surface opens way to multifunctional transistors

French researchers have succeeded in creating a conductive layer on the surface of strontium titanate (SrTiO<sub>3</sub>), a transparent insulating material considered to be very promising for the development of future microelectronics applications. Two nanometers thick, this conductive layer is a two-dimensional metallic electron gas (2DEG) that is part of the insulating material. Easy to produce, it opens new possibilities for electronics based on transition metal oxides (the SrTiO<sub>3</sub>family), taking advantage of these materials' vast range of physical properties (superconductivity, magnetism, thermoelectricity, etc.) to integrate a number of different functions in a single microelectronic device. A paper explaining this unexpected discovery, arising from research at the SOLEIL synchrotron, was published in the January 13, 2011 issue of<i>Nature</i>magazine.

Today's microelectronic components consist of layers of semiconductors on a. In order to sustain the pace of periodic upgrades in the performance of microelectronic devices beyond 2020, alternative technological solutions are being investigated. Researchers are increasingly turning their attention to transition metal oxides , which offer promising physical properties such as superconductivity, magnetoresistance, thermoelectricity, multiferroicity and photocatalytic capacity.

Within this family of materials, strontium titanate (SrTiO3) has been the subject of extensive research. Thisbecomes a good conductor when it is doped, for example by creating a few surface oxygen vacancies. The interfaces between SrTiO3 and other oxides (LaTiO3 or LaAlO3) are conductive, even though the two materials are insulators. Moreover, they offer properties like superconductivity,and thermoelectricity, with very good performances at room temperature. The problem, however, is that interfaces between oxides are very difficult to produce.

Now an unexpected discovery has burst through this technological barrier. An international team led by researchers at CNRS and Université Paris-Sud 11 has produced a two-dimensional metallic(2DEG) on the surface of SrTiO3. This conductive layer, approximately two nanometers thick, was obtained by vacuum-cleaving a piece of strontium titanate, a very simple and economical process. The constituent elements of SrTiO3are natural resources available in large quantities, and the compound is non-toxic, unlike the materials most widely used in microelectronics today (bismuth tellurides). In addition, 2DEGs could probably be created on the surface of other transition metal oxides using a similar technique.

The discovery of a conductive layer of this type (not requiring the addition of a layer of another material) is a significant step forward for oxide-based microelectronics. It could make it possible to combine the intrinsic multifunctional properties of transition metal oxides with those of the two-dimensional metal on their surface. Possible developments could include the coupling of a ferroelectric oxide with the electron gas on its surface to produce non-volatile memories, or the inclusion of transparent circuits on the surface of solar cells or touch screens.

The 2DEG on the surface of strontium titanate was identified and studied in experiments using angle-resolved photoemission spectroscopy (ARPES) at the SOLEIL synchrotron in Saint-Aubin, France, and the Synchrotron Radiation Center at the University of Wisconsin, USA.


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Sunday, January 23, 2011

Cracking a tooth: 3-D map of atoms sheds light on nanoscale interfaces in teeth, may aid materials design

Teeth and bone are important and complex structures in humans and other animals, but little is actually known about their chemical structure at the atomic scale. What exactly gives them their renowned toughness, hardness and strength? How do organisms control the synthesis of these advanced functional composites?

Now, using a highly sophisticated atomic-scale imaging tool on a sea creature's tooth, two Northwestern University researchers have peeled away some of the mystery of organic/inorganic interfaces that are at the heart of tooth and. They are the first to produce a three-dimensional map of the location and identity of millions of individual atoms in the complex hybrid material that allows the animal to literally chew rock.

Demonstrating that atom-probe tomography (APT) can be used to interrogate such materials opens up the possibility of tracking fluoride in teeth and cancer and osteoporosis drugs in bone (at previously inaccessible length scales). The detailed knowledge of organic/inorganic interfaces also will help scientists rationally design useful-- flexible electronics, polymers and nanocomposite materials, such as organic-- that combine the best properties of organic and.

The results will be published Jan. 13 by the journalNature.

"The interface between the organic and inorganic materials plays a large role in controlling properties and structure,"said Derk Joester, senior author of the paper."How do organisms make and control these materials? We need to understand this architecture on the nanoscale level to design new materials intelligently. Otherwise we really have no idea what is going on."

Joester is the Morris E. Fine Junior Professor in Materials and Manufacturing at the McCormick School of Engineering and Applied Science. Lyle Gordon, a doctoral student in Joester's lab, is the other author of the paper.

The two set out to find the organic fibers they knew to be an important part of the tooth's structure, buried in the tough outer layer of the tooth, made of magnetite. Their quantitative mapping of the tooth shows that the carbon-based fibers, each 5 to 10 nanometers in diameter, also contained either sodium or magnesium ions. Joester and Gordon are the first to have direct proof of the location, dimension and chemical composition of organic fibers inside the mineral.

They were surprised by the chemical heterogeneity of the fibers, which hints at how organisms modulate chemistry at the nanoscale. Joester and Gordon are anxious to learn more about how the organic fibers interface with the inorganic minerals, which is key to understanding hybrid materials.

"The tooth's toughness comes from this mix of organic and inorganic materials and the interfaces between them,"Joester said."While this is in principle well known, it is intriguing to think we may have overlooked how subtle changes in the chemical makeup of nanoscale interfaces may play a role in, for instance, bone formation or the diffusion of fluoride into tooth enamel. In this regard, atom-probe tomography has the potential to revolutionize our understanding."

Atom-probe tomography (APT) produces an atom-by-atom, 3-D reconstruction of a sample with sub-nanometer resolution. But many in the field didn't think APT would work to analyze a material made up of organic and inorganic parts.

Fortunately for Joester and Gordon, Northwestern has both David Seidman, a leader in the field who uses APT to study metals, and two of the few APT instruments in the country. (There are less than a dozen.) Seidman, Walter P. Murphy Professor of Materials Science and Engineering, encouraged Joester to take the risk and use APT to study biological architectures. The scientists also were able to exchange ideas with the engineers developing 3-D atom-probe instruments at CAMECA, a scientific instrumentation company in nearby Madison, Wis.

Joester and Gordon imaged teeth of the chiton, a tiny marine mollusk, because much is known about the biomineralization process. The chiton lives in the sea and feeds on algae found on rocks. It continually makes new rows of teeth -- one a day -- to replace mature but worn teeth; in conveyor-belt fashion, the older teeth move down the creature's tongue-like radula toward the mouth where it feeds.

Chiton teeth resemble human teeth in that they have a hard and tough outer layer -- equivalent to our enamel -- and a softer core. Instead of enamel, the rock-chewing chitons use magnetite, a very hard iron oxide, which gives their teeth a black luster.

The researchers extracted micron-sized samples from the leading edge of the tooth. Using a focused ion beam tool at the Northwestern University Atomic and Nanoscale Characterization Experimental Center core facility, these samples were fashioned into very sharp tips (less than 20 nanometers across). The process is reminiscent of sharpening a pencil, albeit with a supercharged stream of gallium ions.

The APT technique applies an extremely high electric field to the sample; atoms on the surface ionize, fly off and hit an imaging detector (similar to those found in night-vision equipment). The atoms are stripped off atom-by-atom and layer-by-layer, like peeling an onion. Computer methods then are used to calculate the original location of the atoms, producing a 3-D map or tomogram of millions of atoms within the sample.

Joester and Gordon now are studying the tooth enamel of a vertebrate and plan to apply APT to bone, which is also made of organic and inorganic parts, to learn more about its nanoscale structure.


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Saturday, January 22, 2011

New 'frozen smoke' material: One ounce could carpet three football fields

New 'frozen smoke' material: One ounce could carpet three football fields

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Scientists are reporting the development of a new, ultra-light form of"frozen smoke"-- renowned as the world's lightest solid material -- with amazing strength and an incredibly large surface area.

The new so-called"multiwalled(MCNT) aerogel"could be used in sensors to detect pollutants and toxic substances, chemical reactors, and electronics components. A report about the material appears inACS Nano.

Lei Zhai and colleagues explain thatmade from(the main ingredient in sand) and other material already are used as thermal insulation in windows and buildings, tennis rackets, sponges to clean up oil spills, and other products.

Aerogels are solid but so light that they have been compared to frozen smoke. However, only a few scientists have succeeded in making aerogels from carbon nanotubes, wisps of carbon so small that almost 50,000 would fit across the width of a human hair.

The report describes a process for making MCNT aerogels and tests to determine their properties. MCNT aerogels infused with a plastic material are flexible, for instance, like a spring that can be stretched thousands of times. If the nanotubes in a one-ounce cube were unraveled and placed side-to-side and end-to-end, they would carpet three football fields.

The MCNT aerogels also are excellent conductors of electricity, making them ideal for sensing applications, such as sensing as little as 0.003527 ounce of a material resting in the palm of one hand, the report indicates.


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Friday, January 21, 2011

A greener path for the production of a vital chemical

A greener path for the production of a vital chemical

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(PhysOrg.com) -- Nanoparticles of gold and palladium (Au-Pd) could lead to a more efficient and environmentally friendly way of producing benzyl benzoate, a chemical compound used widely in the food, pharmaceutical and chemical industries whose applications include a fixative for fragrances, a food additive and a solvent for chemical reactions.

The most common method of producing benzyl benzoate is to react benzoic acid with benzyl alcohol. It can also be generated from benzaldehyde. All three starting materials are derived from toluene, a component of. The manufacture of benzyl alcohol and benzaldehyde requires the use of halogens and acidic solvents, whereas benzoic acid is produced via a more environmentally friendly liquid phase cobalt-catalyzed reaction.

A research team led by Graham Hutchings, professor of chemistry at Cardiff University in Wales in the United Kingdom, and Christopher Kiely, professor of materials science and engineering at Lehigh, has found a way of producing benzyl benzoate directly from toluene in a solvent-free, single-step process using Au-Pd nanoparticles to catalyze the reaction.

“By optimizing the Au-Pd ratio in the nanoparticle, as well as the reaction conditions, we were able to achieve conversion rates of over 95 percent with no conversion to carbon dioxide,” says Hutchings.

A greener path for the production of a vital chemical
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A high resolution electron micrograph of a gold-palladium nanoparticle on a titanium oxide support.

Shining a light on particle size and catalytic activity

The researchers reported their finding Jan. 14 inSciencemagazine in an article titled“Solvent-Free Oxidation of Primary Carbon-Hydrogen Bonds in Toluene Using Au-Pd Alloy.” The article was coauthored by Hutchings and Kiely and 10 other researchers, including Ramchandra Tiruvalam, a Lehigh Ph.D. candidate working with Kiely.

Rather than making the catalysts by conventional support impregnation techniques, the researchers chose a preparation route that involved the sol-immobilization of Au-Pd colloids using amorphous carbon and titanium oxide supports. This technique offers much greater control over particle size and composition than do conventional methods.

Transmission electron microscopy (TEM) studies carried out by Tiruvalam revealed that the average particle sizes were very similar, 3.3 nanometers on carbon and 3.5nm on titanium oxide.

“Despite having a very similar particle-size distribution, the Au-Pd/carbon samples were found to have approximately double the catalytic activity of the Au-Pd/titanium oxide samples,” says Kiely, who directs the Nanocharacterization Laboratory in Lehigh’s Center for Advanced Materials and Nanotechnology.

“This suggests that simple metal surface area considerations are not dominating the catalytic activity.”

Achieving stability and reusability

Using Lehigh’s aberration-corrected TEM, Tiruvalam was able to show that the particles were indeed Au-Pd alloy particles, that those on the titanium oxide were highly faceted and tended to form a flat interface with the support, and that those on the carbon were much more rounded.

“The difference in catalytic activity may be related to differences in the number of low coordination number edge and corner sites available,” explains Kiely.“The more rounded‘rougher’ particles on the carbon support have significantly more of these sites than the flatter particles on thesupport.”

In a final set of experiments, the researchers were able to demonstrate that the Au-Pd/carbon catalysts showed no loss of activity after use and that there was little change in particle shape and size after extended reaction periods.

“It is clear that these highly active catalysts are both stable and reusable,” says Kiely.


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Thursday, January 20, 2011

Effects of atomic-scale roughness on adhesion between diamond surfaces

CNST Project Leader Rachel Cannara and collaborators from the United States Naval Academy (USNA) and the University of Pennsylvania have shown that atomic-scale surface roughness has a strong influence on adhesion for diamond, amorphous carbon, and model diamond nanocomposites.

Using(AFM) measurements performed at the University of Wisconsin-Madison, molecular dynamics (MD) simulations, and ab initio(DFT), they investigated the adhesive physics and mechanics of nanoscale interfaces between diamond surfaces.

For atomically smooth surfaces, the greater density of atoms in the (111) plane would be expected to lead to a higher electrostaticper unit area and a higher work of adhesion than the (001) orientation. However, the AFM measurements, supported by detailed simulations of model diamond nanocomposites, challenge this assumption in a way that can only be explained by variations in atomic-level surface roughness, which for single crystals can arise from orientation-dependent growth mechanisms.

Unlike previous ab initio studies that compared surface energies for diamond (111)(1×1)-H surfaces and unreconstructed diamond (001)(1×1)-H surfaces, the MD simulations performed at USNA simulate the (2×1)-reconstructed C(001)-H surface. The simulations predict that the C(001)(2x1)-H surface is energetically favorable to the unreconstructed surface. Corroborating these simulations, high-precision AFM lateral force images of the (001) surface revealed (2×1) dimer-row domains.

In addition to using the appropriate (001) surface structure, the MD simulations account for long-range van der Waals interactions, as well as surface energies, when calculating the work of adhesion for each interface. Moreover, the ab initio DFT calculations reveal the presence of bond dipoles on single-crystal diamond surfaces.

Using AFM, the contact mechanics of the interface was extracted from the load-dependence of the contact area during sliding friction experiments. Works ofwere then calculated from the appropriate contact mechanics model and from pull-off forces measured during the sliding experiments and quasistatic force-displacement measurements. These results have broad implications for the design of MEMS/NEMS devices that incorporate diamond or diamond-like materials.


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Wednesday, January 19, 2011

No longer just a spectator, silicon oxide gets into the electronics action on computer chips

In the materials science equivalent of a football fan jumping onto the field and scoring a touchdown, scientists are documenting that one fundamental component of computer chips, long regarded as a passive bystander, can actually be made to act like a switch. That potentially allows it to take part in the electronic processes that power cell phones, iPads, computers, and thousands of other products.

In a report in the, the scientists document the multiple ways in which silicon dioxide, long regarded simply as an electric insulator, gets involved in the action. This behavior had formerly confused scientists working in the area of nanoelectronics— they thought that the switching was due to the nano-additive but it turns out that the source of the switching might be from the underlying silicon oxide itself.

Jun Yao, Douglas Natelson, Lin Zhong, and James Tour explain that manufacturers have long used silicon oxide, normally a very poor conductor of electricity, as both a supportive and insulating material in electronics. Silicon, a primary component of beach sand, is the semiconductor material at the heart of modern electronics. When bound to oxygen, the resulting silicon oxide is generally one of the highest quality electronic insulating materials.

The scientists recently showed, however, that the oxide material can be converted to a switchable conductor by an electrical process. This phenomenon may hold the key to developing a new generation of smaller, more powerful, but the mechanism behind this switching was unclear, until now. It also clarifies the possible nature behind the switching events in former molecular and nano-scale systems.

The scientists sandwiched a nano-sized layer of silicon oxide, thousands of times smaller than the width of a human hair, between two electrodes and exposed the device to increasing amounts of electrical current. They demonstrated that electricity can cause theto breakdown into smaller components, nano-sized crystals of silicon, in a way that boosts its electrical conductivity and makes it a player in the working processes of computer chips.


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Tuesday, January 18, 2011

A nanoscale rope, and another step toward complex nanomaterials that assemble themselves

A Nanoscale Rope, and Another Step Toward Complex Nanomaterials That Assemble Themselves

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(PhysOrg.com) -- Scientists at the U.S. Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab) have coaxed polymers to braid themselves into wispy nanoscale ropes that approach the structural complexity of biological materials.

Their work is the latest development in the push to develop self-assembling nanoscale materials that mimic the intricacy and functionality of nature’s handiwork, but which are rugged enough to withstand harsh conditions such as heat and dryness.

Although still early in the development stage, their research could lead to new applications that combine the best of both worlds. Perhaps they’ll be used as scaffolds to guide the construction of nanoscale wires and other structures. Or perhaps they’ll be used to develop drug-delivery vehicles that target disease at the molecular scale, or to develop molecular sensors and sieve-like devices that separate molecules from one another.

Specifically, the scientists created the conditions for synthetic polymers called polypeptoids to assemble themselves into ever more complicated structures: first into sheets, then into stacks of sheets, which in turn roll up into double helices that resemble a rope measuring only 600 nanometers in diameter (a nanometer is a billionth of a meter).

“This hierarchichal self assembly is the hallmark of biological materials such as collagen, but designing synthetic structures that do this has been a major challenge,” says Ron Zuckermann, who is the Facility Director of the Biological Nanostructures Facility in Berkeley Lab’s Molecular Foundry.

In addition, unlike normal polymers, the scientists can control the atom-by-atom makeup of the ropy structures. They can also engineer helices of specific lengths and sequences. This“tunability” opens the door for the development of synthetic structures that mimic’ ability to carry out incredible feats of precision, such as homing in on specific molecules.

“Nature uses exact length and sequence to develop highly functional structures. An antibody can recognize one form of a protein over another, and we’re trying to mimic this,” adds Zuckermann.

Zuckermann and colleagues conducted the research at The Molecular Foundry, which is one of the five DOE Nanoscale Science Research Centers premier national user facilities for interdisciplinary research at the nanoscale. Joining him were fellow Berkeley Lab scientists Hannah Murnen, Adrianne Rosales, Jonathan Jaworski, and Rachel Segalman. Their research was published in a recent issue of theJournal of the American Chemical Society.

The scientists worked with chains of bioinspired polymers called a peptoids. Peptoids are structures that mimic peptides, which nature uses to form proteins, the workhorses of biology. Instead of using peptides to build proteins, however, the scientists are striving to use peptoids to build synthetic structures that behave like proteins.

The team started with a block copolymer, which is a polymer composed of two or more different monomers.

“Simple block copolymers self assemble intostructures, but we wanted to see how the detailed sequence and functionality of bioinspired units could be used to make more complicated structures,” says Rachel Segalman, a faculty scientist at Berkeley Lab and professor of Chemical and Biomolecular Engineering at University of California, Berkeley.

With this in mind, the peptoid pieces were robotically synthesized, processed, and then added to a solution that fosters self assembly.

The result was a variety of self-made shapes and structures, with the braided helices being the most intriguing. The hierarchical structure of the helix, and its ability to be manipulated atom-by-atom, means that it could be used as a template for mineralizing complex structures on a nanometer scale.

“The idea is to assemble structurally complex structures at the nanometer scale with minimal input,” says Hannah Murnen. She adds that the scientists next hope is to capitalize on the fact that they have minute control over the structure’s sequence, and explore how very small chemical changes alter the helical structure.

Says Zuckermann,“These braided helices are one of the first forays into making atomically defined block copolymers. The idea is to take something we normally think of as plastic, and enable it to adopt structures that are more complex and capable of higher function, such as molecular recognition, which is what proteins do really well.”

X-ray diffraction experiments used to characterize the structures were conducted at beamlines 8.3.1 and 7.3.3 of Berkeley Lab’s Advanced Light Source, a national user facility that generates intense x-rays to probe the fundamental properties of substances. This work was supported in part by the Office of Naval Research.


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Monday, January 17, 2011

Controlled heating of gold nanoparticles

Controlled heating of gold nanoparticles

Tiny gold particles are good for transferring heat and could be a promising tool for creating localized heating in, for example, a living cell. In new experiments, German researchers at the Niels Bohr Institute have measured the temperature of nano-sized gold particles with extreme precision and have examined their ability to melt the lipid membranes surrounding cells, paving the way for dissolving sick cells. The results have been published in the esteemed journal<i>Nano Letters</i>.

Gold nano-particles have a strong interaction with light in relation to their size and it is precisely their physical size that gives them different colours. Its colour is the result of how strongly a gold particle scatters and absorbs light at different wavelengths. Therefore, when the light heats up the gold particle, the colour has significance for its temperature.

The research was conducted in the Optical Tweezers Group at the Niels Bohr Institute. Optical tweezers are sophisticated instruments, which using an extremely focused laser light can trap and holdon a. A nanometer is a thousandth of a millimeter and therefore very small. The gold particles are between 60 and 200in size.

"The particles can be heated usingfrom the optical tweezers and by turning the light up and down you can control the heat", explains PhD student in biophysics, Anders Kyrsting, who conducted the research along with his colleagues from thegroup.

But exactly how hot do the extremely small gold particles get? It is important to know the precise temperature in order to have complete control over the situation. The particles are too small to measure directly, so you can instead measure indirectly by their effect.

Anders Kyrsting brought the hot gold particles closer and closer towards an artificialcomprised of lipids. When quite close the lipids melt and if you know exactly when certain lipids melt you can use this to calculate the temperature of the gold particles. It turns out that the gold particles are able to reach several hundred degrees at a light intensity of less than 1 watt.

Gentle and effective

Having a hot particle means that you have a tool that you can use– a tiny little heat source, which is well-defined. By melting the lipids in a cell membrane the cell will be dissolved– killed. But only that cell.

"The heat decreases so rapidly that at just a radius of a gold particle from the surface, the heat is half the temperature than it is at the surface. That is to say, that a typical cell length away from the particle the heat will have decreased so much that it is harmless", explains Anders Kyrsting.

"The technique can also be used as a tool for changing temperatures in a few microseconds. When the temperature from the surface of a heated gold nanoparticle decreases several hundred degrees per micrometer, it is, for example, possible to have two separate states– a liquid and a more solid form in artificial cell systems consisting of smallvesicles. Here the border surface between the two states will be very clear-cut, which is useful if you want to study cell membranes", explains Anders Kyrsting.


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Sunday, January 16, 2011

Fabrication of mosaic nanofilters for molecular transport, separation of macromolecules

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A team led by Dr. Sherif El-Safty, Exploratory Materials Research Laboratory for Energy and Environment, National Institute for Materials Science (NIMS; Japan), fabricated tight mosaic cage silica nanotubes (NTs) inside anodic alumina membranes (AAM) as a promising candidate nanofilter for high-speed (within several seconds) size-exclusion separation of high concentration macromolecules.

To date, separation of proteins into relatively homogeneous groups and sizes has been very important in biopharmaceuticals and medicines. From the practical viewpoint, the requirements for these applications include easy scaling-up, fast separation, suitability for high production volumes, and low cost. Technically, the design of extremely robust filter membranes without formation of air gaps among membrane nanochannels is a remaining challenge, as pore gaps not only reduce the potential of size-exclusion nanofiltration systems, but also limit the long-term storage stability of NTs, making storage difficult even for a month.

For practical control of mosaic nanofilter membranes, a general approach based on densely engineered three-dimensional (3D) mesocage structures insideNTs was adopted. In this design, multifunctionalof the pore channels of the AAM facilitated production of extremely robust constructed sequences of membranes as“real nanofilters” without“detachment pores” (air gaps) between the fabricated nanotubes inside the AAM. The approach used by the NIMS team is ideal for constructing tubular-structured architectures inside membranes with vertical alignment, open surfaces of top-bottom ends, multidirectional (3D) pore connectivity, and stability, which are promising for application to nanofilter systems.

The key to this development was the fact that the nanofilter system efficiently separatessuch as proteins of various sizes over a wide, adjustable range of concentrations. Although conventional processes require as much as 12 hours or more, this technique provides a rapid filtration process that achieves filtration in seconds, despite the blocking effect of the proteins during the filtration process.

The intrinsic properties of the NIMS design (shelf-life or long-term stability, separation efficiency, reusability) are important advantages in comparison with the conventional protein nanofilter techniques used to date. Such advantages will be key to the development of a fabrication approach with the potential to become the optimal method for the design of nanofilters for filtration and molecular transport of multiple species.

The results of this research demonstrated that the NIMS approach offers a time- and cost-efficient alternative tool to current macromolecule analysis methods. This development also offers new insights into control design of devices in the fields of electronics, sensors, and other nanotechnologies.


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Saturday, January 15, 2011

'Nanoscoops' could spark new generation of electric automobile batteries

'Nanoscoops' could spark new generation of electric automobile batteries

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An entirely new type of nanomaterial developed at Rensselaer Polytechnic Institute could enable the next generation of high-power rechargeable lithium (Li)-ion batteries for electric automobiles, as well as batteries for laptop computers, mobile phones, and other portable devices.

The new material, dubbed a"nanoscoop"because its shape resembles a cone with a scoop of ice cream on top, can withstand extremely high rates of charge and discharge that would cause conventional electrodes used in today's Li-ion batteries to rapidly deteriorate and fail. The nanoscoop's success lies in its unique material composition, structure, and size.

The Rensselaer research team, led by Professor Nikhil Koratkar, demonstrated how a nanoscoop electrode could be charged and discharged at a rate 40 to 60 times faster than conventional battery anodes, while maintaining a comparable energy density. This stellar performance, which was achieved over 100 continuous charge/discharge cycles, has the team confident that their new technology holds significant potential for the design and realization of high-power, high-capacity Li-ion rechargeable batteries.

'Nanoscoops' could spark new generation of electric automobile batteries
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Researchers at Rensselaer Polytechnic Institute developed an entirely new type of nanomaterial that could enable the next generation of high-power rechargeable lithium (Li)-ion batteries for electric automobiles, laptop computers, mobile phones and other devices. The material, called a"nanoscoop"because it resembles a cone with a scoop of ice cream on top, is shown in the above scanning electron microscope image. Nanoscoops can withstand extremely high rates of charge and discharge that would cause today's Li-ion batteries to rapidly deteriorate and fail. Credit: Rensselaer/Koratkar

"Charging my laptop or cell phone in a few minutes, rather than an hour, sounds pretty good to me,"said Koratkar, a professor in the Department of Mechanical, Aerospace, and Nuclear Engineering at Rensselaer."By using our nanoscoops as the anode architecture for Li-ion, this is a very real prospect. Moreover, this technology could potentially be ramped up to suit the demanding needs of batteries for electric automobiles."

Batteries for all-electric vehicles must deliver high power densities in addition to high energy densities, Koatkar said. These vehicles today use supercapacitors to perform power-intensive functions, such as starting the vehicle and rapid acceleration, in conjunction with conventional batteries that deliver high energy density for normal cruise driving and other operations. Koratkar said the invention of nanoscoops may enable these two separate systems to be combined into a single, more efficient battery unit.

Results of the study were detailed in the paper"Functionally Strain-Graded Nanoscoops for High Power Li-Ion Battery Anodes,"published Thursday by the journalNano Letters.

The anode structure of a Li-ion battery physically grows and shrinks as the battery charges or discharges. When charging, the addition of Li ions increases the volume of the anode, while discharging has the opposite effect. These volume changes result in a buildup of stress in the. Too great a stress that builds up too quickly, as in the case of a battery charging or discharging at high speeds, can cause the battery to fail prematurely. This is why most batteries in today's portable electronic devices like cell phones and laptops charge very slowly– the slow charge rate is intentional and designed to protect the battery from stress-induced damage.

'Nanoscoops' could spark new generation of electric automobile batteries
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Researchers at Rensselaer Polytechnic Institute developed an entirely new type of nanomaterial that could enable the next generation of high-power rechargeable lithium (Li)-ion batteries for electric automobiles, laptop computers, mobile phones and other devices. The material, called a"nanoscoop"because it resembles a cone with a scoop of ice cream on top, is shown in the above scanning electron microscope image. Nanoscoops can withstand extremely high rates of charge and discharge that would cause today's Li-ion batteries to rapidly deteriorate and fail. Credit: Rensselaer/Koratkar

The Rensselaer team's nanoscoop, however, was engineered to withstand this buildup of stress. Made from a carbon (C) nanorod base topped with a thin layer of nanoscale aluminum (Al) and a"scoop"of nanoscale silicon (Si), the structures are flexible and able to quickly accept and discharge Li ions at extremely fast rates without sustaining significant damage. The segmented structure of the nanoscoop allows the strain to be gradually transferred from the C base to the Al layer, and finally to the Si scoop. This natural strain gradation provides for a less abrupt transition in stress across the material interfaces, leading to improved structural integrity of the electrode.

The nanoscale size of the scoop is also vital since nanostructures are less prone to cracking than bulk materials, according to Koratkar.

"Due to their nanoscale size, our nanoscoops can soak and release Li at high rates far more effectively than the macroscale anodes used in today's Li-ion batteries,"he said."This means our nanoscoop may be the solution to a critical problem facing auto companies and other battery manufacturers– how can you increase the power density of a battery while still keeping thehigh?"

A limitation of the nanoscoop architecture is the relatively low total mass of the electrode, Koratkar said. To solve this, the team's next steps are to try growing longer scoops with greater mass, or develop a method for stacking layers of nanoscoops on top of each other. Another possibility the team is exploring includes growing the nanoscoops on large flexible substrates that can be rolled or shaped to fit along the contours or chassis of the automobile.


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Friday, January 14, 2011

Researchers settle argument over mobility of flexible filaments (w/ Video)

(PhysOrg.com) -- Theo Odijk, you win. The professor of biotechnology at Delft University of Technology in the Netherlands has a new best friend in Rice University's Matteo Pasquali.

Together with collaborators at the French National Center for Scientific Research (CNRS), the University of Bordeaux, France, and Vrije University, Amsterdam, the Rice professor and his team have settled a long-standing controversy in the field of polymer dynamics: The researchers proved once and for all that Odijk was correct in proclaiming that a little flexibility goes a long way for stiffin a solution.

The study in the current issue of the journalScienceshows that even a small ability to bend givesand other tiny, stiff filaments the means to navigate through crowded environments, or even such fixed networks as cell matrices.

The work by Pasquali, a professor in chemical and biomolecular engineering and in chemistry, may bring about new ways to influence the motion of tiny filaments by tailoring their stiffness for a given environment.

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A video of a reptating nanotube

Nanotubes are being studied for potential use in all kinds of sensing, even in the seemingly disparate fields of biological applications and oil exploration. In both, the ability of nanotubes and other fine, filamentous particles to move through their environments is critical, Pasquali said.

Understanding the motion of a single,chain in a network has been key to scientific advances by Odijk and others on, for example, the behavior of DNA. The Rice researchers expect their revelation to have no less impact.

Pasquali and lead author Nikta Fakhri, a former graduate student at Rice now doing postdoctoral research at the University of Gottingen, Germany, set out to break the deadlocked theories by Odijk and two other scientists who disagreed on the Brownian motion of stiff filaments in a crowded environment, and whether stiffness itself played any part.

"There's a long-standing, fundamental question: How does this threadlike object move when it gets crowded? It could be crowded because it's in a gel, or because there are a lot of threadlike objects with it -- which to that one object looks like a gel,"he said.

Crowding constrains the ability of a filament to travel. Think of trying to get from the back to the front of a crowded bus; it takes a certain amount of agility to weave your way through the packed bodies."It turns out that with a little flexibility, a filament can explore the space around it much more effectively,"Pasquali said.

That becomes important when the goal is to get filaments to find and enter a cellular pore to deliver a dose of medication or to act as a fluorescent sensor.

"If you look at the human body, they say we're made of 60 percent water, but we don't slosh around,"Pasquali explained."That's because the water is trapped in pores. Almost all the water in our body is in gel-like structures: inside our cells, which are laden with filamentous networks, or in the interstitial fluid surrounding these cells. We are a big, squishy, porous medium. We need to understand how the nanoparticles move in this medium."

Pasquali and Fakhri mimicked biological networks by using varying concentrations of agarose gel, a porous material often used as a filter in biochemistry and molecular biology for DNA and proteins. The gel forms a matrix of controllable size through which molecules can move.

Nanotubes served as a stand-in for any type of filament, albeit one whose stiffness can be controlled. Like a PVC pipe in the macro world, nanotubes get stiffer as they get thicker; but even the stiffest tubes can flex a bit with length, and these tubes were thousands of times longer than they were wide.

The study started somewhat serendipitously when co-author Laurent Cognet, a researcher at CNRS and the University of Bordeaux, tried to immobilize nanotubes in agarose gels. He noticed in a failed experiment that the nanotubes moved in a"funny way"and discussed it with Pasquali.

Pasquali asked whether the nanotubes were reptating -- scientist lingo for a snakelike motion -- and Cognet said yes. Fakhri, who was studying the dynamics of nanotubes, traveled to the Bordeaux laboratory of Cognet and co-author Brahim Lounis to capture images of the nanotubes in motion.

The resulting spectroscopic and direct still and video images of 35 fluorescent single-walled nanotubes showed them snaking through the gel, probing pores and paths. The nanotubes, like all filaments, obeyed the rules of thermal-induced Brownian motion; they were pushed and pulled by the ever-changing states of the molecules around them.

The research established that flexibility significantly enhances the nanotubes' ability to navigate around obstacles and speeds up their exploration.

Pasquali said Fakhri doggedly pursued her analysis of the nanotubes' motion through computerized image recognition and motion tracking, as well as old-fashioned pencil-and-paper dynamical analysis. He said his longtime collaborator, co-author Frederick MacKintosh, a theoretical physicist at Vrije University, was a tremendous help. MacKintosh has been studying the dynamics of biological networks for nearly two decades.

Pasquali intends to replace the gel with real rocks to see how nanotubes, which can be used as oil-detecting sensors, move in a more structured environment."Rocks can be a little more complicated,"he said."The question here is, what can nanotubes do better than nanoparticles? The answer may be that slender nanotubes may interact with electromagnetic fields more strongly than other nanoparticles of the same volume."


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Thursday, January 13, 2011

Self-assembling structures open door to new class of materials

Self-assembling structures open door to new class of materials

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Researchers at the University of Illinois and Northwestern University have demonstrated bio-inspired structures that self-assemble from simple building blocks: spheres.

The helical"supermolecules"are made of tiny colloid balls instead of atoms or molecules. Similar methods could be used to makewith the functionality of complex colloidal molecules. The team will publish its findings in the Jan. 14 issue of the journalScience.

"We can now make a whole new class of, which opens the door to new functionality that we couldn't imagine before,"said Steve Granick, Founder Professor of Engineering at the University of Illinois and a professor of materials science and engineering, chemistry, and physics.

Granick's team developed tiny latex spheres, dubbed"Janus spheres,"which attract each other in water on one side, but repel each other on the other side. The dual nature is what gives the spheres their ability to form unusual structures, in a similar way to atoms and molecules.

In pure water, the particles disperse completely because their charged sides repel one another. However, when salt is added to the solution, the salt ions soften theso the spheres can approach sufficiently closely for their hydrophobic ends to attract. The attraction between those ends draws the spheres together into clusters.

At low salt concentrations, small clusters of only a few particles form. At higher levels, larger clusters form, eventually self-assembling into chains with an intricate helical structure.

"Just like atoms growing into molecules, these particles can grow into supracolloids,"Granick said."Such pathways would be very conventional if we were talking about atoms and molecules reacting with each other chemically, but people haven't realized that particles can behave in this way also."

The team designed spheres with just the right amount of attraction between their hydrophobic halves so that they would stick to one another but still be dynamic enough to allow for motion, rearrangement, and cluster growth.

"The amount of stickiness really does matter a lot. You can end up with something that's disordered, just small clusters, or if the spheres are too sticky, you end up with a globular mess instead of these beautiful structures,"said graduate student Jonathan Whitmer, a co-author of the paper.

One of the advantages of the team's supermolecules is that they are large enough to observe in real time using a microscope. The researchers were able to watch the Janus spheres come together and the clusters grow– whether one sphere at a time or by merging with other small clusters– and rearrange into different structural configurations the team calls isomers.

"We design these smart materials to fall into useful shapes that nature wouldn't choose,"Granick said.

Surprisingly, theoretical calculations and computer simulations by Erik Luijten, Northwestern University professor of materials science and engineering and of engineering sciences and applied mathematics, and Whitmer, a student in his group, showed that the most common helical structures are not the most energetically favorable. Rather, the spheres come together in a way that is the most kinetically favorable– that is, the first good fit that they encounter.

Next, the researchers hope to continue to explore the colloid properties with a view toward engineering more unnatural structures. Janus particles of differing sizes or shapes could open the door to building other supermolecules and to greater control over their formation.

"These particular particles have preferred structures, but now that we realize the general mechanism, we can apply it to other systems– smaller, different interactions– and try to engineer clusters that switch in shape,"Granick said.


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Wednesday, January 12, 2011

Novel technique selects molecules according to their chemical properties and dimensions

Selection by size and substance

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Separating molecules is an important part of many manufacturing and testing processes, including pharmaceutical production and some biomedical tests. One way of carrying out such separation is by using nanofilters -- materials with holes of a precisely controlled tiny diameter, to allow molecules up to that size to pass through while blocking any that are larger. But a new system devised by researchers at MIT could add an important new capability: a way to selectively filter out molecules of the same size that have different chemical properties.

Karen Gleason, an MIT professor of chemical engineering and associate dean of engineering for research, and postdoctoral fellow Ayse Asatekin described the process in a paper published this month in the journal.

This is“a fundamentally different way” of separating, Gleason says.“People usually think of size as being the defining factor,” but by making the pores in the filter small enough so that there is a significant chemical interaction between the pore walls and the molecules passing through them, it becomes possible to discriminate according to other characteristics, she explains. In this case, the selection was based on the molecules’ affinity for water. Because the walls of the pores were hydrophobic (water repelling), other hydrophobic molecules were more easily drawn to the pores and propelled through them than were other, less hydrophobic molecules.

In living organisms, cell walls routinely perform this kind of chemical separation, letting certain specific kinds of molecules— for example, nutrients, enzymes or signaling molecules— pass freely through pores in a cell membrane, while blocking all others. But this is the first time, Asatekin says, that such chemical separation has been demonstrated in a synthetic membrane.

Many biological molecules that are similar in size yet have very different functions or properties, so the ability to separate them efficiently could be important. In this initial proof-of-concept demonstration, the molecules selected were two dyes, chosen because of their similar size and ease of detection. Using a polycarbonate membrane (a type of plastic) treated with a vapor-deposited layer of another polymer, the researchers were able to separate the two dyes very effectively, with more than 200 times more of one type passing through than the other. The coating process they used not only adds the capability for discriminating between molecules based on their differing affinities for water, but by coating the insides of tube-like pores in the material it also provides a way of creating extremely small pores of uniform size— much smaller than can be produced by conventional methods.

Joerg Lahann, an associate professor of chemical engineering at the University of Michigan who was not involved in this work, says that the team’s ability to produce tiny, uniform pores smaller than 10 nanometers (billionths of a meter) across is itself a significant accomplishment that solves a major problem in existing nanoseparation technology.

To test how the system works, the team tried making two different kinds of pores— some that were uniformly sized tubes, others that had a narrow bottleneck at one point and then widened out. The uniform cylinders were much more effective, demonstrating that the key factor is the interaction of the molecules with the wall of the pore over its entire length, which in this case was about 4,000 times the width.

In pharmaceutical manufacturing, many processes involve chemical reactions in which both the reactants and the chemical being produced are very similar in molecular size, so being able to separate the two efficiently could be a significant advance in allowing large-throughput processing instead of small-batch production as is done currently, Asatekin says.

In addition to possible applications in drug manufacturing, such membranes could be important for the detection of biologically significant molecules. For example, the U.S. military, which funded this research through the Institute for Soldier Nanotechnology, is interested in their possible use in detectors that could identify a chemical marker the body produces when an inflammatory response is triggered, which could be a way of quickly revealing that the body had been exposed to a toxin even without knowing what the toxin was.

As a next step, Asatekin and Gleason plan to try the technique to separate biomolecules that are of real relevance to biological processes, to demonstrate that it works for materials that would be of interest for actual applications.

Professor Mathias Ulbricht, chair of technical chemistry at the University of Duisburg-Essen in Germany, calls this a“powerful experimental demonstration” of a new technique that he says holds great promise for practical applications.

“This study opens a new avenue for truly‘tailored’ nanoporous membranes with different selectivities than those of traditional membranes,” he says.“More experimental work toward preparation of membranes with varied structure and other separation experiments are to be done. However, I am optimistic that the promising prospects can be demonstrated practically in such follow-up studies.”


This story is republished courtesy of MIT News (http://web.mit.edu/newsoffice/), a popular site that covers news about MIT research, innovation and teaching.


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Tuesday, January 11, 2011

Polymer membranes with molecular-sized channels that assemble themselves

Polymer membranes with molecular-sized channels that assemble themselves

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(PhysOrg.com) -- Many futurists envision a world in which polymer membranes with molecular-sized channels are used to capture carbon, produce solar-based fuels, or desalinating sea water, among many other functions. This will require methods by which such membranes can be readily fabricated in bulk quantities. A technique representing a significant first step down that road has now been successfully demonstrated.

Researchers with the U.S. Department of Energy's Lawrence Berkeley National Laboratory (Berkeley Lab) and the University of California (UC) Berkeley have developed a solution-based method for inducing the self-assembly ofmembranes with highly aligned subnanometer channels. Fully compatible with commercial membrane-fabrication processes, this new technique is believed to be the first example of organicfabricated into a functional membrane over macroscopic distances.

"We've used nanotube-forming cyclic peptides and block co-polymers to demonstrate a directed co-assembly technique for fabricating subnanometer porous membranes over macroscopic distances,"says Ting Xu, a polymer scientist who led this project."This technique should enable us to generate porous thin films in the future where the size and shape of the channels can be tailored by the molecular structure of the organic nanotubes."

Polymer membranes with molecular-sized channels that assemble themselves
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Schematic drawing depicts process by which a polymer is tethered to cyclic peptides (8CP)then blended with block copolymers (BCPs) to make a membrane permeated with subnanometer channels in the form of organic nanotubes.

Xu, who holds joint appointments with Berkeley Lab's Materials Sciences Division and the University of California Berkeley's Departments of Materials Sciences and Engineering, and Chemistry, is the lead author of a paper describing this work, which has been published in the journalACS Nano. The paper is titled"Subnanometer Porousby the Co-assembly of Nanotube Subunits and."Co-authoring the paper with Xu were Nana Zhao, Feng Ren, Rami Hourani, Ming Tsang Lee, Jessica Shu, Samuel Mao, and Brett Helms, who is with the Molecular Foundry, a DOE nanoscience center hosted at Berkeley Lab.

Channeled membranes are one of nature's most clever and important inventions. Membranes perforated with subnanometer channels line the exterior and interior of a biological cell, controlling– by virtue of size– the transport of essential molecules and ions into, through, and out of the cell. This same approach holds enormous potential for a wide range of human technologies, but the challenge has been finding a cost-effective means of orienting vertically-aligned subnanometer channels over macroscopic distances on flexible substrates.

"Obtaining molecular level control over the pore size, shape, and surface chemistry of channels in polymer membranes has been investigated across many disciplines but has remained a critical bottleneck,"Xu says."Composite films have been fabricated using pre-formed carbon nanotubes and the field is making rapid progess, however, it still presents a challenge to orient pre-formed nanotubes normal to the film surface over macroscopic distances."

For their subnanometer channels, Xu and her research group used the organic nanotubes naturally formed by cyclic peptides - polypeptide protein chains that connect at either end to make a circle. Unlike pre-formed carbon nanotubes, these organic nanotubes are"reversible,"which means their size and orientation can be easily modified during the fabrication process. For the membrane, Xu and her collaborators used block copolymers - long sequences or"blocks"of one type of monomer molecule bound to blocks of another type of monomer molecule. Just as cyclic peptides self-assemble into nanotubes, block copolymers self-assemble into well-defined arrays of nanostructures over macroscopic distances. A polymer covalently linked to the cyclic peptide was used as a"mediator"to bind together these two self-assembling systems

"The polymer conjugate is the key,"Xu says."It controls the interface between theand the block copolymers and synchronizes their self-assembly. The result is that nanotube channels only grow within the framework of the polymer membrane. When you can make everything work together this way, the process really becomes very simple."

Xu and her colleagues were able to fabricate subnanometer porous membranes measuring several centimeters across and featuring high-density arrays of channels. The channels were tested via gas transport measurements of carbon dioxide and neopentane. These tests confirmed that permeance was higher for the smaller carbon dioxide molecules than for the larger molecules of neopentane. The next step will be to use this technique to make thicker membranes.

"Theoretically, there are no size limitations for our technique so there should be no problem in making membranes over large area,"Xu says."We're excited because we believe this demonstrates the feasibility of synchronizing multiple self-assembly processes by tailoring secondary interactions between individual components. Our work opens a new avenue to achieving hierarchical structures in a multicomponent system simultaneously, which in turn should help overcome the bottleneck to achieving functional materials using a bottom-up approach."


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Monday, January 10, 2011

Researchers 'recalculate' efficiency paradigm for thin film solar panels

In recent years, developers have been investigating light-harvesting thin film solar panels made from nanotechnology -- and promoting efficiency metrics to make the technology marketable. Now a Tel Aviv University researcher is providing new evidence to challenge recent"charge"measurements for increasing solar panel efficiency.

Offering a less expensive, smaller solution than traditional panels, Prof. Eran Rabani of Tel Aviv University's School of Chemistry at the Raymond and Beverly Sackler Faculty of Exact Sciences puts a lid on some current hype that promises to increase efficiencies in thin film panels. His research, published recently in the journalsNano Lettersand Chemical Physics Letters, may bring the development of new solar energy technologies more down to earth.

Prof. Rabani combines a new theoretical approach with."Our theory shows that current predictions to increase efficiencies won't work. The increase in efficiencies cannot be achieved yet through Multiexciton Generation, a process by which several charge carriers (electrons and holes) are generated from one photon,"he says.

Inefficient as"charged"

But both new and existing theories bode well for the development of other strategies in future solar energy technology, he points out. Newer approaches published in journals such as Science may provide means for increasing the efficiencies of, and perhaps would also be useful in storage of solar energy, Prof. Rabani and his team of researchers believe.

A chemical physicist, Prof. Rabani investigates how to separate charges from the sun efficiently. In 2004, physicists suggested that more than one electron-hole pair could be pulled from one photon in a complicated process in. If this were possible, the charge would be doubled, and so the solar energy efficiency would increase."We've shown that this idea doesn't work,"Prof. Rabani says.

One step closer to marketing the sun

The development of more efficient and less expensive devices to make use ofis one of the greatest challenges in science today. Billions of dollars are being spent to find the best methods to collect electron"charges"from the sun.

Typically, one photon from the sun absorbed in a thin film solar panel can excite one electron-hole pair, which is then converted to electricity. Currently there are claims that if more electron-hole pairs can be excited after the photon is absorbed, a larger fraction of the photon energy can successfully be converted into electricity, thus increasing device efficiency.

The theory that Prof. Rabani developed with his Israeli colleagues shows why this process is not as efficient as originally conceived. It's bad news for panel producers looking to create more efficient, but good news for researchers who are now free to look to the next realistic step for developing a technology that works.


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Sunday, January 9, 2011

New solar cell self-repairs like natural plant systems

New solar cell self-repairs like natural plant systems

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(PhysOrg.com) -- Researchers are creating a new type of solar cell designed to self-repair like natural photosynthetic systems in plants by using carbon nanotubes and DNA, an approach aimed at increasing service life and reducing cost.

"We've created artificial photosystems using opticalto harvestthat is converted to electrical power,"said Jong Hyun Choi, an assistant professor of mechanical engineering at Purdue University.

The design exploits the unusualof structures called single-wall carbon nanotubes, using them as"molecular wires in light harvesting cells,"said Choi, whose research group is based at the Birck Nanotechnology and Bindley Bioscience centers at Purdue's Discovery Park.

"I think our approach offers promise for industrialization, but we're still in the basic research stage,"he said.

Photoelectrochemical cells convert sunlight into electricity and use an- a liquid that conducts electricity - to transport electrons and create the current. The cells contain light-absorbing dyes called chromophores, chlorophyll-like molecules that degrade due to exposure to sunlight.

"The critical disadvantage of conventionalis this degradation,"Choi said.

The new technology overcomes this problem just as nature does: by continuously replacing the photo-damaged dyes with new ones.

"This sort of self-regeneration is done in plants every hour,"Choi said.

The new concept could make possible an innovative type of photoelectrochemical cell that continues operating at full capacity indefinitely, as long as new chromophores are added.

Findings were detailed in a November presentation during the International Mechanical Engineering Congress and Exhibition in Vancouver. The concept also was unveiled in anonline articlefeatured on the Web site for SPIE, an international society for optics and.

The talk and article were written by Choi, doctoral students Benjamin A. Baker and Tae-Gon Cha, and undergraduate students M. Dane Sauffer and Yujun Wu.

The carbon nanotubes work as a platform to anchor strands of DNA. The DNA is engineered to have specific sequences of building blocks called nucleotides, enabling them to recognize and attach to the chromophores.

"The DNA recognizes the dye molecules, and then the system spontaneously self-assembles,"Choi said

When the chromophores are ready to be replaced, they might be removed by using chemical processes or by adding new DNA strands with different nucleotide sequences, kicking off the damaged dye molecules. New chromophores would then be added.

Two elements are critical for the technology to mimic nature's self-repair mechanism: molecular recognition and thermodynamic metastability, or the ability of the system to continuously be dissolved and reassembled.

The research is an extension of work that Choi collaborated on with researchers at the Massachusetts Institute of Technology and the University of Illinois. The earlier work used biological chromophores taken from bacteria, and findings were detailed in a researchpaper publishedin November in the journalNature Chemistry.

However, using natural chromophores is difficult, and they must be harvested and isolated from bacteria, a process that would be expensive to reproduce on an industrial scale, Choi said.

"So instead of using biological chromophores, we want to use synthetic ones made of dyes called porphyrins,"he said.


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Saturday, January 8, 2011

Graphene electrodes for organic solar cells

Graphene electrodes for organic solar cells

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A promising approach for making solar cells that are inexpensive, lightweight and flexible is to use organic (that is, carbon-containing) compounds instead of expensive, highly purified silicon. But one stubborn problem has slowed the development of such cells: Researchers have had a hard time coming up with appropriate materials for the electrodes to carry the current to and from the cells. Specifically, it has been hard to make electrodes using materials that can match the organic cells’ flexibility, transparency and low cost.

The standard material used so far for these electrodes is indium-tin-oxide, or ITO. But indium is expensive and relatively rare, so the search has been on for a suitable replacement. Now, a team of MIT researchers has come up with a practical way of using a possible substitute made from inexpensive and ubiquitous carbon. The proposed material is graphene, a form of carbon in which the atoms form a flat sheet just one atom thick, arranged in a chicken-wire-like formation.

An analysis of how to use graphene as an electrode for such solar cellswas published on Dec. 17in the journalNanotechnology, in a paper by MIT professors Jing Kong and Vladimir Bulović along with two of their students and a postdoctoral researcher.

Graphene is transparent, so that electrodes made from it can be applied to the transparentwithout blocking any of the incoming light. In addition, it is flexible, like the organic solar cells themselves, so it could be part of installations that require the panel to follow the contours of a structure, such as a patterned roof. ITO, by contrast, is stiff and brittle.

The biggest problem with getting graphene to work as an electrode for organic solar cells has been getting the material to adhere to the panel. Graphene repels water, so typical procedures for producing an electrode on the surface by depositing the material from a solution won’t work.

The team tried a variety of approaches to alter the surface properties of the cell or to use solutions other than water to deposit the carbon on the surface, but none of these performed well, Kong says. But then they found that“doping” the surface— that is, introducing a set of impurities into the surface— changed the way it behaved, and allowed the graphene to bond tightly. As a bonus, it turned out the doping also improved the material’s electrical conductivity.

While the specific characteristics of the graphene electrode differ from those of the ITO it would replace, its overall performance in a solar cell is very similar, Kong says. And the flexibility and light weight of organic solar cells with graphene electrodes could open up a variety of different applications that would not be possible with today’s conventional silicon-based solar panels, she says. For example, because of their transparency they could be applied directly to windows without blocking the view, and they could be applied to irregular wall or rooftop surfaces. In addition, they could be stacked on top of other solar panels, increasing the amount of power generated from a given area. And they could even be folded or rolled up for easy transportation.

While this research looked at how to adapt graphene to replace one of the two electrodes on a solar panel, Kong and her co-workers are now trying to adapt it to the other electrode as well. In addition, widespread use of this technology will require new techniques for large-scale manufacturing of graphene— an area of very active research. The ongoing work has been funded by the Eni-MIT Alliance Solar Frontiers Center and an NSF research fellowship.

Peter Peumans, an assistant professor of electrical engineering at Stanford University, who was not involved in this study, says organicwill probably become practical only with the development of transparent electrode technology that is both cheaper and more robust than conventional metal oxides. Other materials are being studied as possible substitutes, he says, but this work represents“very important progress” toward making graphene a credible replacement transparent electrode.

“Other groups had already shown that graphene exhibits good combinations of transparency and sheet resistance, but no one was able to achieve a performance with graphene electrodes that matches that of devices on conventional metal oxide (ITO),” Peumans says.“This work is a substantial push toward making graphene a leading candidate.”


This story is republished courtesy of MIT News (http://web.mit.edu/newsoffice/), a popular site that covers news about MIT research, innovation and teaching.


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Friday, January 7, 2011

Extending Moore's Law: Expitaxial graphene shows promise for replacing silicon in electronics

Expitaxial Graphene Shows Promise for Replacing Silicon in Electronics

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(PhysOrg.com) -- Move over silicon. There's a new electronic material in town, and it goes fast. That material, the focus of the 2010 Nobel Prize in physics, is graphene -- a fancy name for extremely thin layers of ordinary carbon atoms arranged in a"chicken-wire"lattice. These layers, sometimes just a single atom thick, conduct electricity with virtually no resistance, very little heat generation -- and less power consumption than silicon.

Withdevice fabrication approaching its physical limits, many researchers believe graphene can provide a new platform material that would allow theto continue its march toward ever-smaller and faster electronic devices -- progress described in Moore's Law. Though graphene will likely never replace silicon for everyday electronic applications, it could take over as the material of choice for high-performance devices.

And graphene could ultimately spawn a new generation of devices designed to take advantage of its unique properties.

Since 2001, Georgia Tech has become a world leader in developing epitaxial graphene, a specific type of graphene that can be grown on large wafers and patterned for use in electronics manufacturing. In a recent paper published in theNanotechnology, Georgia Tech researchers reported fabricating an array of 10,000 top-gated transistors on a 0.24 square centimeter chip, an achievement believed to be the highest density reported so far in graphene devices.

In creating that array, they also demonstrated a clever new approach for growing complex graphene patterns on templates etched into. The new technique offered the solution to one of the most difficult issues that had been facing graphene electronics.

"This is a significant step toward electronics manufacturing with graphene,"said Walt de Heer, a professor in Georgia Tech's School of Physics who pioneered the development of graphene for high-performance electronics."This is another step showing that our method of working with epitaxial graphene grown on silicon carbide is the right approach and the one that will probably be used for making graphene electronics."

Unrolled Carbon Nanotubes

For de Heer, the story of graphene begins with carbon nanotubes, tiny cylindrical structures considered miraculous when they first began to be studied by scientists in 1991. De Heer was among the researchers excited about the properties of nanotubes, whose unique arrangement ofgave them physical and electronic properties that scientists believed could be the foundation for a new generation of electronic devices.

Carbon nanotubes still have attractive properties, but the ability to grow them consistently -- and to incorporate them in high-volume electronics applications -- has so far eluded researchers. De Heer realized before others that carbon nanotubes would probably never be used for high-volume electronic devices.

But he also realized that the key to the attractive electronic properties of the nanotubes was the lattice created by the carbon atoms. Why not simply grow that lattice on a flat surface, and use fabrication techniques proven in the microelectronics industry to create devices in much the same way as silicon integrated circuits?

By heating silicon carbide -- a widely-used electronic material -- de Heer and his colleagues were able to drive silicon atoms from the surface, leaving just the carbon lattice in thin layers of graphene large enough to grow the kinds of electronic devices familiar to a generation of electronics designers.

That process was the basis for a patent filed in 2003, and for initial research support from chip-maker Intel. Since then, de Heer's group has published dozens of papers and helped spawn other research groups also using epitaxial graphene for electronic devices. Though scientists are still learning about the material, companies such as IBM have launched research programs based on epitaxial graphene, and agencies such as the National Science Foundation (NSF) and Defense Advanced Research Projects Agency (DARPA) have invested in developing the material for future electronics applications.

Georgia Tech's work on developing epitaxial graphene for manufacturing electronic devices was recognized in the background paper produced by the Royal Swedish Academy of Sciences as part of the Nobel Prize documentation.

The race to find commercial applications for graphene is intense, with researchers from the United States, Europe, Japan and Singapore engaged in well-funded efforts. Since awarding of the Nobel to a group from the United Kingdom, the flood of news releases about graphene developments has grown.

"Our epitaxial graphene is now used around the world by many research laboratories,"de Heer noted."We are probably at the stage where silicon was in the 1950s. This is the beginning of something that is going to be very large and important."

Silicon"Running Out of Gas"

A new electronics material is needed because silicon is running out of miniaturization room.

"Primarily, we've gotten the speed increases from silicon by continually shrinking feature sizes and improving interconnect technology,"said Dennis Hess, director of the National Science Foundation-sponsored Materials Research Science and Engineering Center (MRSEC) established at Georgia Tech to study future electronic materials, starting with epitaxial graphene."We are at the point where in less than 10 years, we won't be able to shrink feature sizes any farther because of the physics of the device operation. That means we will either have to change the type of device we make, or change the electronic material we use."

It's a matter of physics. At the very small size scales needed to create ever more dense device arrays, silicon generates too much resistance to electron flow, creating more heat than can be dissipated and consuming too much power.

Graphene has no such restrictions, and in fact, can provide electron mobility as much as 100 times better than silicon. De Heer believes his group has developed the roadmap for the future of high-performance electronics -- and that it is paved with epitaxial graphene.

"We have basically developed a whole scheme for making electronics out of graphene,"he said."We have set down what we believe will be the ground rules for how that will work, and we have the key patents in place."

Silicon, of course, has matured over many generations through constant research and improvement. De Heer and Hess agree that silicon will always be around, useful for low-cost consumer products such as iPods, toasters, personal computers and the like.

De Heer expects graphene to find its niche doing things that couldn't otherwise be done.

"We're not trying to do something cheaper or better; we're going to do things that can't be done at all with silicon,"he said."Making electronic devices as small as a molecule, for instance, cannot be done with silicon, but in principle could be done with graphene. The key question is how to extend Moore's Law in a post-CMOS world."

Unlike the carbon nanotubes he studied in the 1990s, de Heer sees no major problems ahead for the development of epitaxial graphene.

"That graphene is going to be a major player in the electronics of the future is no longer in doubt,"he said."We don't see any real roadblocks ahead. There are no flashing red lights or other signs that seem to say that this won't work. All of the issues we see relate to improving technical issues, and we know how to do that."

Making the Best Graphene

Since beginning the exploration of graphene in 2001, de Heer and his research team have made continuous improvements in the quality of the material they produce, and those improvements have allowed them to demonstrate a number of physical properties -- such as the Quantum Hall Effect -- that verify the unique properties of the material.

"The properties that we see in our epitaxial graphene are similar to what we have calculated for an ideal theoretical sheet of graphene suspended in the air,"said Claire Berger, a research scientist in the Georgia Tech School of Physics who also has a faculty appointment at the Centre National de la Recherche Scientifique in France."We see these properties in the electron transport and we see these properties in all kinds of spectroscopy. Everything that is supposed to be occurring in a single sheet of graphene we are seeing in our systems."

Key to the material's future, of course, is the ability to make electronic devices that work consistently. The researchers believe they have almost reached that point.

"All of the properties that epitaxial graphene needs to make it viable for electronic devices have been proven in this material,"said Ed Conrad, a professor in Georgia Tech's School of Physics who is also a MRSEC member."We have shown that we can make macroscopic amounts of this material, and with the devices that are scalable, we have the groundwork that could really make graphene take off."

Reaching higher and higher device density is also important, along with the ability to control the number of layers of graphene produced. The group has demonstrated that in their multilayer graphene, each layer retains the desired properties.

"Multilayer graphene has different stacking than graphite, the material found in pencils,"Conrad noted."In graphite, every layer is rotated 60 degrees and that's the only way that nature can do it. When we grow graphene on silicon carbide, the layers are rotated 30 degrees. When that happens, the symmetry of the system changes to make the material behave the way we want it to."

Epitaxial Versus Exfoliated

Much of the world's graphene research -- including work leading to the Nobel -- involved the study of exfoliated graphene: layers of the material removed from a block of graphite, originally with tape. While that technique produces high-quality graphene, it's not clear how that could be scaled up for industrial production.

While agreeing that the exfoliated material has produced useful information about graphene properties, de Heer dismisses it as"a science project"unlikely to have industrial electronics application.

"Electronics companies are not interested in graphene flakes,"he said."They need industrial graphene, a material that can be scaled up for high-volume manufacturing. Industry is now getting more and more interested in what we are doing."

De Heer says Georgia Tech's place in the new graphene world is to focus on electronic applications.

"We are not really trying to compete with these other groups,"he said."We are really trying to create a practical electronic material. To do that, we will have to do many things right, including fabricating a scalable material that can be made as large as a wafer. It will have to be uniform and able to be processed using industrial methods."

Resolving Technical Issues

Among the significant technical issues facing graphene devices has been electron scattering that occurs at the boundaries of nanoribbons. If the edges aren't perfectly smooth -- as usually happens when the material is cut with electron beams -- the roughness bounces electrons around, creating resistance and interference.

To address that problem, de Heer and his team recently developed a new"templated growth"technique for fabricating nanometer-scale graphene devices. The technique involves etching patterns into the silicon carbide surfaces on which epitaxial graphene is grown. The patterns serve as templates directing the growth of graphene structures, allowing the formation of nanoribbons of specific widths without the use of e-beams or other destructive cutting techniques. Graphene nanoribbons produced with these templates have smooth edges that avoid electron-scattering problems.

"Using this approach, we can make very narrow ribbons of interconnected graphene without the rough edges,"said de Heer."Anything that can be done to make small structures without having to cut them is going to be useful to the development of graphene electronics because if the edges are too rough, electrons passing through the ribbons scatter against the edges and reduce the desirable properties of graphene."

In nanometer-scale graphene ribbons, quantum confinement makes the material behave as a semiconductor suitable for creation of electronic devices. But in ribbons a micron or so wide, the material acts as a conductor. Controlling the depth of the silicon carbide template allows the researchers to create these different structures simultaneously, using the same growth process.

"The same material can be either a conductor or a semiconductor depending on its shape,"noted de Heer."One of the major advantages of graphene electronics is to make the device leads and the semiconducting ribbons from the same material. That's important to avoid electrical resistance that builds up at junctions between different materials."

After formation of the nanoribbons, the researchers apply a dielectric material and metal gate to construct field-effect transistors. While successful fabrication of high-quality transistors demonstrates graphene's viability as an electronic material, de Heer sees them as only the first step in what could be done with the material.

"When we manage to make devices well on the nanoscale, we can then move on to make much smaller and finer structures that will go beyond conventional transistors to open up the possibility for more sophisticated devices that use electrons more like light than particles,"he said."If we can factor quantum mechanical features into electronics, that is going to open up a lot of new possibilities."

Collaborations with Other Groups

Before engineers can use epitaxial graphene for the next generation of electronic devices, they will have to understand its unique properties. As part of that process, Georgia Tech researchers are collaborating with scientists at the National Institute of Standards and Technology (NIST). The collaboration has produced new insights into how electrons behave in graphene.

In a recent paper published in the journalNature Physics, the Georgia Tech-NIST team described for the first time how the orbits of electrons are distributed spatially by magnetic fields applied to layers of epitaxial graphene. They also found that these electron orbits can interact with the substrate on which the graphene is grown, creating energy gaps that affect how electron waves move through the multilayer material.

"The regular pattern of magnetically-induced energy gaps in the graphene surface creates regions where electron transport is not allowed,"said Phillip N. First, a professor in the Georgia Tech School of Physics and MRSEC member."Electron waves would have to go around these regions, requiring new patterns of electron wave interference. Understanding this interference would be important for some bi-layer graphene devices that have been proposed."

Earlier NIST collaborations led to improved understanding of graphene electron states, and the way in which low temperature and high magnetic fields can affect energy levels. The researchers also demonstrated that atomic-scale moiré patterns, an interference pattern that appears when two or more graphene layers are overlaid, can be used to measure how sheets of graphene are stacked.

In a collaboration with the U.S. Naval Research Laboratory and University of Illinois at Urbana-Champaign, a group of Georgia Tech professors developed a simple and quick one-step process for creating nanowires on graphene oxide.

"We've shown that by locally heating insulating graphene oxide, both the flakes and the epitaxial varieties, with an atomic force microscope tip, we can write nanowires with dimensions down to 12 nanometers,"said Elisa Riedo, an associate professor in the Georgia Tech School of Physics and a MRSEC member."And we can tune their electronic properties to be up to four orders of magnitude more conductive."

A New Industrial Revolution?

Though graphene can be grown and fabricated using processes similar to those of silicon, it is not easily compatible with silicon. That means companies adopting it will also have to build new fabrication facilities -- an expensive investment. Consequently, de Heer believes industry will be cautious about moving into a new graphene world.

"Silicon technology is completely entrenched and well developed,"he admitted."We can adopt many of the processes of silicon, but we can't easily integrate ourselves into silicon. Because of that, we really need a major paradigm shift. But for the massive electronics industry, that will not happen easily or gently."

He draws an analogy to steamships and passenger trains at the dawn of the aviation age. At some point, it became apparent that airliners were going to replace both ocean liners and trains in providing first-class passenger service. Though the cost of air travel was higher, passengers were willing to pay a premium for greater speed.

"We are going to see a coexistence of technologies for a while, and how the hybridization of graphene and silicon electronics is going to happen remains up in the air,"de Heer predicted."That is going to take decades, though in the next ten years we are probably going to see real commercial devices that involve."


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