Using carbon nanotubes as a terahertz polarizer

Researchers at Rice University are using carbon nanotubes as the critical component of a robust terahertz polarizer that could accelerate the development of new security and communication devices, sensors and noninvasive medical imaging systems as well as fundamental studies of low-dimensional condensed matter systems.

The polarizer developed by the Rice lab of Junichiro Kono, a professor of electrical and computer engineering and of physics and astronomy, is the most effective ever reported; it selectively allows 100 percent of a terahertz wave to pass or blocks 99.9 percent of it, depending on its polarization. The research was published this week in the online version of the American Chemical Society journal, Nano Letters.

The broadband polarizer handles waves from 0.5 to 2.2 terahertz, far surpassing the range of commercial polarizers that consist of fragile grids wrapped in gold or tungsten wires.

Kono said technologies that make use of the optical and electrical regions of the electromagnetic spectrum are mature and common, as in lasers and telescopes on one end and computers and microwaves on the other. But until recent years, the terahertz region in between was largely unexplored. "Over the past decade or two, people have been making impressive progress," he said, particularly in the development of such sources of radiation as the terahertz quantum cascade laser.

"We have pretty good terahertz emitters and detectors, but we need a way to manipulate light in this range," Kono said. "Our work is in this category, manipulating the polarization state -- the direction of the electric field -- of terahertz radiation."

A triple layer of carbon nanotube arrays on a sapphire base is the basis for a new type of terahertz polarizer invented at Rice University. The polarizer could lead to new security and communication devices, sensors and noninvasive medical imaging systems.

Terahertz waves exist at the transition between infrared and microwaves and have unique qualities. They are not harmful and penetrate fabric, wood, plastic and even clouds, but not metal or water. In combination with spectroscopy, they can be used to read what Kono called "spectral fingerprints in the terahertz range"; he said they would, for instance, be useful in a security setting to identify the chemical signatures of specific explosives. The work by Kono and lead author Lei Ren, who recently earned his doctorate at Rice, makes great use of the basic research into carbon nanotubes for which the university is famous. Co-authors Robert Hauge, a distinguished faculty fellow in chemistry, and his former graduate student Cary Pint developed a way to grow nanotube carpets and to transfer well-aligned arrays of nanotubes from a catalyst to any substrate they chose, limited only by the size of the growth platform.

While Hauge and Pint were developing their nanotube arrays, Kono and his team were thinking about terahertz. Four years ago they came across a semiconducting material, indium antimonide, that would stop or pass terahertz waves, but only in a strong magnetic field and at very low temperatures.

At about the same time, Kono's lab began working with carbon nanotube arrays transferred onto a sapphire substrate by Pint and Hauge. Those aligned arrays -- think of a field of wheat run over by a steamroller -- turned out to be very effective at filtering terahertz waves, as Kono and his team reported in a 2009 paper.

"When the polarization of the terahertz wave was perpendicular to the nanotubes, there was absolutely no attenuation," Kono recalled. "But when the polarization was parallel to the nanotubes, the thickness was not enough to completely kill the transmission, which was still at 30-50 percent."

The answer was clear: Make the polarizer thicker. The current polarizer has three decks of aligned nanotubes on sapphire, enough to effectively absorb all of the incident terahertz radiation. "Our method is unique, and it's simple," he said.

Kono sees use for the device beyond spectroscopy by manipulating it with an electric field, but that will become possible only when all of the nanotubes in an array are of a semiconducting type. As they're made now, batches of nanotubes are a random mix of semiconductors and metallics; recent work by Erik Hároz, a graduate student in Kono's lab, detailed the reasons that nanotubes separated through ultracentrifugation have type-dependent colors. But finding a way to grow specific types of nanotubes is the focus of a great deal of research at Rice and elsewhere.

Co-authors are former Rice postdoctoral researcher Takashi Arikawa and research associate Iwao Kawayama and Professor Masayoshi Tonouchi of the Institute of Laser Engineering at Osaka University, Japan.

The Department of Energy, the National Science Foundation and the Robert A. Welch Foundation supported the research.

Contact: David Ruth david@rice.edu 713-348-6327 Rice University

New type of miniature medical sensor powered by acoustic waves

WEST LAFAYETTE, Ind. – The driving bass rhythm of rap music can be harnessed to power a new type of miniature medical sensor designed to be implanted in the body.

Acoustic waves from music, particularly rap, were found to effectively recharge the pressure sensor. Such a device might ultimately help to treat people stricken with aneurisms or incontinence due to paralysis.

The heart of the sensor is a vibrating cantilever, a thin beam attached at one end like a miniature diving board. Music within a certain range of frequencies, from 200-500 hertz, causes the cantilever to vibrate, generating electricity and storing a charge in a capacitor, said Babak Ziaie, a Purdue University professor of electrical and computer engineering and biomedical engineering.

"The music reaches the correct frequency only at certain times, for example, when there is a strong bass component," he said. "The acoustic energy from the music can pass through body tissue, causing the cantilever to vibrate."

When the frequency falls outside of the proper range, the cantilever stops vibrating, automatically sending the electrical charge to the sensor, which takes a pressure reading and transmits data as radio signals. Because the frequency is continually changing according to the rhythm of a musical composition, the sensor can be induced to repeatedly alternate intervals of storing charge and transmitting data.

This graphic illustrates the principles behind the operation of a new type of miniature medical sensor powered by acoustic waves, including those found in music such as rap, blues, jazz and rock. The device, a pressure sensor, might ultimately help to treat people stricken with aneurisms or incontinence due to paralysis. (Birck Nanotechnology Center, Purdue University) Researchers have created a new type of miniature pressure sensor, shown here, designed to be implanted in the body. Acoustic waves from music or plain tones drive a vibrating device called a cantilever, generating a charge to power the sensor. (Birck Nanotechnology Center, Purdue University)

"You would only need to do this for a couple of minutes every hour or so to monitor either blood pressure or pressure of urine in the bladder," Ziaie said. "It doesn't take long to do the measurement." Findings are detailed in a paper to be presented during the IEEE MEMS conference, which will be Jan. 29 to Feb. 2 in Paris. The paper was written by doctoral student Albert Kim, research scientist Teimour Maleki and Ziaie. "This paper demonstrates the feasibility of the concept," he said. The device is an example of a microelectromechanical system, or MEMS, and was created in the Birck Nanotechnology Center at the university's Discovery Park. The cantilever beam is made from a ceramic material called lead zirconate titanate, or PZT, which is piezoelectric, meaning it generates electricity when compressed. The sensor is about 2 centimeters long. Researchers tested the device in a water-filled balloon. A receiver that picks up the data from the sensor could be placed several inches from the patient. Playing tones within a certain frequency range also can be used instead of music. "But a plain tone is a very annoying sound," Ziaie said. "We thought it would be novel and also more aesthetically pleasing to use music." Researchers experimented with four types of music: rap, blues, jazz and rock. "Rap is the best because it contains a lot of low frequency sound, notably the bass," Ziaie said.

The sensor is capable of monitoring pressure in the urinary bladder and in the sack of a blood vessel damaged by an aneurism. Such a technology could be used in a system for treating incontinence in people with paralysis by checking bladder pressure and stimulating the spinal cord to close the sphincter that controls urine flow from the bladder. More immediately, it could be used to diagnose incontinence. The conventional diagnostic method now is to insert a probe with a catheter, which must be in place for several hours while the patient remains at the hospital.

"A wireless implantable device could be inserted and left in place, allowing the patient to go home while the pressure is monitored," Ziaie said.

The new technology offers potential benefits over conventional implantable devices, which either use batteries or receive power through a property called inductance, which uses coils on the device and an external transmitter. Both approaches have downsides. Batteries have to be replaced periodically, and data are difficult to retrieve from devices that use inductance; coils on the implanted device and an external receiver must be lined up precisely, and they can only be about a centimeter apart.

A patent application has been filed for the design.

Writer: Emil Venere, 765-494-4709, venere@purdue.edu Source: Babak Ziaie, 765-494-0725, bziaie@purdue.edu

A property of "bilayer graphene" (BLG) that the researchers say is analogous to finding the Higgs boson in particle physics

Bilayer graphene works as an insulator. Research by UC Riverside-led team has potential applications in digital and infrared technologies.

RIVERSIDE, Calif. – A research team led by physicists at the University of California, Riverside has identified a property of "bilayer graphene" (BLG) that the researchers say is analogous to finding the Higgs boson in particle physics.

Graphene, nature's thinnest elastic material, is a one-atom thick sheet of carbon atoms arranged in a hexagonal lattice. Because of graphene's planar and chicken wire-like structure, sheets of it lend themselves well to stacking.

BLG is formed when two graphene sheets are stacked in a special manner. Like graphene, BLG has high current-carrying capacity, also known as high electron conductivity. The high current-carrying capacity results from the extremely high velocities that electrons can acquire in a graphene sheet.

The physicists report online Jan. 22 in Nature Nanotechnology that in investigating BLG's properties they found that when the number of electrons on the BLG sheet is close to 0, the material becomes insulating (that is, it resists flow of electrical current) – a finding that has implications for the use of graphene as an electronic material in the semiconductor and electronics industries.

"BLG becomes insulating because its electrons spontaneously organize themselves when their number is small," said Chun Ning (Jeanie) Lau, an associate professor of physics and astronomy and the lead author of the research paper. "Instead of moving around randomly, the electrons move in an orderly fashion. This is called 'spontaneous symmetry breaking' in physics, and is a very important concept since it is the same principle that 'endows' mass for particles in high energy physics."

Caption: The image shows a bilayer graphene schematic. The blue beads represent carbon atoms. Credit: Lau lab, UC Riverside. Usage Restrictions: None. Caption: Photo shows a scanning electron microscope image of a graphene sheet (red) suspended between two electrodes. The length of the graphene sheet shown is about 1/100 of the width of a human hair. Credit: Lau lab, UC Riverside. Usage Restrictions: None.

Lau explained that a typical conductor has a huge number of electrons, which move around randomly, rather like a party with ten thousand guests with no assigned seats at dining tables. If the party only has four guests, however, then the guests will have to interact with each other and sit down at a table. Similarly, when BLG has only a few electrons the interactions cause the electrons to behave in an orderly manner. New quantum particle Allan MacDonald, the Sid W. Richardson Foundation Regents Chair in the Department of Physics at The University of Texas at Austin and a coauthor on the research paper, noted that team has measured the mass of a new type of massive quantum particle that can be found only inside BLG crystals. "The physics which gives these particles their mass is closely analogous to the physics which makes the mass of a proton inside an atomic nucleus very much larger than the mass of the quarks from which it is formed," he said. "Our team's particle is made of electrons, however, not quarks." MacDonald explained that the experiment the research team conducted was motivated by theoretical work which anticipated that new particles would emerge from the electron sea of a BLG crystal. "Now that the eagerly anticipated particles have been found, future experiments will help settle an ongoing theoretical debate on their properties," he said. Practical applications An important finding of the research team is that the intrinsic "energy gap" in BLG grows with increasing magnetic field.

In solid state physics, an energy gap (or band gap) refers to an energy range in a solid where no electron states can exist. Generally, the size of the energy gap of a material determines whether it is a metal (no gap), semiconductor (small gap) or insulator (large gap). The presence of an energy gap in silicon is critical to the semiconductor industry since, for digital applications, engineers need to turn the device 'on' or conductive, and 'off' or insulating.

Single layer graphene (SLG) is gapless, however, and cannot be completely turned off because regardless of the number of electrons on SLG, it always remains metallic and a conductor.

"This is terribly disadvantageous from an electronics point of view," said Lau, a member of UC Riverside's Center for Nanoscale Science and Engineering. "BLG, on the other hand, can in fact be turned off. Our research is in the initial phase, and, presently, the band gap is still too small for practical applications. What is tremendously exciting though is that this work suggests a promising route – trilayer graphene and tetralayer graphene, which are likely to have much larger energy gaps that can be used for digital and infrared technologies. We already have begun working with these materials."

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Lau and MacDonald were joined in the research by J. Velasco Jr. (the first author of the research paper), L. Jing, W. Bao, Y. Lee, P. Kratz, V. Aji, M. Bockrath, and C. Varma at UCR; R. Stillwell and D. Smirnov at the National High Magnetic Field Laboratory, Tallahassee, Fla.; and Fan Zhang and J. Jung at The University of Texas at Austin.

The research was supported by grants from the National Science Foundation, Office of Naval Research, FENA Focus Center, and other agencies.

The University of California, Riverside (www.ucr.edu) is a doctoral research university, a living laboratory for groundbreaking exploration of issues critical to Inland Southern California, the state and communities around the world. Reflecting California's diverse culture, UCR's enrollment has exceeded 20,500 students. The campus will open a medical school in 2013 and has reached the heart of the Coachella Valley by way of the UCR Palm Desert Center. The campus has an annual statewide economic impact of more than $1 billion.

A broadcast studio with fiber cable to the AT&T Hollywood hub is available for live or taped interviews. UCR also has ISDN for radio interviews. To learn more, call 951-UCR-NEWS.

Contact: Iqbal Pittalwala iqbal@ucr.edu 951-827-6050 University of California - Riverside

Invisible to Water, thinness of Graphene Enables Near Perfect Wetting Transparency

Nature Materials Study: Graphene “Invisible” to Water. Engineers at Rensselaer Polytechnic Institute and Rice University Discover How the Extreme Thinness of Graphene Enables Near-Perfect Wetting Transparency.

Graphene is the thinnest material known to science. The nanomaterial is so thin, in fact, water often doesn’t even know it’s there.

Engineering researchers at Rensselaer Polytechnic Institute and Rice University coated pieces of gold, copper, and silicon with a single layer of graphene, and then placed a drop of water on the coated surfaces. Surprisingly, the layer of graphene proved to have virtually no impact on the manner in which water spreads on the surfaces.

Results of the study were published Sunday in the journal Nature Materials. The findings could help inform a new generation of graphene-based flexible electronic devices. Additionally, the research suggests a new type of heat pipe that uses graphene-coated copper to cool computer chips.

The discovery stemmed from a cross-university collaboration led by Rensselaer Professor Nikhil Koratkar and Rice Professor Pulickel Ajayan.

“We coated several different surfaces with graphene, and then put a drop of water on them to see what would happen. What we saw was a big surprise—nothing changed. The graphene was completely transparent to the water,” said Koratkar, a faculty member in the Department of Mechanical, Aerospace, and Nuclear Engineering and the Department of Materials Science and Engineering at Rensselaer. “The single layer of graphene was so thin that it did not significantly disrupt the non-bonding van der Waals forces that control the interaction of water with the solid surface. It’s an exciting discovery, and is another example of the unique and extraordinary characteristics of graphene.”

Essentially an isolated layer of the graphite found commonly in our pencils or the charcoal we burn on our barbeques, graphene is single layer of carbon atoms arranged like a nanoscale chicken-wire fence. Graphene is known to have excellent mechanical properties. The material is strong and tough and because of its flexibility can evenly coat nearly any surface. Many researchers and technology leaders see graphene as an enabling material that could greatly advance the advent of flexible, paper-thin devices and displays. Used as a coating for such devices, the graphene would certainly come into contact with moisture. Understanding how graphene interacts with moisture was the impetus behind this new study.

The spreading of water on a solid surface is called wetting. Calculating wettability involves placing a drop of water on a surface, and then measuring the angle at which the droplet meets the surface. The droplet will ball up and have a high contact angle on a hydrophobic surface. Inversely, the droplet will spread out and have a low contact angle on a hydrophilic surface.

The contact angle of gold is about 77 degrees. Koratkar and Ajayan found that after coating a gold surface with a single layer of graphene, the contact angle became about 78 degrees. Similarly, the contact angle of silicon rose from roughly 32 degrees to roughly 33 degrees, and copper increased from around 85 degrees to around 86 degrees, after adding a layer of graphene.

These results surprised the researchers. Graphene is impermeable, as the tiny spaces between its linked carbon atoms are too small for water,or a single proton, or anything else to fit through. Because of this, one would expect that water would not act as if it were on gold, silicon, or copper, since the graphene coating prevents the water from directly contacting these surfaces. But the research findings clearly show how the water is able to sense the presence of the underlying surface, and spreads on those surfaces as if the graphene were not present at all.

As the researchers increased the number of layers of graphene, however, it became less transparent to the water and the contact angles jumped significantly. After adding six layers of graphene, the water no longer saw the gold, copper, or silicon and instead behaved as if it was sitting on graphite.

The reason for this perplexing behavior is subtle. Water forms chemical or hydrogen bonds with certain surfaces, while the attraction of water to other surfaces is dictated by non-bonding interactions called van der Waals forces. These non-bonding forces are not unlike a nanoscale version of gravity, Koratkar said. Similar to how gravity dictates the interaction between the Earth and sun, van der Waals forces dictate the interaction between atoms and molecules.

In the case of gold, copper, silicon, and other materials, the van der Waals forces between the surface and water droplet determine the attraction of water to the surface and dictate how water spreads on the solid surface. In general, these forces have a range of at least several nanometers. Because of the long range, these forces are not disrupted by the presence of a single-atom-thick layer of graphene between the surface and the water. In other words, the van der Waals forces are able to “look through” ultra-thin graphene coatings, Koratkar said.

If you continue to add additional layers of graphene, however, the van der Waals forces increasingly “see” the carbon coating on top of the material instead of the underlying surface material. After stacking six layers of graphene, the separation between the graphene and the surface is sufficiently large to ensure that the van der Waals forces can now no longer sense the presence of the underlying surface and instead only see the graphene coating. On surfaces where water forms hydrogen bonds with the surface, the wetting transparency effect described above does not hold because such chemical bonds cannot form through the graphene layer.

Along with conducting physical experiments, the researchers verified their findings with molecular dynamics modeling as well as classical theoretical modeling.

“We found that van der Waals forces are not disrupted by graphene. This effect is an artifact of the extreme thinness of graphene—which is only about 0.3 nanometers thick,” Koratkar said. “Nothing can rival the thinness of graphene. Because of this, graphene is the ideal material for wetting angle transparency.”

“Moreover, graphene is strong and flexible, and it does not easily crack or break apart,” he said. “Additionally, it is easy to coat a surface with graphene using chemical vapor deposition, and it is relatively uncomplicated to deposit uniform and homogeneous graphene coatings over large areas. Finally, graphene is chemically inert, which means a graphene coating will not oxidize away. No single material system can provide all of the above attributes that graphene is able to offer.”

A practical application of this new discovery is to coat copper surfaces used in dehumidifiers. Because of its exposure to water, copper in dehumidifier systems oxidizes, which in turn decreases its ability to transfer heat and makes the entire device less efficient. Coating the copper with graphene prevents oxidation, the researchers said, and the operation of the device is unaffected because graphene does not change the way water interacts with copper. This same concept may be applied to improve the ability of heat pipes to dissipate heat from computer chips, Koratkar said.

“It’s an interesting idea. The graphene doesn’t cause any significant change to the wettability of copper, and at the same time it passivates the copper surface and prevents it from oxidizing,” he said.

Along with Koratkar and Ajayan, co-authors of the paper are Yunfeng Shi, assistant professor in the Department of Materials Science and Engineering at Rensselaer; Rensselaer mechanical engineering graduate students Javad Rafiee, Abhay Thomas, and Fazel Yavari; Rensselaer physics graduate student Xi Mi; and Rice mechanical and materials engineering graduate student Hemtej Gullapalli.

This research was supported in part by the Advanced Energy Consortium (AEC); the National Science Foundation (NSF); and the Office of Naval Research (ONR) graphene Multidisciplinary University Research Initiative (MURI).

Results of the study are detailed in the Nature Materials paper “Wetting transparency of graphene.” See the paper online at: Wetting transparency of graphene

Contact: Michael Mullaney: mullam@rpi.edu 518-276-6161 Rensselaer Polytechnic Institute

Tweaking small parts dramatically increases amount of sunlight solar cells convert into electricity

In Solar Cells, Tweaking the Tiniest of Parts Yields Big Jump in Efficiency.

Company led by university researchers employs charged quantum dots to increase the efficiency of solar cell technology

Summary: -- Researchers from the University at Buffalo, Army Research Laboratory and Air Force Office of Scientific Research have developed a new, nanomaterials-based technology that has the potential to increase the efficiency of photovoltaic cells up to 45 percent.

-- Specifically, the researchers have shown that embedding charged quantum dots into solar cells can improve electrical output by enabling the cells to harvest infrared light, and by increasing the lifetime of photoelectrons. The technology can be applied to many different photovoltaic structures.

-- A new company the researchers founded, OPtoElectronic Nanodevices LLC. (OPEN LLC), is commercializing this technology.

BUFFALO, N.Y. -- By tweaking the smallest of parts, a trio of University at Buffalo engineers is hoping to dramatically increase the amount of sunlight that solar cells convert into electricity.

With military colleagues, the UB researchers have shown that embedding charged quantum dots into photovoltaic cells can improve electrical output by enabling the cells to harvest infrared light, and by increasing the lifetime of photoelectrons.

Electrical engineer Vladimir Mitin and colleagues have significantly increased the electrical output of solar cells by embedding charged quantum dots in them.

The research appeared online last May in the journal Nano Letters. The research team included Vladimir Mitin, Andrei Sergeev and Nizami Vagidov, faculty members in UB's electrical engineering department; Kitt Reinhardt of the Air Force Office of Scientific Research; and John Little and advanced nanofabrication expert Kimberly Sablon of the U.S. Army Research Laboratory. Mitin, Sergeev and Vagidov have founded a company, OPtoElectronic Nanodevices LLC. (OPEN LLC.), to bring the innovation to the market.

The idea of embedding quantum dots into solar panels is not new: According to Mitin, scientists had proposed about a decade ago that this technique could improve efficiency by allowing panels to harvest invisible, infrared light in addition to visible light. However, intensive efforts in this direction have previously met with limited success.

The UB researchers and their colleagues have not only successfully used embedded quantum dots to harvest infrared light; they have taken the technology a step further, employing selective doping so that quantum dots within the solar cell have a significant built-in charge.

This built-in charge is beneficial because it repels electrons, forcing them to travel around the quantum dots. Otherwise, the quantum dots create a channel of recombination for electrons, in essence "capturing" moving electrons and preventing them from contributing to electric current.

The technology has the potential to increase the efficiency of solar cells up to 45 percent, said Mitin, a SUNY Distinguished Professor. Through UB's Office of Science, Technology Transfer and Economic Outreach (STOR), he and his colleagues have filed provisional patent applications to protect their technology.

"Clean technology will really benefit the region, the state, the country," Mitin said. "With high-efficiency solar cells, consumers can save money and providers can have a smaller solar field that produces more energy."

Mitin and his colleagues have already invested significant amounts of time in developing the quantum dots with a built-in-charge, dubbed "Q-BICs." To further enhance the technology and bring it to the market, OPEN LLC is now seeking funding from private investors and federal programs.

The University at Buffalo is a premier research-intensive public university, a flagship institution in the State University of New York system and its largest and most comprehensive campus. UB's more than 28,000 students pursue their academic interests through more than 300 undergraduate, graduate and professional degree programs. Founded in 1846, the University at Buffalo is a member of the Association of American Universities.

Contact: Charlotte Hsu chsu22@buffalo.edu 716-645-4655 University at Buffalo