Microelectromechanical based systems

Researchers with the U.S. Department of Energy (DOE)’s Lawrence Berkeley National Laboratory (Berkeley Lab) have shed light on the role of temperature in controlling a fabrication technique for drawing chemical patterns as small as 20 nanometers. This technique could provide an inexpensive, fast route to growing and patterning a wide variety of materials on surfaces to build electrical circuits and chemical sensors, or study how pharmaceuticals bind to proteins and viruses.

One way of directly writing nanoscale structures onto a substrate is to use an atomic force microscope (AFM) tip as a pen to deposit ink molecules through molecular diffusion onto the surface. Unlike conventional nanofabrication techniques that are expensive, require specialized environments and usually work with only a few materials, this technique, called dip-pen nanolithography, can be used in almost any environment to write many different chemical compounds. A cousin of this technique — called thermal dip-pen nanolithography — extends this technique to solid materials by turning an AFM tip into a tiny soldering iron.

Dip-pen nanolithography can be used to pattern features as small as 20 nanometers, more than forty thousand times smaller than the width of a human hair. What’s more, the writing tip also performs as a surface profiler, allowing a freshly-writ surface to be imaged with nanoscale precision immediately after patterning.

“Tip-based manufacturing holds real promise for precise fabrication of nanoscale devices,” says Jim DeYoreo, interim director of Berkeley Lab’s Molecular Foundry, a DOE nanoscience research center. “However, a robust technology requires a scientific foundation built on an understanding of material transfer during this process. Our study is the first to provide this fundamental understanding of thermal dip-pen nanolithography.”

In this study, DeYoreo and coworkers systematically investigated the effect of temperature on feature size. Using their results, the team developed a new model to deconstruct how ink molecules travel from the writing tip to the substrate, assemble into an ordered layer and grow into a nanoscale feature.

“By carefully considering the role of temperature in thermal dip-pen nanolithography, we may be able to design and fabricate nanoscale patterns of materials ranging from small molecules to polymers with better control over feature sizes and shapes on a variety of substrates,” says Sungwook Chung, a staff scientist in Berkeley Lab’s Physical Biosciences Division, and Foundry user working with DeYoreo. “This technique helps overcome fundamental length scale limitations without the need for complex growth methods.”

DeYoreo and Chung collaborated with a research team from the University of Illinois at Urbana-Champaign that specializes in fabricating specialized tips for AFMs. Here, these collaborators developed a silicon-based AFM tip with a gradient of charge-carrying atoms sprinkled into the silicon such that a higher number reside at the base while fewer sit at the tip. This makes the tip heat up when electricity flows through it, much like the burner on an electric stove.

This ‘nanoheater’ can then be used to heat up inks applied to the tip, causing them to flow to the surface for fabricating microscale and nanoscale features. The group demonstrated this by drawing dots and lines of the organic molecule mercaptohexadecanoic acid on gold surfaces. The hotter the tip, the larger the feature size the team could draw.

“We are excited about this collaboration with Berkeley Lab, which combines their remarkable nanoscience capabilities with our technology to control temperature and heat flow on the nanometer scale,” says co-author William P. King, a University of Illinois professor of mechanical sciences and engineering. “Our ability to control the temperature within a nanometer-scale spot enabled this study of molecular-scale transport. By tuning the hotspot temperature, we can probe how molecules flow to a surface.”

“This thermal control over tip-to-surface transfer developed by Professor King’s group adds versatility by enabling on-the-fly variations in feature size and patterning of both liquid and solid materials,” DeYoreo adds.

Chung is the lead author and DeYoreo the corresponding author of a paper reporting this research in the journal Applied Physics Letters. The paper is titled “Temperature-dependence of ink transport during thermal dip-pen nanolithography.” Co-authoring the paper with Chung, DeYoreo and King were Jonathan Felts and Debin Wang.

This work at the Molecular Foundry was supported by DOE’s Office of Science and the Defense Advanced Research Projects Agency.

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The Molecular Foundry is one of five DOE Nanoscale Science Research Centers (NSRCs), national user facilities for interdisciplinary research at the nanoscale, supported by the DOE Office of Science. Together the NSRCs comprise a suite of complementary facilities that provide researchers with state-of-the-art capabilities to fabricate, process, characterize and model nanoscale materials, and constitute the largest infrastructure investment of the National Nanotechnology Initiative. The NSRCs are located at DOE’s Argonne, Brookhaven, Lawrence Berkeley, Oak Ridge and Sandia and Los Alamos National Laboratories. For more information about the DOE NSRCs, please visit science.energy.gov

DOE’s Office of Science is the single largest supporter of basic research in the physical sciences in the United States, and is working to address some of the most pressing challenges of our time. For more information, please visit the Office of Science website at science.energy.gov/

Lawrence Berkeley National Laboratory addresses the world’s most urgent scientific challenges by advancing sustainable energy, protecting human health, creating new materials, and revealing the origin and fate of the universe. Founded in 1931, Berkeley Lab’s scientific expertise has been recognized with 13 Nobel prizes. The University of California manages Berkeley Lab for the U.S. Department of Energy’s Office of Science. For more, visit www.lbl.gov

Additional Information: For more information about the Molecular Foundry visit the Website at foundry.lbl.gov/

Contact: Aditi Risbud asrisbud@lbl.gov 510-486-4861 DOE/Lawrence Berkeley National Laboratory

Finding reported in Nature Materials journal could boost role of solar-generated electricity as alternative to fossil fuels

NEW BRUNSWICK, N.J. – Physicists at Rutgers University have discovered new properties in a material that could result in efficient and inexpensive plastic solar cells for pollution-free electricity production.

The discovery, posted online and slated for publication in an upcoming issue of the journal Nature Materials, reveals that energy-carrying particles generated by packets of light can travel on the order of a thousand times farther in organic (carbon-based) semiconductors than scientists previously observed. This boosts scientists’ hopes that solar cells based on this budding technology may one day overtake silicon solar cells in cost and performance, thereby increasing the practicality of solar-generated electricity as an alternate energy source to fossil fuels.

“Organic semiconductors are promising for solar cells and other uses, such as video displays, because they can be fabricated in large plastic sheets,” said Vitaly Podzorov, assistant professor of Physics at Rutgers. “But their limited photo-voltaic conversion efficiency has held them back. We expect our discovery to stimulate further development and progress.”

An organic single-crystal transistor made out of rubrene (red crystal). This is an optoelectronic device similar to those used by Rutgers physicists to measure exciton diffusion. Credit: Rutgers University.

Podzorov and his colleagues observed that excitons – particles that form when semiconducting materials absorb photons, or light particles – can travel a thousand times farther in an extremely pure crystal organic semiconductor called rubrene. Until now, excitons were typically observed to travel less than 20 nanometers – billionths of a meter – in organic semiconductors. “This is the first time we observed excitons migrating a few microns,” said Podzorov, noting that they measured diffusion lengths from two to eight microns, or millionths of a meter. This is similar to exciton diffusion in inorganic solar cell materials such as silicon and gallium arsenide.

“Once the exciton diffusion distance becomes comparable to the light absorption length, you can collect most of the sunlight for energy conversion,” he said.

Excitons are particle-like entities consisting of an electron and an electron hole (a positive charge attributed to the absence of an electron). They can generate a photo-voltage when they hit a semiconductor boundary or junction, and the electrons move to one side and the holes move to the other side of the junction. If excitons diffuse only tens of nanometers, only those closest to the junctions or boundaries generate photo-voltage. This accounts for the low electrical conversion efficiencies in today’s organic solar cells.

“Now we lose 99 percent of the sunlight,” Podzorov noted.

While the extremely pure rubrene crystals fabricated by the Rutgers physicists are suitable only for laboratory research at this time, the research shows that the exciton diffusion bottleneck is not an intrinsic limitation of organic semiconductors. Continuing development could result in more efficient and manufacturable materials.

The scientists discovered that excitons in their rubrene crystals behaved more like the excitons observed in inorganic crystals – a delocalized form known as Wannier-Mott, or WM, excitons. Scientists previously believed that only the more localized form of excitons, called Frenkel excitons, were present in organic semiconductors. WM excitons move more rapidly through crystal lattices, resulting in better opto-electronic properties.

Podzorov noted that the research also produced a new methodology of measuring excitons based on optical spectroscopy. Since excitons are not charged, they are hard to measure using conventional methods. The researchers developed a technique called polarization resolved photocurrent spectroscopy, which dissociates excitons at the crystal’s surface and reveals a large photocurrent. The technique should be applicable to other materials, Podzorov claims. ###

Collaborating with Podzorov on the research were postdoctoral researcher Hikmat Najafov, graduate students Bumsu Lee and Qibin Zhou, and Leonard Feldman, director of the Rutgers Institute for Advanced Materials, Devices and Nanotechnology (IAMDN). Najafov and Podzorov are also affiliated with IAMDN.

Funding was provided by the National Science Foundation’s Division of Materials Research and Japan’s New Energy and Industrial Technology Development Organization (NEDO).

Contact: Carl Blesch cblesch@ur.rutgers.edu 732-932-7084 x616 Rutgers University

EDITOR’S NOTE: Professor Podzorov may be contacted at 848-391-5371 or podzorov@physics.rutgers.edu.

Applied physics professor Chris Marianetti figures out how to shatter the world’s strongest material

New York, NY November 29, 2010 In 2008, experiments at The Fu Foundation School of Engineering and Applied Science at Columbia University established pure graphene, a single layer of graphite only one atom thick, as the strongest material known to mankind. This raised a question for Chris Marianetti, Assistant Professor in Columbia Engineering’s Department of Applied Physics and Applied Mathematics: how and why does graphene break?

Using quantum theory and supercomputers, Marianetti has revealed the mechanisms of mechanical failure of pure graphene under tensile stress. In a paper recently accepted for publication in the journal Physical Review Letters, he shows that, when graphene is subject to strain equal in all directions, it morphs into a new structure which is mechanically unstable.

Marianetti says this failure mechanism is a novel soft-mode phonon instability. A phonon is a collective vibrational mode of atoms within a crystal, similar to a wave in a liquid.

A schematic of the soft phonon-mode in graphene. The undistorted graphene lattice is shown in yellow. Image credit: Chris Marianetti.

The fact that a phonon becomes “soft” under tensile strain means that the system can lower its energy by distorting the atoms along the vibrational mode and transitioning to a new crystalline arrangement. Under sufficient strain, graphene develops a particular soft-mode that causes the honeycomb arrangement of carbon atoms to be driven towards isolated hexagonal rings. This new crystal is structurally weaker, resulting in the mechanical failure of the graphene sheet.

“This is exciting on many different levels,” Marianetti notes. “Soft modes were first recognized in the 1960s in the context of ferroelectric phase transitions, but they have never been directly linked to fracture. Typically, defects in a material will always cause failure to happen prematurely, but the pristine nature of graphene allows one to test our prediction. We have already outlined some interesting new experiments to directly observe our theoretical prediction of the soft mode.”

Marianetti added that this is the first time a soft optical phonon has ever been linked to mechanical failure and that therefore it is likely that this novel failure mechanism is not exclusive to graphene but may be prevalent in other very thin materials. “With nanotechnology becoming increasingly ubiquitous, understanding the nature of mechanical behavior in low dimensional systems such as graphene is of great importance. We think strain may be a means to engineer the properties of graphene, and therefore understanding its limits is critical.” The research was funded by the National Science Foundation.

Marianetti’s research interests lie in the use of classical and quantum mechanics to model the behavior of materials at the atomic scale. In particular, he is focused on applying these techniques to materials with potential for energy storage and conversion. Current applications in his research program range from nuclear materials such as plutonium to rechargeable battery materials such as cobalt oxides. ###

Marianetti received his BS and MS degrees from Ohio State University and his PhD in materials science and engineering from MIT. Before joining the faculty at Columbia Engineering, he did post-doctoral research in the Department of Physics at Rutgers University and in the Materials Chemistry Division of Lawrence Livermore National Laboratory.

Columbia Engineering

Columbia University’s Fu Foundation School of Engineering and Applied Science offers programs to both undergraduate and graduate students who undertake a course of study leading to the bachelor’s, master’s, or doctoral degree in engineering and applied science. With facilities specifically designed and equipped to meet the laboratory and research needs of faculty and students, Columbia Engineering is home to a broad array of basic and advanced research installations, from the Columbia Center for Electron Transport in Molecular Nanostructures to the Columbia Genome Center. These interdisciplinary centers in science and engineering, materials research, nanoscale research, and genomic research are leading the way in their respective fields while individual groups of engineers and scientists collaborate to solve some of society’s more vexing challenges. www.engineering.columbia.edu/

Contact: Holly Evarts holly@engineering.columbia.edu 212-854-3206 Columbia University