Shooting light a curve: New tool may yield smaller, faster optoelectronics

 One of the earliest lessons in science that students learn is that a ray or beam of light travels in a straight line. Students also learn that light rays fan out or diffract as they travel. Recently it was discovered that light rays can travel without diffraction in a curved arc in free space. These rays of light were dubbed "Airy beams," after the English astronomer Sir George Biddell Airy, who studied what appears to be the parabolic trajectory of light in a rainbow.

Now, scientists with the Lawrence Berkeley National Laboratory (Berkeley Lab) have demonstrated the first technique that provides dynamic control in real-time of the curved trajectories of Airy beams over metallic surfaces. This development paves the way for fast-as-light, ultra-compact communication systems and optoelectronic devices,and could also stimulate revolutions in chemistry, biology and medicine.

The key to the success of this work was their ability to directly couple free-space Airy beams -- using a standard tool of optics called a "grating coupler" -- to quasi-particles called surface plasmon polaritons (SPPs). Directing a laser beam of light across the surface of a metal nanostructure generates electronic surface waves -- called plasmons -- that roll through the metal's conduction electrons (those loosely attached to molecules and atoms). The resulting interaction between plasmons and photons creates SPPs. By directly coupling Airy beams to SPPs, the researchers are able to manipulate light at an extremely small scale beyond the diffraction limit.

"Dynamic controllability of SPPs is extremely desirable for reconfigurable optical interconnections," says Xiang Zhang, the leader of this research. "We have provided a novel approach of plasmonic Airy beam to manipulate SPPs without the need of any waveguide structures over metallic surfaces, providing dynamic control of their ballistic trajectories despite any surface roughness and defects, or even getting around obstacles. This is promising not only for applications in reconfigurable optical interconnections but also for precisely manipulating particles on extremely small scales."

Zhang, a principal investigator with Berkeley Lab's Materials Sciences Division and director of the University of California at Berkeley's Nano-scale Science and Engineering Center (SINAM), is the corresponding author of a paper published in the journal Optics Letters. The paper is titled "Plasmonic Airy beams with dynamically controlled trajectories." Coauthoring the paper were Peng Zhang, Sheng Wang, Yongmin Liu, Xiaobo Yin, Changgui Lu and Zhigang Chen.

"Up to now, different plasmonic elements for manipulating surface plasmons were realized either through structuring metal surfaces or by placing dielectric structures on metals," says Peng Zhang, lead author of the Optics Letters paper and member of Xiang Zhang's research group. "Both approaches are based on the fabrication of permanent nanostructures on the metal surface, which are very difficult if not impossible to reconfigure in real time. Reconfigurability is crucial to optical interconnections, which in turn are crucial for high performance optical computing and communication systems. The reconfigurability of our technique is a huge advantage over previous approaches."

Adds co-author Zhigang Chen, a principal investigator with the Department of Physics and Astronomy at San Francisco State University, "With the reconfigurability of our plasmonic Airy beams, a small number of optical devices can be employed to perform a large number of functions within a compact system. In addition, the unique properties of the plasmonic Airy beams open new opportunities for on-chip energy routing along arbitrary trajectories in plasmonic circuitry, and allows for dynamic manipulations of nano-particles on metal surfaces and in magneto-electronic devices."

Dynamic control of the plasmonic Airy beams is provided by a computer-controlled spatial light modulator, a device similar to a liquid crystal display that can be used to offset the incoming light waves from a laser beam with respect to a cubic phase system mask and a Fourier lens. This generates a plasmonic Airy beam on the surface of a metal whose ballistic motion can be modified.

"The direction and speed of the displacement between the incoming light and the cubic phase mask can be controlled with ease simply by displaying an animation of the shifting mask pattern as well as a shifting slit aperture in the spatial light modulator," Peng Zhang says. "Depending on the refresh rate of the spatial light modulator this can be done in real time. Furthermore, our spatial light modulator not only sets the plasmonic Airy beam into a general ballistic motion, it also enables us to control the Airy beam's peak intensity at different positions along its curved path."

The ability of the spatial light modulator to dynamically control the ballistic motions of plasmonic Airy beams without the need of any permanent guiding structures should open doors to a number of new technologies, according to Xiang and Peng Zhang and their collaborators. For example, in nano-photonics, it enables researchers to design practical reconfigurable plasmonic sensors or perform nano-particle tweezing on microchips. In biology and chemistry, it allows researchers to dynamically manipulate molecules.

Says Sheng Wang, second lead author of the Optics Letters paper, "The ultrafine nature of SPPs is extremely promising for applications of nanolithography or nanoimaging. Having dynamic tunable plasmonic Airy beams should also be useful for ultrahigh resolution bioimaging. For example, we can directly illuminate a target, for example a protein, bypassing any obstacles or reducing the background."

Adds third lead author Yongmin Liu, "Our findings may inspire researchers to explore other types of non-diffracting surface waves, such as electron spin waves, in other two-dimensional systems, including graphene and topological insulators."

This work was supported by the U.S. Army Research Office, the U.S. Air Force Office of Scientific Research, and the National Science Foundation Nanoscale Science and Engineering Center.

Story Source:

The above story is reprinted (with editorial adaptations ) from materials provided by DOE/Lawrence Berkeley National Laboratory.

Journal Reference:

Peng Zhang, Sheng Wang, Yongmin Liu, Xiaobo Yin, Changgui Lu, Zhigang Chen, Xiang Zhang. Plasmonic Airy beams with dynamically controlled trajectories. Optics Letters, 2011; 36 (16): 3191 DOI: 10.1364/OL.36.003191

Catalyst that makes hydrogen gas breaks speed record

Looking to nature for their muse, researchers have used a common protein to guide the design of a material that can make energy-storing hydrogen gas. The synthetic material works 10 times faster than the original protein found in water-dwelling microbes, the researchers report in the August 12 issue of the journal Science, clocking in at 100,000 molecules of hydrogen gas every second.

This step is just one part of a series of reactions to split water and make hydrogen gas, but the researchers say the result shows they can learn from nature how to control those reactions to make durable synthetic catalysts for energy storage, such as in fuel cells.

In addition, the natural protein, an enzyme, uses inexpensive, abundant metals in its design, which the team copied. Currently, these materials -- called catalysts, because they spur reactions along -- rely on expensive metals such as platinum.

"This nickel-based catalyst is really very fast," said coauthor Morris Bullock of the Department of Energy's Pacific Northwest National Laboratory. "It's about a hundred times faster than the previous catalyst record holder. And from nature, we knew it could be done with abundant and inexpensive nickel or iron."

Stuffing Bonds

Electrical energy is nothing more than electrons. These same electrons are what tie atoms together when they are chemically bound to each other in molecules such as hydrogen gas. Stuffing electrons into chemical bonds is one way to store electrical energy, which is particularly important for renewable, sustainable energy sources like solar or wind power. Converting the chemical bonds back into flowing electricity when the sun isn't shining or the wind isn't blowing allows the use of the stored energy, such as in a fuel cell that runs on hydrogen.

Electrons are often stored in batteries, but Bullock and his colleagues want to take advantage of the closer packing available in chemicals.

"We want to store energy as densely as possible. Chemical bonds can store a huge amount of energy in a small amount of physical space," said Bullock, director of the Center for Molecular Electrocatalysis at PNNL, one of DOE's Energy Frontier Research Centers. The team also included visiting researcher Monte Helm from Fort Lewis College in Durango, Colo.

Biology stores energy densely all the time. Plants use photosynthesis to store the sun's energy in chemical bonds, which people use when they eat food. And a common microbe stores energy in the bonds of hydrogen gas with the help of a protein called a hydrogenase.

Because the hydrogenases found in nature don't last as long as ones that are built out of tougher chemicals (think paper versus plastic), the researchers wanted to pull out the active portion of the biological hydrogenase and redesign it with a stable chemical backbone.

Two Plus Two Equals One

In this study, the researchers looked at only one small part of splitting water into hydrogen gas, like fast-forwarding to the end of a movie. Of the many steps, there's a part at the end when the catalyst has a hold of two hydrogen atoms that it has stolen from water and snaps the two together.

The catalyst does this by completely dismantling some hydrogen atoms from a source such as water and moving the pieces around. Due to the simplicity of hydrogen atoms, those pieces are positively charged protons and negatively charged electrons. The catalyst arranges those pieces into just the right position so they can be put together correctly. "Two protons plus two electrons equals one molecule of hydrogen gas," says Bullock.

In real life, the protons would come from water, but since the team only examined a portion of the reaction, the researchers used water stand-ins such as acids to test their catalyst.

"We looked at the hydrogenase and asked what is the important part of this?" said Bullock. "The hydrogenase moves the protons around in what we call a proton relay. Where the protons go, the electrons will follow."

A Bauble for Energy

Based on the hydrogenase's proton relay, the experimental catalyst contained regions that dangled off the main structure and attracted protons, called "pendant amines." A pendant amine moves a proton into position on the edge of the catalyst, while a nickel atom in the middle of the catalyst offers a hydrogen atom with an extra electron (that's a proton and two electrons for those counting).

The pendant amine's proton is positive, while the nickel atom is holding on to a negatively charged hydrogen. Positioned close to each other, the opposites attract and the conglomerate solidifies into a molecule, forming hydrogen gas.

With that plan in mind, the team built potential catalysts and tested them. On their first try, they put a bunch of pendant amines around the nickel center, thinking more would be better. Testing their catalyst, they found it didn't work very fast. An analysis of how the catalyst was moving protons and electrons around suggested too many pendant amines got in the way of the perfect reaction. An overabundance of protons made for a sticky catalyst, which pinched it and slowed the hydrogen-gas-forming reaction down.

Like good gardeners, the team trimmed a few pendant amines off their catalyst, leaving only enough to make the protons stand out, ready to accept a negatively charged hydrogen atom.

Fastest Cat in the West

Testing the trimmed catalyst, the team found it performed much better than anticipated. At first they used conditions in which no water was present (remember, they used water stand-ins), and the catalyst could create hydrogen gas at a rate of about 33,000 molecules per second. That's much faster than their natural inspiration, which clocks in at around 10,000 per second.

However, most real-life applications will have water around, so they added water to the reaction to see how it would perform. The catalyst ran three times as fast, creating more than 100,000 hydrogen molecules every second. The researchers think the water might help by moving protons to a more advantageous spot on the pendant amine, but they are still studying the details.

Their catalyst has a drawback, however. It's fast, but it's not efficient. The catalyst runs on electricity -- after all, it needs those electrons to stuff into the chemical bonds -- but it requires more electricity than practical, a characteristic called the overpotential.

Bullock says the team has some ideas on how to reduce the inefficiency. Also, future work will require assembling a catalyst that splits water in addition to making hydrogen gas. Even with a high overpotential, the researchers see high potential for this catalyst.

Story Source:

The above story is reprinted (with editorial adaptations) from materials provided by DOE/Pacific Northwest National Laboratory.

Journal Reference:

M. L. Helm, M. P. Stewart, R. M. Bullock, M. R. DuBois, D. L. DuBois. A Synthetic Nickel Electrocatalyst with a Turnover Frequency Above 100,000 s-1 for H2 Production. Science, 2011; 333 (6044): 863 DOI: 10.1126/science.1205864

Inexpensive catalyst that makes hydrogen gas 10 times faster than natural enzyme

Looking to nature for their muse, researchers have used a common protein to guide the design of a material that can make energy-storing hydrogen gas. The synthetic material works 10 times faster than the original protein found in water-dwelling microbes, the researchers report in the August 12 issue of the journal Science, clocking in at 100,000 molecules of hydrogen gas every second.

This step is just one part of a series of reactions to split water and make hydrogen gas, but the researchers say the result shows they can learn from nature how to control those reactions to make durable synthetic catalysts for energy storage, such as in fuel cells.

In addition, the natural protein, an enzyme, uses inexpensive, abundant metals in its design, which the team copied. Currently, these materials -- called catalysts, because they spur reactions along -- rely on expensive metals such as platinum.

"This nickel-based catalyst is really very fast," said coauthor Morris Bullock of the Department of Energy's Pacific Northwest National Laboratory. "It's about a hundred times faster than the previous catalyst record holder. And from nature, we knew it could be done with abundant and inexpensive nickel or iron."

Stuffing Bonds

Electrical energy is nothing more than electrons. These same electrons are what tie atoms together when they are chemically bound to each other in molecules such as hydrogen gas. Stuffing electrons into chemical bonds is one way to store electrical energy, which is particularly important for renewable, sustainable energy sources like solar or wind power. Converting the chemical bonds back into flowing electricity when the sun isn't shining or the wind isn't blowing allows the use of the stored energy, such as in a fuel cell that runs on hydrogen.

Electrons are often stored in batteries, but Bullock and his colleagues want to take advantage of the closer packing available in chemicals.

"We want to store energy as densely as possible. Chemical bonds can store a huge amount of energy in a small amount of physical space," said Bullock, director of the Center for Molecular Electrocatalysis at PNNL, one of DOE's Energy Frontier Research Centers. The team also included visiting researcher Monte Helm from Fort Lewis College in Durango, Colo.

Biology stores energy densely all the time. Plants use photosynthesis to store the sun's energy in chemical bonds, which people use when they eat food. And a common microbe stores energy in the bonds of hydrogen gas with the help of a protein called a hydrogenase.

Because the hydrogenases found in nature don't last as long as ones that are built out of tougher chemicals (think paper versus plastic), the researchers wanted to pull out the active portion of the biological hydrogenase and redesign it with a stable chemical backbone.

Two Plus Two Equals One

In this study, the researchers looked at only one small part of splitting water into hydrogen gas, like fast-forwarding to the end of a movie. Of the many steps, there's a part at the end when the catalyst has a hold of two hydrogen atoms that it has stolen from water and snaps the two together.

The catalyst does this by completely dismantling some hydrogen atoms from a source such as water and moving the pieces around. Due to the simplicity of hydrogen atoms, those pieces are positively charged protons and negatively charged electrons. The catalyst arranges those pieces into just the right position so they can be put together correctly. "Two protons plus two electrons equals one molecule of hydrogen gas," says Bullock.

In real life, the protons would come from water, but since the team only examined a portion of the reaction, the researchers used water stand-ins such as acids to test their catalyst.

"We looked at the hydrogenase and asked what is the important part of this?" said Bullock. "The hydrogenase moves the protons around in what we call a proton relay. Where the protons go, the electrons will follow."

A Bauble for Energy

Based on the hydrogenase's proton relay, the experimental catalyst contained regions that dangled off the main structure and attracted protons, called "pendant amines." A pendant amine moves a proton into position on the edge of the catalyst, while a nickel atom in the middle of the catalyst offers a hydrogen atom with an extra electron (that's a proton and two electrons for those counting).

The pendant amine's proton is positive, while the nickel atom is holding on to a negatively charged hydrogen. Positioned close to each other, the opposites attract and the conglomerate solidifies into a molecule, forming hydrogen gas.

With that plan in mind, the team built potential catalysts and tested them. On their first try, they put a bunch of pendant amines around the nickel center, thinking more would be better. Testing their catalyst, they found it didn't work very fast. An analysis of how the catalyst was moving protons and electrons around suggested too many pendant amines got in the way of the perfect reaction. An overabundance of protons made for a sticky catalyst, which pinched it and slowed the hydrogen-gas-forming reaction down.

Like good gardeners, the team trimmed a few pendant amines off their catalyst, leaving only enough to make the protons stand out, ready to accept a negatively charged hydrogen atom.

Fastest Cat in the West

Testing the trimmed catalyst, the team found it performed much better than anticipated. At first they used conditions in which no water was present (remember, they used water stand-ins), and the catalyst could create hydrogen gas at a rate of about 33,000 molecules per second. That's much faster than their natural inspiration, which clocks in at around 10,000 per second.

However, most real-life applications will have water around, so they added water to the reaction to see how it would perform. The catalyst ran three times as fast, creating more than 100,000 hydrogen molecules every second. The researchers think the water might help by moving protons to a more advantageous spot on the pendant amine, but they are still studying the details.

Their catalyst has a drawback, however. It's fast, but it's not efficient. The catalyst runs on electricity -- after all, it needs those electrons to stuff into the chemical bonds -- but it requires more electricity than practical, a characteristic called the overpotential.

Bullock says the team has some ideas on how to reduce the inefficiency. Also, future work will require assembling a catalyst that splits water in addition to making hydrogen gas. Even with a high overpotential, the researchers see high potential for this catalyst.

More information: Monte L. Helm, Michael P. Stewart, R. Morris Bullock, M. Rakowski DuBois, Daniel L. DuBois, A Synthetic Nickel Electrocatalyst With a Turnover Frequency Above 100,000 s-1 for H2 Production, Science, August 12, 2011, DOI:10.1126/science.1205864

Provided by Pacific Northwest National Laboratory (news : web)

Disorder is key to nanotube mystery

Scientists often find strange and unexpected things when they look at materials at the nanoscale -- the level of single atoms and molecules. This holds true even for the most common materials, such as water.

Case in point: In the last couple of years, researchers have observed that water spontaneously flows into extremely small tubes of graphite or graphene, called carbon nanotubes. This unexpected observation is intriguing because carbon nanotubes hold promise in the emerging fields of nanofluidics and nanofiltration, where nanotubes might be able to help maintain tiny flows or separate impurities from water. However, no one has managed to explain why, at the molecular level, a stable liquid would want to confine itself to such a small area.

Now, using a novel method to calculate the dynamics of water molecules, Caltech researchers believe they have solved the mystery. It turns out that entropy, a measurement of disorder, has been the missing key.

"It's a pretty surprising result," says William Goddard, the Charles and Mary Ferkel Professor of Chemistry, Materials Science, and Applied Physics at Caltech and director of the Materials and Process Simulation Center. "People normally focus on energy in this problem, not entropy."

That's because water forms an extensive network of hydrogen bonds, which makes it very stable. Breaking those strong interactions requires energy. And since some bonds have to be broken in order for water to flow into small nanotubes, it would seem unlikely that water would do so freely.

"What we found is that it's actually a trade off," Goddard says. "You lose some of that good energy stabilization from the bonding, but in the process you gain in entropy."

Entropy is one of the driving forces that determine whether a process will occur spontaneously. It represents the number of ways a system can exist in a particular state. The more arrangements available to a system, the greater its disorder, and the higher the entropy. And in general, nature proceeds toward disorder.

When water is ideally bonded, all of the hydrogen bonds lock the molecules into place, restricting their freedom and keeping water's entropy low. What Goddard and postdoctoral scholar Tod Pascal found is that in the case of some nanotubes, water gains enough entropy by entering the tubes to outweigh the energy losses incurred by breaking some of its hydrogen bonds. Therefore, water flows spontaneously into the tubes.

Goddard and Pascal explain their findings in a paper recently published in the Proceedings of the National Academy of Sciences (PNAS). They looked at carbon nanotubes with diameters between 0.8 and 2.7 nanometers and found three different reasons why water would flow freely into the tubes, depending on diameter.

For the smallest nanotubes -- those between 0.8 and 1.0 nanometers in diameter -- the tubes are so minuscule that water molecules line up nearly single file within them and take on a gaslike state. That means the normal bonded structure of liquid water breaks down, giving the molecules greater freedom of motion. This increase in entropy draws water into the tubes.

At the next level, where the nanotubes have diameters between 1.1 and 1.2 nanometers, confined water molecules arrange themselves in stacked, icelike crystals. Goddard and Pascal found such nanotubes to be the perfect size -- a kind of Goldilocks match -- to accommodate crystallized water. These crystal-bonding interactions, not entropy, make it favorable for water to flow into the tubes.

On the largest scale studied -- involving tubes whose diameters are still only 1.4 to 2.7 nanometers wide -- the researchers found that the confined water molecules behave more like liquid water. However, once again, some of the normal hydrogen bonds are broken, so the molecules exhibit more freedom of motion within the tubes. And the gains in entropy more than compensate for the loss in hydrogen bonding energy.

Because the insides of the carbon nanotubes are far too small for researchers to examine experimentally, Goddard and Pascal studied the dynamics of the confined water molecules in simulations. Using a new method developed by Goddard's group with a supercomputer, they were able to calculate the entropy for the individual water molecules. In the past, such calculations have been difficult and extremely time-consuming. But the new approach, dubbed the two-phase thermodynamic model, has made the determination of entropy values relatively easy for any system.

"The old methods took eight years of computer processing time to arrive at the same entropies that we're now getting in 36 hours," Goddard says.

The team also ran simulations using an alternative description of water -- one where water had its usual properties of energy, density, and viscosity, but lacked its characteristic hydrogen bonding. In that case, water did not want to flow into the nanotubes, providing additional proof that water's naturally occurring low entropy due to extensive hydrogen bonding leads to it spontaneously filling carbon nanotubes when the entropy increases.

Goddard believes that carbon nanotubes could be used to design supermolecules for water purification. By incorporating pores with the same diameters as carbon nanotubes, he thinks a polymer could be made to suck water out of solution. Such a potential application points to the need for a greater understanding of water transport through carbon nanotubes.

Story Source:

The above story is reprinted (with editorial adaptations) from materials provided by California Institute of Technology.

Journal Reference:

T. A. Pascal, W. A. Goddard, Y. Jung. From the Cover: Entropy and the driving force for the filling of carbon nanotubes with water. Proceedings of the National Academy of Sciences, 2011; 108 (29): 11794 DOI: 10.1073/pnas.1108073108