From Rutgers: “Rutgers-Led Research Team Makes Major Stride in Explaining 30-Year-Old ‘Hidden Order’ Physics Mystery”

Rutgers University

February 12, 2015

Findings may lead to new kinds of materials for electronics and superconducting magnets.

A new explanation for a type of order, or symmetry, in an exotic material made with uranium may lead to enhanced computer displays and data storage systems, and more powerful superconducting magnets for medical imaging and levitating high-speed trains, according to a Rutgers-led team of research physicists.

The team’s findings are a major step toward explaining a puzzle that physicists worldwide have been struggling with for 30 years, when scientists first noticed a change in the material’s electrical and magnetic properties but were unable to describe it fully. This subtle change occurs when the material is cooled to 17.5 degrees above absolute zero or lower (a bone-chilling minus 428 degrees Fahrenheit).

Physicists Hsiang-Hsi Kung and Girsh Blumberg with instrumentation they used to examine hidden order. Photo: Carl Blesch

“This ‘hidden order’ has been the subject of nearly a thousand scientific papers since it was first reported in 1985 at Leiden University in the Netherlands,” said Girsh Blumberg, professor in the Department of Physics and Astronomy in the School of Arts and Sciences.

Collaborators from Rutgers University, the Los Alamos National Laboratory in New Mexico, and Leiden University published their findings this week in the web-based journal Science Express, which features selected research papers in advance of their appearance in the journal Science. Blumberg and two Rutgers colleagues, graduate student Hsiang-Hsi Kung and professor Kristjan Haule, led the collaboration.

Changes in order are what make liquid crystals, magnetic materials and superconductors work and perform useful functions. While the Rutgers-led discovery won’t transform high-tech products overnight, this kind of knowledge is vital to ongoing advances in electronic technology.

“The Los Alamos collaborators produced a crystalline sample of the uranium, ruthenium and silicon compound with unprecedented purity, a breakthrough we needed to make progress in solving the puzzle of hidden order,” said Blumberg. Uranium is commonly known as an element in nuclear reactor fuel or weapons material, but in this case, physicists value it as a heavy metal with electrons that behave differently than those in common metals.

Below the hidden order temperature of 17.5 degrees Kelvin, uranium electron orbital patterns in adjacent crystal layers become mirror images of each other (right side of illustration). Above that temperature, uranium electron orbitals are the same (left side of illustration).Image: Hsiang-Hsi Kung

Under these cold conditions, the orbital patterns made by electrons in uranium atoms from adjacent crystal layers become mirror images of each other. Above the hidden order temperature, these electron orbitals are the same. The Rutgers researchers discovered this so-called “broken mirror symmetry” using instrumentation they developed – based on a principle known as Raman scattering – to distinguish the pattern of the mirror images in the electron orbitals.

Blumberg also credits two theoretical physics professors at Rutgers for predicting the phenomenon that his team discovered.

“In this field, it’s rare to have such predictive power,” he said, noting that Gabriel Kotliar developed a computational technique that led to the prediction of the hidden order symmetry. Haule and Kotliar applied this technique to predict the changes in electron orbitals that Kung and Blumberg detected.

At still colder temperatures of 1.5 degrees above absolute zero, the material becomes superconducting – losing all resistance to the flow of electricity. While not practical for today’s products and systems that rely on superconductivity, the material provides new insights into ways that materials can become superconducting.

Kristjan Haule, left, reviews prediction of hidden order symmetry with Hsiang-Hsi Kung and Girsh Blumberg. Photo: Carl Blesch

The hidden order puzzle has also been a focus of other Rutgers researchers. Two years ago, professors Premala Chandra and Piers Coleman, along with alumna Rebecca Flint, published another theoretical explanation of the phenomenon in the journal Nature.

The Leiden University collaborator, John Mydosh, is a member of the laboratory that discovered hidden order in 1985.

“The work of Blumberg and his team is an important and viable step towards the understanding of hidden order,” Mydosh said. “We are well on our way after 30 years towards the final solution.”

Working with Kung, Blumberg and Haule at Rutgers were Verner Thorsmølle and Weilu Zhang. The Los Alamos National Laboratory collaborators are Ryan Baumbach and Eric Bauer.

The research was funded by the National Science Foundation and the U.S. Department of Energy’s Office of Basic Energy Sciences, Division of Materials Sciences and Engineering.

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Rutgers, The State University of New Jersey, is a leading national research university and the state’s preeminent, comprehensive public institution of higher education. Rutgers is dedicated to teaching that meets the highest standards of excellence; to conducting research that breaks new ground; and to providing services, solutions, and clinical care that help individuals and the local, national, and global communities where they live.

Founded in 1766, Rutgers teaches across the full educational spectrum: preschool to precollege; undergraduate to graduate; postdoctoral fellowships to residencies; and continuing education for professional and personal advancement.

From Caltech: “How Iron Feels the Heat”

Caltech

02/13/2015
Jessica Stoller-Conrad

As you heat up a piece of iron, the arrangement of the iron atoms changes several times before melting. This unusual behavior is one reason why steel, in which iron plays a starring role, is so sturdy and ubiquitous in everything from teapots to skyscrapers. But the details of just how and why iron takes on so many different forms have remained a mystery. Recent work at Caltech in the Division of Engineering and Applied Science, however, provides evidence for how iron’s magnetism plays a role in this curious property—an understanding that could help researchers develop better and stronger steel.

“Humans have been working with regular old iron for thousands of years, but this is a piece about its thermodynamics that no one has ever really understood,” says Brent Fultz, the Barbara and Stanley R. Rawn, Jr., Professor of Materials Science and Applied Physics.

The laws of thermodynamics govern the natural behavior of materials, such as the temperature at which water boils and the timing of chemical reactions. These same principles also determine how atoms in solids are arranged, and in the case of iron, nature changes its mind several times at high temperatures. At room temperature, the iron atoms are in an unusual loosely packed open arrangement; as iron is heated past 912 degrees Celsius, the atoms become more closely packed before loosening again at 1,394 degrees Celsius and ultimately melting at 1,538 degrees Celsius.

Iron is magnetic at room temperature, and previous work predicted that iron’s magnetism favors its open structure at low temperatures, but at 770 degrees Celsius iron loses its magnetism. However, iron maintains its open structure for more than a hundred degrees beyond this magnetic transition. This led the researchers to believe that there must be something else contributing to iron’s unusual thermodynamic properties.

For this missing link, graduate student Lisa Mauger and her colleagues needed to turn up the heat. Solids store heat as small atomic vibrations—vibrations that create disorder, or entropy. At high temperatures, entropy dominates thermodynamics, and atomic vibrations are the largest source of entropy in iron. By studying how these vibrations change as the temperature goes up and magnetism is lost, the researchers hoped to learn more about what is driving these structural rearrangements.

To do this, the team took its samples of iron to the High Pressure Collaborative Access Team beamline of the Advanced Photon Source [APS] at Argonne National Laboratory [ANL] in Argonne, Illinois. This synchrotron facility produces intense flashes of x-rays that can be tuned to detect the quantum particles of atomic vibration—called phonon excitations—in iron.

APS at ANL

When coupling these vibrational measurements with previously known data about the magnetic behavior of iron at these temperatures, the researchers found that iron’s vibrational entropy was much larger than originally suspected. In fact, the excess was similar to the entropy contribution from magnetism—suggesting that magnetism and atomic vibrations interact synergistically at moderate temperatures. This excess entropy increases the stability of the iron’s open structure even as the sample is heated past the magnetic transition.

The technique allowed the researchers to conclude, experimentally and for the first time, that magnons—the quantum particles of electron spin (magnetism)—and phonons interact to increase iron’s stability at high temperatures.

Because the Caltech group’s measurements matched up with the theoretical calculations that were simultaneously being developed by collaborators in the laboratory of Jörg Neugebauer at the Max-Planck-Institut für Eisenforschung GmbH (MPIE), Mauger’s results also contributed to the validation of a new computational model.

“It has long been speculated that the structural stability of iron is strongly related to an inherent coupling between magnetism and atomic motion,” says Fritz Körmann, postdoctoral fellow at MPIE and the first author on the computational paper. “Actually finding this coupling, and that the data of our experimental colleagues and our own computational results are in such an excellent agreement, was indeed an exciting moment.”

“Only by combining methods and expertise from various scientific fields such as quantum mechanics, statistical mechanics, and thermodynamics, and by using incredibly powerful supercomputers, it became possible to describe the complex dynamic phenomena taking place inside one of the technologically most used structural materials,” says Neugebauer. “The newly gained insight of how thermodynamic stability is realized in iron will help to make the design of new steels more systematic.”

For thousands of years, metallurgists have been working to make stronger steels in much the same way that you’d try to develop a recipe for the world’s best cookie: guess and check. Steel begins with a base of standard ingredients—iron and carbon—much like a basic cookie batter begins with flour and butter. And just as you’d customize a cookie recipe by varying the amounts of other ingredients like spices and nuts, the properties of steel can be tuned by adding varying amounts of other elements, such as chromium and nickel.

With a better computational model for the thermodynamics of iron at different temperatures—one that takes into account the effects of both magnetism and atomic vibrations—metallurgists will now be able to more accurately predict the thermodynamic properties of iron alloys as they alter their recipes.

The experimental work was published in a paper titled Nonharmonic Phonons in α-Iron at High Temperatures,” in the journal Physical Review B. In addition to Fultz and first author Mauger, other Caltech coauthors include Jorge Alberto Muñoz (PhD ’13) and graduate student Sally June Tracy. The computational paper, Temperature Dependent Magnon-Phonon Coupling in bcc Fe from Theory and Experiment, was coauthored by Fultz and Mauger, led by researchers at the Max Planck Institute, and published in the journal Physical Review Letters. Fultz’s and Mauger’s work was supported by funding from the U.S. Department of Energy.

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The California Institute of Technology (commonly referred to as Caltech) is a private research university located in Pasadena, California, United States. Caltech has six academic divisions with strong emphases on science and engineering. Its 124-acre (50 ha) primary campus is located approximately 11 mi (18 km) northeast of downtown Los Angeles. “The mission of the California Institute of Technology is to expand human knowledge and benefit society through research integrated with education. We investigate the most challenging, fundamental problems in science and technology in a singularly collegial, interdisciplinary atmosphere, while educating outstanding students to become creative members of society.”

From phys.org: “Exotic states materialize with supercomputers”

phys.org

Feb 12, 2015
Jorge Salazar

Scientists used supercomputers to find a new class of materials that possess an exotic state of matter known as the quantum spin Hall effect. The researchers published their results in the journal Science in December 2014, where they propose a new type of transistor made from these materials.

The science team included Ju Li, Liang Fu, Xiaofeng Qian, and Junwei Liu, experts in topological phases of matter and two-dimensional materials research at the Massachusetts Institute of Technology (MIT). They calculated the electronic structures of the materials using the Stampede and Lonestar supercomputers of the Texas Advanced Computing Center.

Stampede

Lonestar

The computational allocation was made through XSEDE, the Extreme Science and Engineering Discovery Environment, a single virtual system funded by the National Science Foundation (NSF) that scientists use to interactively share computing resources, data and expertise. The study was funded by the U.S. Department of Energy and the NSF.

“To me, national computing resources like XSEDE, or specifically the Stampede and Lonestar supercomputers, are extremely helpful to computational scientists,” Xiaofeng Qian said. In January 2015, Qian left MIT to join Texas A&M University as the first tenure-track assistant professor at its newly formed Department of Materials Science and Engineering.

What Qian and colleagues did was purely theoretical work, using Stampede for part of the calculations that modeled the interactions of atoms in the novel materials, two-dimensional transition metal dichalcogenides (TMDC). Qian used the molecular dynamics simulation software Vienna Ab initio Simulation Package to model a unit cell of atoms, the basic building block of the crystal lattice of TMDC.

Qian and colleagues found that the topological phases in the TMDC materials can be turned on and off by simply applying a vertical electric field that is perpendicular to the atomic plane of the material. That’s shown here in calculations by the red crossing lines that conduct electricity along the edges of the material when the electric field is turned off. When the electric field is turned on the red lines are broken and a black gap appears between the valence and conducting bands of TMDC, which indicate the edges no longer conduct. Credit: Qian et. al.


This picture tells quite a story to scientists. It’s a portrait of what they call a topological insulator, materials that conduct only at their edges. Technically it shows the edge density of states calculated for a monolayer transition metal dichalcogenide in the 1T’-MoS2 structural phase. There’s a black gap between the purple blobs at the bottom and top. What’s more, there’s crisscrossing reddish lines that bridge the gap. The lines indicate the edge state of the material, allowing electrons to cross the gap and conduct electricity. Credit: Qian et. al.

“If you look at the unit cell, it’s not large. They are just a few atoms. However, the problem is that we need to predict the band structure of charge carriers in their excited states in the presence of spin coupling as accurately as possible,” Qian said.

Scientists diagram the electronic band structure of materials to show the energy ranges an electron is allowed, with the band gap showing forbidden zones that basically block the flow of current. Spin coupling accounts for the electromagnetic interactions between electron’s spin and magnetic field generated from the electron’s motion around the nucleus.

The complexity lies in the details of these interactions, for which Qian applied many-body perturbation theory with the GW approximation, a state-of-the-art first principles method, to calculate the quasiparticle electronic structures for electrons and holes. The ‘G’ is short for Green’s Function and ‘W’ for screened Coulomb interaction, Qian explained.

This diagram illustrates the concept behind the MIT team’s vision of a new kind of electronic device based on 2-D materials. The 2-D material is at the middle of a layered “sandwich,” with layers of another material, boron nitride, at top and bottom (shown in gray). When an electric field is applied to the material, by way of the rectangular areas at top, it switches the quantum state of the middle layer (yellow areas). The boundaries of these “switched” regions act as perfect quantum wires, potentially leading to new electronic devices with low losses. (Credit: Yan Lian, MIT.) “In order to carry out these calculations to obtain reasonable convergence in the results, we have to use 96 cores, sometimes even more,” Qian said. “And then we need them for 24 hours. The Stampede computer is very efficient and powerful. The work that we have been showing is not just one material; we have several other materials as well as different conditions. In this sense, access to the resources, especially Stampede, is very helpful to our project.”

The big picture for Qian and his colleagues is the hunt for new kinds of materials with extraordinarily useful properties. Their target is room-temperature quantum spin Hall insulators, which are basically near-two-dimensional materials that block current flow everywhere except along their edges. “Along the edges you have the so-called spin up electron flow in one direction, and at the same time you have spin down electrons and flows away in the opposite direction,” Qian explained. “Basically, you can imagine, by controlling the injection of charge carriers, one can come up with spintronics, or electronics.”

The scientists in this work proposed a topological field-effect transistor, made of sheets of hexagonal boron interlaced with sheets of TMDC. “We found a very convenient method to control the topological phase transition in these quantum spin Hall interlayers,” Qian said. “This is very important because once we have this capability to control the phase transition, we can design some electronic devices that can be controlled easily through electrical fields.”

Qian stressed that this work lays the theoretical ground for future real experiments in the lab. He hopes it might develop into an actual transistor suitable for a quantum computer, basically an as-yet-unrealized machine that manipulates data beyond just the binary of ones and zeros.

“So far, we haven’t looked into the detailed applications for quantum computing yet,” Qian said. “However, it is possible to combine these materials with superconductors and come up with the so-called Majorana fermion zero mode for quantum computing.”

Read more at: http://phys.org/news/2015-02-exotic-states-materialize-supercomputers.html#jCp

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From LBL: “New Design Tool for Metamaterials”

Berkeley Lab

February 9, 2015
Lynn Yarris (510) 486-5375

Confocal microscopy confirmed that the nonlinear optical properties of metamaterials can be predicted using a
theory about light passing through nanostructures.

Metamaterials – artificial nanostructures engineered with electromagnetic properties not found in nature – offer tantalizing future prospects such as high resolution optical microscopes and superfast optical computers. To realize the vast potential of metamaterials, however, scientists will need to hone their understanding of the fundamental physics behind them. This will require accurately predicting nonlinear optical properties – meaning that interaction with light changes a material’s properties, for example, light emerges from the material with a different frequency than when it entered. Help has arrived.

Scientists with the U.S. Department of Energy (DOE)’s Lawrence Berkeley National Laboratory (Berkeley Lab) and the University of California (UC) Berkeley have shown, using a recent theory for nonlinear light scattering when light passes through nanostructures, that it is possible to predict the nonlinear optical properties of metamaterials.

“The key question has been whether one can determine the nonlinear behavior of metamaterials from their exotic linear behavior,” says Xiang Zhang, director of Berkeley Lab’s Materials Sciences Division and an international authority on metamaterial engineering who led this study. “We’ve shown that the relative nonlinear susceptibility of large classes of metamaterials can be predicted using a comprehensive nonlinear scattering theory. This will allow us to efficiently design metamaterials with strong nonlinearity for important applications such as coherent Raman sensing, entangled photon generation and frequency conversion.”

Xiang Zhang, Haim Suchowski and Kevin O’Brien were part of the team that discovered a way to predict thenon-linear optical properties of metamaterials. (Photo by Roy Kaltschmidt)

Zhang, who holds the Ernest S. Kuh Endowed Chair at UC Berkeley and is a member of the Kavli Energy NanoSciences Institute at Berkeley (Kavli ENSI), is the corresponding author of a paper describing this research in the journal Nature Materials. The paper is titled Predicting nonlinear properties of metamaterials from the linear response. The other authors are Kevin O’Brien, Haim Suchowski, Junsuk Rho, Alessandro Salandrino, Boubacar Kante and Xiaobo Yin.

The unique electromagnetic properties of metamaterials stem from their physical structure rather than their chemical composition. This structure, for example, provides certain metamaterials with a negative refractive index, an optical property in which the phase front of light moving through a material propagates backward towards the source. The phase front light moving through natural materials always propagates forward, away from its source.

Zhang and his group have already exploited the linear optical properties of metamaterials to create the world’s first optical invisibility cloak and mimic black holes. Most recently they used a nonlinear metamaterial with a refractive index of zero to generate “phase mismatch–free nonlinear light,” meaning light waves moved through the material gaining strength in all directions. However, engineering nonlinear metamaterials remains in its infancy, with no general conclusion on the relationship between linear and nonlinear properties.

Metamaterial arrays whose geometry varied gradually from a symmetric bar to an asymmetric U-shape were used to compare the predictive abilities of Miller’s rule and a non-linear light scattering theory.

For the past several decades, scientists have estimated the nonlinear optical properties in natural crystals using a formulation known as “Miller’s rule,” for the physicist Robert Miller who authored it. In this new study, Zhang and his group found that Miller’s rule doesn’t work for a number of metamaterials. That’s the bad news. The good news is that a nonlinear light scattering theory, developed for nanostructures by Dutch scientist Sylvie Roke, does.

“From the linear properties, one calculates the nonlinear polarization and the mode of the nanostructure at the second harmonic,” says Kevin O’Brien, co-lead author of the Nature Materials paper and a member of Zhang’s research group. “We found the nonlinear emission is proportional to the overlap integral between these, not simply determined by their linear response.”

Zhang, O’Brien, Suchowski, and the other contributors to this study evaluated Miller’s rule and the nonlinear light scattering theory by comparing their predictions to experimental results obtained using a nonlinear stage-scanning confocal microscope.

“Nonlinear stage-scanning confocal microscopy is critical because it allows us to rapidly measure the nonlinear emission from thousands of different nanostructures while minimizing the potential systematic errors, such as intensity or beam pointing variations, often associated with tuning the wavelength of an ultrafast laser,” O’Brien says.

The researchers used confocal microscopy to observe the second harmonic generation from metamaterial arrays whose geometry was gradually shifted from a symmetric bar-shape to an asymmetric U-shape. Second harmonic light is a nonlinear optical property in which photons with the same frequency interact with a nonlinear material to produce new photons at twice the energy and half the wavelength of the originals. It was the discovery of optical second harmonic generation in 1961 that started modern nonlinear optics.

“Our results show that nonlinear scattering theory can be a valuable tool in the design of nonlinear metamaterials not only for second-order but also higher order nonlinear optical responses over a broad range of wavelengths,” O’Brien says. “We’re now using these experimental and theoretical techniques to explore other nonlinear processes in metamaterials, such as parametric amplification and entangled photon generation.”

This research was supported by the DOE Office of Science.

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From Discovery: “New Steel Alloy Stronger Than Titanium”

Discovery News

Feb 4, 2015
Glenn McDonald

Annealed microstructure of high-specific-strength steel (HSSS). Fine FeAl-type B2 precipitates form during annealing in between the B2 stringer bands in steel matrix. The specimen was annealed for 15 min at 900 C. Hansoo Kim

Big news from the metallurgy desk this week: It looks like steel is about to get a lot steelier.

According to a report published today in the prestigious journal Nature, researchers in South Korea have developed a new recipe for making a high-strength, low-density steel alloy that can outperform titanium in terms of strength and ductility.

In materials science, ductility is a measure of a substance’s ability to be stretched or bent without breaking. It’s a big deal in manufacturing — particularly auto manufacturing — because steel alloys designed to make the metal lighter usually result in a more brittle metal.

As a result, manufacturers looking to make lighter cars have turned to alternative materials. In statistics cited in the Nature report, the share by weight of steel and iron in an average light vehicle decreased from 68.1 percent in 1995 to 60.1 percent in 2011.

But the new steel alloy proposed by the South Korean team actually strengthens the steel in the same fabrication process that makes it lighter and more flexible. The specifics get pretty complicated, but the recipe essentially improves on existing steel-aluminum alloying processes.

As such, deployment of the new technique could be rapid and the breakthrough could have wide-reaching implications in manufacturing, construction and engineering.

“The balance of lightness, strength and ductility in metallic alloys has been explored since the Bronze Age,” the research team writes in the Nature report. “There is increasing demand for a broad range of structural materials for environmentally benign, energy-efficient, lightweight engineering systems.”

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From BNL: “Self-Assembled Nanotextures Create Antireflective Surface on Silicon Solar Cells”

Brookhaven Lab

January 21, 2015
Karen McNulty Walsh, (631) 344-8350 or Peter Genzer, (631) 344-3174

Nanostructured surface textures—with shapes inspired by the structure of moths’ eyes—prevent the reflection of light off silicon, improving conversion of sunlight to electricity

Chuck Black of the Center for Functional Nanomaterials displays a nanotextured square of silicon on top of an ordinary silicon wafer. The nanotextured surface is completely antireflective and could boost the production of solar energy from silicon solar cells.

Reducing the amount of sunlight that bounces off the surface of solar cells helps maximize the conversion of the sun’s rays to electricity, so manufacturers use coatings to cut down on reflections. Now scientists at the U.S. Department of Energy’s Brookhaven National Laboratory show that etching a nanoscale texture onto the silicon material itself creates an antireflective surface that works as well as state-of-the-art thin-film multilayer coatings.

The surface nanotexture … drastically cut down on reflection of many wavelengths of light simultaneously.

Their method, described in the journal Nature Communications and submitted for patent protection, has potential for streamlining silicon solar cell production and reducing manufacturing costs. The approach may find additional applications in reducing glare from windows, providing radar camouflage for military equipment, and increasing the brightness of light-emitting diodes.

“For antireflection applications, the idea is to prevent light or radio waves from bouncing at interfaces between materials,” said physicist Charles Black, who led the research at Brookhaven Lab’s Center for Functional Nanomaterials (CFN), a DOE Office of Science User Facility.

Preventing reflections requires controlling an abrupt change in “refractive index,” a property that affects how waves such as light propagate through a material. This occurs at the interface where two materials with very different refractive indices meet, for example at the interface between air and silicon. Adding a coating with an intermediate refractive index at the interface eases the transition between materials and reduces the reflection, Black explained.

“The issue with using such coatings for solar cells,” he said, “is that we’d prefer to fully capture every color of the light spectrum within the device, and we’d like to capture the light irrespective of the direction it comes from. But each color of light couples best with a different antireflection coating, and each coating is optimized for light coming from a particular direction. So you deal with these issues by using multiple antireflection layers. We were interested in looking for a better way.”

For inspiration, the scientists turned to a well-known example of an antireflective surface in nature, the eyes of common moths. The surfaces of their compound eyes have textured patterns made of many tiny “posts,” each smaller than the wavelengths of light. This textured surface improves moths’ nighttime vision, and also prevents the “deer in the headlights” reflecting glow that might allow predators to detect them.

“We set out to recreate moth eye patterns in silicon at even smaller sizes using methods of nanotechnology,” said Atikur Rahman, a postdoctoral fellow working with Black at the CFN and first author of the study.

A closeup shows how the nanotextured square of silicon completely blocks reflection compared with the surrounding silicon wafer.

The scientists started by coating the top surface of a silicon solar cell with a polymer material called a “block copolymer,” which can be made to self-organize into an ordered surface pattern with dimensions measuring only tens of nanometers. The self-assembled pattern served as a template for forming posts in the solar cell like those in the moth eye using a plasma of reactive gases—a technique commonly used in the manufacture of semiconductor electronic circuits.

The resulting surface nanotexture served to gradually change the refractive index to drastically cut down on reflection of many wavelengths of light simultaneously, regardless of the direction of light impinging on the solar cell.

“Adding these nanotextures turned the normally shiny silicon surface absolutely black,” Rahman said.

Solar cells textured in this way outperform those coated with a single antireflective film by about 20 percent, and bring light into the device as well as the best multi-layer-coatings used in the industry.

“We are working to understand whether there are economic advantages to assembling silicon solar cells using our method, compared to other, established processes in the industry,” Black said.

Hidden layer explains better-than-expected performance

One intriguing aspect of the study was that the scientists achieved the antireflective performance by creating nanoposts only half as tall as the required height predicted by a mathematical model describing the effect. So they called upon the expertise of colleagues at the CFN and other Brookhaven scientists to help sort out the mystery.

Details of the nanotextured antireflective surface as revealed by a scanning electron microscope at the Center for Functional Nanomaterials. The tiny posts, each smaller than the wavelengths of light, are reminiscent of the structure of moths’ eyes, an example of an antireflective surface found in nature.

“This is a powerful advantage of doing research at the CFN—both for us and for academic and industrial researchers coming to use our facilities,” Black said. “We have all these experts around who can help you solve your problems.”

Using a combination of computational modeling, electron microscopy, and surface science, the team deduced that a thin layer of silicon oxide similar to what typically forms when silicon is exposed to air seemed to be having an outsized effect.

“On a flat surface, this layer is so thin that its effect is minimal,” explained Matt Eisaman of Brookhaven’s Sustainable Energy Technologies Department and a professor at Stony Brook University. “But on the nanopatterned surface, with the thin oxide layer surrounding all sides of the nanotexture, the oxide can have a larger effect because it makes up a significant portion of the nanotextured material.”

Said Black, “This ‘hidden’ layer was the key to the extra boost in performance.”

The scientists are now interested in developing their self-assembly based method of nanotexture patterning for other materials, including glass and plastic, for antiglare windows and coatings for solar panels.

This research was supported by the DOE Office of Science.

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One of ten national laboratories overseen and primarily funded by the Office of Science of the U.S. Department of Energy (DOE), Brookhaven National Laboratory conducts research in the physical, biomedical, and environmental sciences, as well as in energy technologies and national security. Brookhaven Lab also builds and operates major scientific facilities available to university, industry and government researchers. The Laboratory’s almost 3,000 scientists, engineers, and support staff are joined each year by more than 5,000 visiting researchers from around the world.Brookhaven is operated and managed for DOE’s Office of Science by Brookhaven Science Associates, a limited-liability company founded by Stony Brook University, the largest academic user of Laboratory facilities, and Battelle, a nonprofit, applied science and technology organization.

From BNL: “Self-destructive Effects of Magnetically-doped Ferromagnetic Topological Insulators”

Brookhaven Lab

January 19, 2015
Karen McNulty Walsh, (631) 344-8350 or Peter Genzer, (631) 344-3174

Séamus Davis

The discovery of “topologically protected” electrical conductivity on the surface of some materials whose bulk interior acts as an insulator was among the most sensational advances in the last decade of condensed matter physics—with predictions of numerous unusual electronic states and new potential applications. But many of these predicted phenomena have yet to be observed. Now, a new atomic-scale study of the surface properties of one of these ferromagnetic topological insulators reveals that these materials may not be what they had seemed.

The research—conducted at the U.S. Department of Energy’s Brookhaven National Laboratory and published in the Early Edition of the Proceedings of the National Academy of Sciences—revealed extreme disorder in a fundamental property of the surface electrons known as the “Dirac mass.” Like the mass imparted to fundamental particles by their interactions with the recently confirmed Higgs field, Dirac mass results from surface particles’ interactions with magnetic fields. These fields are created by the presence of magnetic atoms substituted into the material’s crystal lattice to convert it into a ferromagnetic topological insulator.

“What we have discovered is that the Dirac mass is extremely disordered at the nanoscale, which was completely unanticipated,” said J.C. Séamus Davis, a senior physicist at Brookhaven Lab and a professor at Cornell University and St. Andrew’s University in Scotland, who led the research. “The analogous situation in elementary particles would be if the Higgs field was random throughout space so that the electron mass (and the mass of a car or a person) was randomly different at every location. It would be an extremely chaotic universe!”

In the ferromagnetic topological insulators, Davis said, the chaos eventually destroys the exotic surface state.

“Our findings explain why many of the electronic phenomena expected to be present in ferromagnetic topological insulators are in fact suppressed by the very atoms that generate this state, and offer insight into the true atomic-scale mechanism by which the observed properties arise,” Davis said. “This new understanding will likely result in revisions of the basic research directions in this field.”

Precision studies

Under Davis’ guidance, Brookhaven Lab postdoctoral fellows Inhee Lee and Chung Koo Kim studied nearly perfect ferromagnetic topological insulator crystals grown by Brookhaven physicist Genda Gu. They used a spectroscopic imaging, scanning tunneling microscope (SI-STM) designed and built by Davis at Brookhaven to scan the surface of these crystals atom-by-atom. This tool has the precision to simultaneously reveal the positions of the magnetic dopant atoms and the resulting Dirac mass.

Prior to this work, scientists had assumed that these magnetic dopant atoms were not detrimental to the topological surface states. But no one had directly studied how the spatial arrangements of the magnetic dopant atoms at the atomic scale influenced the Dirac-mass because there were no reliable techniques to do so, until now.

The new atom-by-atom SI-STM data revealed not only the intense nanoscale disorder in the Dirac mass, but also showed that this disorder is directly related to fluctuations in the density of the magnetic dopant atoms on different parts of the crystal surface. In the paper, the scientists also provide the first direct evidence for the actual mechanism of how surface ferromagnetism arises in a topological insulator, and determine directly the strength of the surface-state magnetic-dopant interactions.

“The Dirac-mass ‘gapmap’ technique introduced here reveals radically new perspectives on the physics of ferromagnetic topological insulators,” Davis said.

“The key realization from these discoveries—aside from a clear and direct picture of what is going on at the atomic scale—is that, in ferromagnetic topological insulators dominated by this magnetic-dopant atom phenomena, many of the exotic and potentially valuable phenomena expected for these materials are actually being quantum mechanically short circuited by the random variations of Dirac mass,” he said.

Of course, there may still be a way to achieve all the exotic physics expected of ferromagnetic topological insulators—if scientists can develop ways to control the dopant-induced Dirac-mass gap disorder. Hence the idea of a whole new research direction for this field.

This research was funded by the DOE Office of Science.

See the full article here.

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One of ten national laboratories overseen and primarily funded by the Office of Science of the U.S. Department of Energy (DOE), Brookhaven National Laboratory conducts research in the physical, biomedical, and environmental sciences, as well as in energy technologies and national security. Brookhaven Lab also builds and operates major scientific facilities available to university, industry and government researchers. The Laboratory’s almost 3,000 scientists, engineers, and support staff are joined each year by more than 5,000 visiting researchers from around the world.Brookhaven is operated and managed for DOE’s Office of Science by Brookhaven Science Associates, a limited-liability company founded by Stony Brook University, the largest academic user of Laboratory facilities, and Battelle, a nonprofit, applied science and technology organization.

From LBL: “From the Bottom Up: Manipulating Nanoribbons at the Molecular Level”

Berkeley Lab

January 12, 2015
Rachel Berkowitz 510.486.7254

Narrow strips of graphene called nanoribbons exhibit extraordinary properties that make them important candidates for future nanoelectronic technologies. A barrier to exploiting them, however, is the difficulty of controlling their shape at the atomic scale, a prerequisite for many possible applications.

Now, researchers at the US Department of Energy’s (DOE) Lawrence Berkeley National Laboratory (Berkeley Lab) and the University of California, Berkeley, have developed a new precision approach for synthesizing graphene nanoribbons from pre-designed molecular building blocks. Using this process the researchers have built nanoribbons that have enhanced properties—such as position-dependent, tunable bandgaps—that are potentially very useful for next-generation electronic circuitry.

The results appear in a paper titled Molecular bandgap engineering of bottom-up synthesized graphene nanoribbon heterojunctions, published in Nature Nanotechnology.

“This work represents progress towards the goal of controllably assembling molecules into whatever shapes we want,” says Mike Crommie, senior scientist at Berkeley Lab, professor at UC Berkeley, and a leader of the study. “For the first time we have created a molecular nanoribbon where the width changes exactly how we designed it to.”

Felix Fischer (on left) and Mike Crommie

Nanoribbons past and present

Previously, scientists made nanoribbons that have a constant width throughout. “That makes for a nice wire or a simple switching element,” says Crommie, “but it does not provide a lot of functionality. We wanted to see if we could change the width within a single nanoribbon, controlling the structure inside the nanoribbon at the atomic scale to give it new behavior that is potentially useful.”

Felix Fischer, Professor of Chemistry at UC Berkeley who jointly led the study, designed the molecular components to find out whether this would be possible. Together, Fischer and Crommie discovered that molecules of different widths can indeed be made to chemically bond such that width is modulated along the length of a single resulting nanoribbon.

“Think of the molecules as different sized Lego blocks,” explains Fischer. Each block has a certain defined structure and when pieced together they result in a particular shape for the whole nanoribbon. “We want to see if we can understand the exotic properties that emerge when we assemble these molecular structures, and to see if we can exploit them to build new functional devices.”

Until now, nanoribbon synthesis has mostly involved etching ribbons out of larger 2D sheets of graphene. The problem, according to Fischer, is that this lacks precision and each resulting nanoribbon has a unique, slightly random structure. Another method has been to unzip nanotubes to yield nanoribbons. This produces smoother edges than the “top-down” etching technique, but it is difficult to control because nanotubes have different widths and chiralities.

A third route, discovered by Roman Fasel of Swiss Federal Laboratories for Materials Science & Technology along with his co-workers, involves placing molecules on a metal surface and chemically fusing them together to form perfectly uniform nanoribbons. Crommie and Fischer modified this last approach and have shown that if the shapes of the constituent molecules are varied then so is the shape of the resulting nanoribbon.

“What we’ve done that is new is to show that it is possible to create atomically-precise nanoribbons with non-uniform shape by changing the shapes of the molecular building blocks,” says Crommie.

Controlling quantum properties

Electrons within the nanoribbons set up quantum mechanical standing-wave patterns that determine the nanoribbon’s electronic properties, such as its “bandgap”. This determines the energetics of how electrons move through a nanoribbon, including which regions they accumulate in and which regions they avoid.

In the past, scientists spatially engineered the bandgap of micron-scale devices through doping, the addition of impurities to a material. For the smaller nanoribbons, however, it is possible to change the bandgap by modifying their width in sub-nanometer increments, a process that Crommie and Fischer have dubbed “molecular bandgap engineering.” This kind of engineering allows the researchers to tailor the quantum mechanical properties of nanoribbons so they might be flexibly used for future nanoelectronic devices.

Figure 1: Bottom-up synthesis of graphene nanoribbons from molecular building blocks 1 and 2. (a) The resulting ribbon, or heterojunction, has varied widths as a result of different width molecules 1 and 2. (b) Scanning transmission microscope image of graphene nanoribbon heterojunction, with larger-scale inset of multiple ribbons.

To test their molecular bandgap engineering, Crommie’s group used scanning tunneling microscopy (STM), a technique that can spatially map the behavior of electrons inside a single nanoribbon. “We needed to know the atomic-scale shape of the nanoribbons, and we also needed to know how the electrons inside adapt to that shape,” says Crommie. UC Berkeley professor of physics Steven Louie and his student Ting Cao calculated the electronic structure of the nanribbons in order to correctly interpret the STM images. This “closed the loop” between nanoribbon design, fabrication, and characterization.

New directions toward new devices

A major question in this work is how best to build useful devices from these tiny molecular structures. While the team has shown how to fabricate width-varying nanoribbons, it has not yet incorporated them into actual electronic circuits. Crommie and Fischer hope to use this new type of nanoribbon to eventually create new device elements – such as diodes, transistors, and LEDs – that are smaller and more powerful than those in current use. Ultimately they hope to incorporate nanoribbons into complex circuits that yield better performance than today’s computer chips. To this end they are collaborating with UC Berkeley electrical engineers such as Jeffrey Bokor and Sayeef Salahuddin.

The required spatial precision already exists: the team can modulate nanoribbon width from 0.7 nm to 1.4nm, creating junctions where narrow nanoribbons fuse seamlessly into wider ones. “Varying the width by a factor of two allows us to modulate the bandgap by more than 1eV,” says Fischer. For many applications this is sufficient for building useful devices.

While the potential applications are exciting, Crommie points out that a central motivation for the research is the desire to answer basic scientific questions like how nanoribbons with non-uniform width actually behave. “We set out to answer an interesting question, and we answered it,” he concludes.

The complete list of authors on the paper includes Yen-Chia Chen, Ting Cao, Chen Chen, Zahra Pedramrazi, Danny Haberer, Dimas de Oteyza, Felix Fischer, Steven Louie, and Michael Crommie.

This research was supported by the Office of Naval Research BRC Program (molecular synthesis and characterization), and by the DOE Office of Science (instrumentation development, STM operation and simulations); and by the National Science Foundation (image analysis, theory formalism).

See the full article here.

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Stem Education Coalition

A U.S. Department of Energy National Laboratory Operated by the University of California

From Brookhaven Lab: “Microscopy Reveals how Atom-High Steps Impede Oxidation of Metal Surfaces”

Brookhaven Lab

December 29, 2014
Karen McNulty Walsh, (631) 344-8350 or Peter Genzer, (631) 344-3174

Rust never sleeps. Whether a reference to the 1979 Neil Young album or a product designed to protect metal surfaces, the phrase invokes the idea that corrosion from oxidation.—the more general chemical name for rust and other reactions of metal with oxygen—is an inevitable, persistent process. But a new study performed at the Center for Functional Nanomaterials (CFN) at the U.S. Department of Energy’s (DOE) Brookhaven National Laboratory reveals that certain features of metal surfaces can stop the process of oxidation in its tracks.

Low-energy electron microscopy images of the nickel-aluminum surface before and after oxidation. The faint lines before oxidation indicate the atom-high steps that separate flat terrace sections of the crystal surface. As oxidation begins at a point on one terrace, the oxide spreads in elongated stripes along that terrace, pushing steps out of the way and bunching them closer and closer together. Eventually the bunching of steps stops the growth of the oxide stripe and another begins to form, often at right angles, to produce a grid-like pattern.

“As the oxide stripes grow … one ends up with these patterns of blocks and lines that are reminiscent of the grid-based paintings by Mondrian.”
— Peter Sutter

The findings, published in the Proceedings of the National Academy of Sciences, could be relevant to understanding and perhaps controlling oxidation in a wide range of materials—from catalysts to the superalloys used in jet engine turbines and the oxides in microelectronics.

The experiments were performed by a team led by Guangwen Zhou of Binghamton University, in collaboration with Peter Sutter of the CFN, a DOE Office of Science User Facility. The team used a low-energy electron microscope (LEEM) to capture changes in the surface structure of a nickel-aluminum alloy as “stripes” of metal oxide formed and grew under a range of elevated temperatures.

“These microscopes are not that frequently found in ordinary research labs; there are only a handful around the U.S.,” Sutter said. “We have a pretty lively ‘user community’ of scientists who come to the CFN just to use this type of instrument.”

Peter Sutter with one of the low-energy electron microscopes at Brookhaven Lab’s Center for Functional Nanomaterials.

The metal Zhou wanted to study, nickel-aluminum, has a characteristic common to all crystal surfaces: a stepped structure composed of a series of flat terraces at different heights. The steps between terraces are only one atom high, but they can have a significant effect on material properties. Being able to see the steps and how they change is essential to understanding how the surface will behave in different environments, in this case in response to oxygen, Sutter said.

Said Zhou, “The acquisition of this kind of knowledge is essential for gaining control over the response of a metal surface to the environment.”

Scientists have known for a while that the atoms at the edges of atomic steps are especially reactive. “They are not as completely surrounded as the atoms that are part of the flat terraces, so they are more free to interact with the environment,” Sutter said. “That plays a role in the material’s surface chemistry.”

The new study showed that the aluminum atoms involved in forming aluminum oxide stripes came exclusively from the steps, not the terraces. But the LEEM images revealed even more: The growing oxide stripes could not “climb” up or down the steps, but were confined to the flat terraces. To continue to grow, they had to push the steps away as oxygen continued to grab aluminum atoms from the edges. This forced the steps to bunch closer and closer together, eventually slowing the rate of oxide stripe growth, and then completely stopping it.

“For the first time we show that atomic steps can slow surface oxidation at the earliest stages,” Zhou said.
Guangwen Zhou

Guangwen Zhou at Binghamton University’s Analytical and Diagnostics Laboratory. Photo credit: Jonathan Cohen, Binghamton University

However, as one stripe stops growing, another begins to form. “As the oxide stripes grow along the two possible directions on the crystal, which are at right angles to one another, one ends up with these patterns of blocks and lines that are reminiscent of the grid-based paintings by Mondrian,” Sutter said. “They are quite beautiful…” and persistent after all.

In fact, scientists who’ve studied a different “cut,” or facet, of the crystalline nickel-aluminum alloy have observed that steps on that surface had no effect on oxide growth. In addition, on that surface, aluminum atoms throughout the bulk of the crystal could participate in the formation of aluminum oxide, and the oxide stripes could overrun the steps, Zhou said.

Still the details and differences of the two types of surfaces could offer new ways scientists might attempt to control oxidation depending on their purpose.

“Oxides are not all bad,” Sutter said. “They form as a protective layer against corrosion attack. They play important roles in chemistry, for example in catalysis. Silicon oxide is the insulating material on microelectronic circuits, where it plays a central role in directing the flow of current.”

Knowing which kind of surface a material has and its effects on oxidation—or how to engineer surfaces with desired properties—might improve the design of these and other materials.

This work was supported by the DOE Office of Science.

sic 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 science.energy.gov.

See the full article here.

Please help promote STEM in your local schools.

Stem Education Coalition

One of ten national laboratories overseen and primarily funded by the Office of Science of the U.S. Department of Energy (DOE), Brookhaven National Laboratory conducts research in the physical, biomedical, and environmental sciences, as well as in energy technologies and national security. Brookhaven Lab also builds and operates major scientific facilities available to university, industry and government researchers. The Laboratory’s almost 3,000 scientists, engineers, and support staff are joined each year by more than 5,000 visiting researchers from around the world.Brookhaven is operated and managed for DOE’s Office of Science by Brookhaven Science Associates, a limited-liability company founded by Stony Brook University, the largest academic user of Laboratory facilities, and Battelle, a nonprofit, applied science and technology organization.

From LBL: “Piezoelectricity in a 2D Semiconductor”

Berkeley Lab

December 22, 2014
Lynn Yarris (510) 486-5375

A door has been opened to low-power off/on switches in micro-electro-mechanical systems (MEMS) and nanoelectronic devices, as well as ultrasensitive bio-sensors, with the first observation of piezoelectricity in a free standing two-dimensional semiconductor by a team of researchers with the U.S. Department of Energy (DOE)’s Lawrence Berkeley National Laboratory (Berkeley Lab).

Xiang Zhang, director of Berkeley Lab’s Materials Sciences Division and an international authority on nanoscale engineering, led a study in which piezoelectricity – the conversion of mechanical energy into electricity or vice versa – was demonstrated in a free standing single layer of molybdenum disulfide, a 2D semiconductor that is a potential successor to silicon for faster electronic devices in the future.

“Piezoelectricity is a well-known effect in bulk crystals, but this is the first quantitative measurement of the piezoelectric effect in a single layer of molecules that has intrinsic in-plane dipoles,” Zhang says. “The discovery of piezoelectricity at the molecular level not only is fundamentally interesting, but also could lead to tunable piezo-materials and devices for extremely small force generation and sensing.”

Xiang Zhang directs Berkeley Lab’s Materials Sciences Division (photo by Roy Kaltschmidt, Berkeley Lab)

Zhang, who holds the Ernest S. Kuh Endowed Chair at the University of California (UC) Berkeley and is a member of the Kavli Energy NanoSciences Institute at Berkeley, is the corresponding author of a paper in Nature Nanotechnology describing this research. The paper is titled Observation of Piezoelectricity in Free-standing Monolayer MoS2. The co-lead authors are Hanyu Zhu and Yuan Wang, both members of Zhang’s UC Berkeley research group. (See below for a complete list of co-authors.)

Since its discovery in 1880, the piezoelectric effect has found wide application in bulk materials, including actuators, sensors and energy harvesters. There is rising interest in using nanoscale piezoelectric materials to provide the lowest possible power consumption for on/off switches in MEMS and other types of electronic computing systems. However, when material thickness approaches a single molecular layer, the large surface energy can cause piezoelectric structures to be thermodynamically unstable.

Over the past couple of years, Zhang and his group have been carrying out detailed studies of molybdenum disulfide, a 2D semiconductor that features high electrical conductance comparable to that of graphene, but, unlike graphene, has natural energy band-gaps, which means its conductance can be switched off.

“Transition metal dichalcogenides such as molybdenum disulfide can retain their atomic structures down to the single layer limit without lattice reconstruction, even in ambient conditions,” Zhang says. “Recent calculations predicted the existence of piezoelectricity in these 2D crystals due to their broken inversion symmetry. To test this, we combined a laterally applied electric field with nano-indentation in an atomic force microscope for the measurement of piezoelectrically-generated membrane stress.”

To maximize piezoelectric coupling, electrodes (yellow dashed lines) were defined parallel to the zigzag edges (white dashed lines) of the MoS2 monolayer. Green and red colors denote the intensity of reflection and photoluminescence respectively.

Zhang and his group used a free-standing molybdenum disulfide single layer crystal to avoid any substrate effects, such as doping and parasitic charge, in their measurements of the intrinsic piezoelectricity. They recorded a piezoelectric coefficient of 2.9×10-10 C/m, which is comparable to many widely used materials such as zinc oxide and aluminum nitride.

“Knowing the piezoelectric coefficient is important for designing atomically thin devices and estimating their performance,” says Nature paper co-lead author Zhu. “The piezoelectric coefficient we found in molybdenum disulfide is sufficient for use in low-power logic switches and biological sensors that are sensitive to molecular mass limits.”

Zhang, Zhu and their co-authors also discovered that if several single layers of molybdenum disulfide crystal were stacked on top of one another, piezoelectricity was only present in the odd number of layers (1,3,5, etc.)

“This discovery is interesting from a physics perspective since no other material has shown similar layer-number sensitivity,” Zhu says. “The phenomenon might also prove useful for applications in which we want devices consisting of as few as possible material types, where some areas of the device need to be non-piezoelectric.”

In addition to logic switches and biological sensors, piezoelectricity in molybdenum disulfide crystals might also find use in the potential new route to quantum computing and ultrafast data-processing called “valleytronics.” In valleytronics, information is encoded in the spin and momentum of an electron moving through a crystal lattice as a wave with energy peaks and valleys.

“Some types of valleytronic devices depend on absolute crystal orientation, and piezoelectric anisotropy can be employed to determine this,’ says Nature paper co-lead author Wang. “We are also investigating the possibility of using piezoelectricity to directly control valleytronic properties such as circular dichroism in molybdenum disulfide.”

In addition to Zhang, Zhu and Wang, other co-authors of the Nature paper were Jun Xiao, Ming Liu, Shaomin Xiong, Zi Jing Wong, Ziliang Ye, Yu Ye and Xiaobo Yin.

This research was supported by Light-Material Interactions in Energy Conversion, an Energy Frontier Research Center led by the California Institute of Technology, in which Berkeley Lab is a major partner. The Energy Frontier Research Center program is supported by DOE’s Office of Science.

See the full article here.

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A U.S. Department of Energy National Laboratory Operated by the University of California