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Researchers from MIPT’s Laboratory of 2D Materials’ Optoelectronics, Institute of Radioengineering and Electronics, and Tohoku University (Japan) have theoretically demonstrated the possibility of creating compact sources of coherent plasmons, which are the basic building blocks for future optoelectronic circuits. The way in which the device would operate is based on the unique properties of van der Waals heterostructures — composites of graphene and related layered materials. A paper detailing the study has been published in the Physical Review B journal.

The plasmon is a quasi-particle that is a “mixture” of oscillating electrons and the electromagnetic field coupled with them. Plasmons can be used to generate, transmit, and receive signals in integrated circuits. Plasmons can act as mediators between electrons and light waves in highly efficient photodetectors and sources, particularly in the actively explored terahertz range. It is interesting to note that plasmon energy can be stored at a length scale much smaller than the wavelength of light. This means that plasmonic devices can be far more compact than their photonic counterparts. The most “compressed” plasmons are those that are bound to the conducting planes, and these plasmons can be used to make the most compact optoelectronic devices.

But where can one find a conducting plane that supports ultra-confined plasmons? For more than forty years, such objects have been created by sequential growth on nanometer-thin semiconductors with affine crystal structures. In this process, certain layers are enriched with electrons and obtain good electrical conductivity. These “layer-cakes” are called heterostructures — Russian physicist Zhores Alferov was awarded the 2000 Nobel Prize in Physics for their development.

However, growing nanoscale layers is not the only way of obtaining flat semiconductors. During the last decade, researchers’ attention has been focused on a different, intrinsically two-dimensional material — graphene. Graphene is a one-atom-thick layer of carbon, and it can be obtained by simply slicing a graphite crystal. The study of the unique electronic properties of graphene (which are radically different from those of classical heterostructures) was marked by another Nobel prize awarded to the MIPT alumni Andre Geim and Konstantin Novoselov (2010). A great number of graphene-based devices have already been created, including transistors receiving high-frequency signals, ultrafast photodetectors and even the first prototypes of lasers. The properties of graphene can be further enhanced by placing it on another material with a similar crystal structure. Materials similar to graphene can essentially be used to create the “layer-cake” heterostructures mentioned above. In this case, however, the building blocks of the structures are joined by van der Waals forces, which is why they are called van der Waals heterostructures.

Band diagram of the graphene -- tungsten disulphide -- graphene structure explaining the principle of plasmon generation. The application of interlayer voltage V results in the enrichment of one layer by electrons (blue), and the emergence of free states (called holes) in the opposite layer (red). An electron can tunnel from an occupied state to an empty state (dashed line), and its excess energy can be spent to excite a plasmon (red wavy line). CREDIT © MIPT

Band diagram of the graphene — tungsten disulphide — graphene structure explaining the principle of plasmon generation. The application of interlayer voltage V results in the enrichment of one layer by electrons (blue), and the emergence of free states (called holes) in the opposite layer (red). An electron can tunnel from an occupied state to an empty state (dashed line), and its excess energy can be spent to excite a plasmon (red wavy line). CREDIT © MIPT

In their work, the researchers show that a heterostructure comprising two graphene layers separated by a thin layer of tungsten disulphide not only supports the compact two-dimensional plasmons, but can also generate them upon the application of interlayer voltage.

“The structure we are modeling is essentially the gain medium for plasmons,” explains Dmitry Svintsov, the first author of the research. “More common examples of gain media are the neon-helium mixture in a gas laser, or a semiconductor diode in a laser pointer. When passing through such a medium, the light is amplified, and if the medium is placed between two mirrors, the medium will generate the light by itself. The combination ‘gain medium plus mirrors’ is at the heart of any laser, while the gain medium for plasmons is a necessary element of a plasmonic laser, or spaser. If the gain medium is switched on and off, the plasmonic pulses can be obtained on demand, which could be used for signal transmission in integrated circuits. The plasmons generated in the gain medium can also be uncoupled from the graphene layers and propagate as photons in free space. This allows one to create tunable sources of terahertz and far infrared radiation.”

<> Band diagram of the graphene — tungsten disulphide — graphene structure explaining the principle of plasmon generation. The application of interlayer voltage V results in the enrichment of one layer by electrons (blue), and the emergence of free states (called holes) in the opposite layer (red). An electron can tunnel from an occupied state to an empty state (dashed line), and its excess energy can be spent to excite a plasmon (red wavy line).

Apparently, the gain medium is not a perpetuum mobile, and the particles created by it — either photons or plasmons–must get their energy from a certain source. In neon-helium lasers, this energy is taken from an electron thrown onto a high atomic orbital by the electric discharge. In semiconductor lasers, the photon takes its energy from collapsing positive and negative charge carriers — electrons and holes, which are supplied by the current source. In the proposed double graphene layer structure, the plasmon takes its energy from an electron hopping from a layer with high potential energy to a layer with low potential energy, as shown in the figure. The creation of a plasmon as a result of this jump is similar to the way in which waves form as a diver enters the water.

To be more precise, the electron transition from one layer to another is more like soaking through the barrier rather than jumping over it. This phenomenon is called tunneling, and typically the probability of tunneling is very low already for nanometer-thin barriers. One exception is the case of resonant tunneling, when each electron from one layer has a “well-prepared” place in the opposite layer.

“The principle of plasmon generation studied by our group is similar to the principle of the quantum cascade laser proposed by the Russian scientists Kazarinov and Suris and realized in the USA (Faist and Capasso) more than twenty years afterwards. In this laser, the photons take energy from electrons tunneling between gallium arsenide layers through the AlGaAs barriers. Our calculations show that in this principal scheme, one can profitably replace gallium arsenide with graphene, while tungsten disulphide can act as a barrier material. This structure is able to generate not only photons, but also their compressed counterparts–plasmons. The generation and amplification of plasmons was previously thought to be a very challenging problem, but the structure we have proposed brings us one step closer to the solution,” says Dmitry Svintsov.

A research team at Worcester Polytechnic Institute (WPI) has developed a revolutionary, light-activated semiconductor nanocomposite material that can be used in a variety of applications, including microscopic actuators and grippers for surgical robots, light-powered micro-mirrors for optical telecommunications systems, and more efficient solar cells and photodetectors.

“This is a new area of science,” said Balaji Panchapakesan, associate professor of mechanical engineering at WPI and lead author of a paper about the new material published in Scientific Reports, an open access journal from the publishers of Nature. “Very few materials are able to convert photons directly into mechanical motion. In this paper, we present the first semiconductor nanocomposite material known to do so. It is a fascinating material that is also distinguished by its high strength and its enhanced optical absorption when placed under mechanical stress.

“Tiny grippers and actuators made with this material could be used on Mars rovers to capture fine dust particles.” Panchapakesan noted. “They could travel through the bloodstream on tiny robots to capture cancer cells or take minute tissue samples. The material could be used to make micro-actuators for rotating mirrors in optical telecommunications systems; they would operate strictly with light, and would require no other power source.”

Like other semiconductor materials, molybdenum disulfide, the material described in the Scientific Reports paper (“Chromatic Mechanical Response in 2-D Layered Transition Metal Dichalcogenide (TMDs)-based Nanocomposites”), is characterized by the way electrons are arranged and move about within its atoms. In particular, electrons in semiconductors are able to move from a group of outer orbitals called the valence band to another group of orbitals known as the conduction band only when adequately excited by an energy source, like an electromagnetic field or the photons in a beam of light. Crossing the “band gap,” the electrons create a flow of electricity, which is the principal that makes computer chips and solar cells possible.

When the negatively-charged electrons move between orbitals, they leave behind positively charged voids known as holes. A pair of a bound electron and an electron hole is called an exciton.

In their experiments, Panchapakesan and his team, which included graduate students Vahid Rahneshin and Farhad Khosravi, as well as colleagues at the University of Louisville and the University of Warsaw Pasteura, observed that the atomic orbitals of the molybdenum and sulfur atoms in molybdenum disulfide are arranged in a unique way that permits excitons within the conduction band to interact with what are known as the p-orbitals of the sulfur atoms. This “exciton resonance” contributes to the strong sigma bonds that give the two dimensional array of atoms in molybdenum sulfide its extraordinary strength. The strength of this resonance is also responsible for a unique effect that can generate heat within the material. It is the heat that gives rise to the material’s chromatic (light-induced) mechanical response.

To take advantage of the later phenomenon, Panchapakesan’s team created thin films made up of just one to three layers of molybdenum disulfide encased in layers of a rubber-like polymer. They exposed these nanocomposites to various wavelengths of light and found that the heat generated as a result of the exciton resonance caused the polymer to expand and contract, depending on the wavelength of the light used. In previous work, Panchapakesan’s team harnessed this photo-mechanical response by fabricating tiny grippers that open and close in response to light pulses. The grippers can capture plastic beads the size of a single human cell.

In further testing, Panchapakesan and his team discovered another unique behavior of the molybdenum disulfide composite that opens the door to a different set of applications. Employing what is known as strain engineering, they stretched the material and discovered that mechanical stresses increased its ability to absorb light.

“This is something that cannot be done with conventional thin-film semiconductors,” Panchapakesan said, “because when you stretch them, they will prematurely break. But with its unique material strength, molybdenum disulfide can be stretched. And its increased optical absorption under strain makes it a good candidate for more efficient solar cells, photodetectors, and detectors for thermal and infrared cameras.

“The exciton resonance, photomechanical response, and increased optical absorption under strain make this an extraordinary material and an intriguing subject for further investigation,” he added.

Detailing the molecular makeup of materials — from solar cells to organic light-emitting diodes (LEDs) and transistors, and medically important proteins — is not always a crystal-clear process.

To understand how materials work at these microscopic scales, and to better design materials to improve their function, it is necessary to not only know all about their composition but also their molecular arrangement and microscopic imperfections.

Now, a team of researchers working at the Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab) has demonstrated infrared imaging of an organic semiconductor known for its electronics capabilities, revealing key nanoscale details about the nature of its crystal shapes and orientations, and defects that also affect its performance.

This image shows the crystal shape and height of a material known as PTCDA, with height represented by the shading (white is taller, darker orange is lowest). The white scale bar represents 500 nanometers. The illustration at bottom is a representation of the crystal shape. Credit: Berkeley Lab, CU-Boulder

This image shows the crystal shape and height of a material known as PTCDA, with height represented by the shading (white is taller, darker orange is lowest). The white scale bar represents 500 nanometers. The illustration at bottom is a representation of the crystal shape. Credit: Berkeley Lab, CU-Boulder

To achieve this imaging breakthrough, researchers from Berkeley Lab’s Advanced Light Source (ALS) and the University of Colorado-Boulder (CU-Boulder) combined the power of infrared light from the ALS and infrared light from a laser with a tool known as an atomic force microscope. The ALS, a synchrotron, produces light in a range of wavelengths or “colors” — from infrared to X-rays — by accelerating electron beams near the speed of light around bends.

The researchers focused both sources of infrared light onto the tip of the atomic force microscope, which works a bit like a record-player needle — it moves across the surface of a material and measures the subtlest of surface features as it lifts and dips.

The technique, detailed in a recent edition of the journal Science Advances, allows researchers to tune the infrared light in on specific chemical bonds and their arrangement in a sample, show detailed crystal features, and explore the nanoscale chemical environment in samples.

“Our technique is broadly applicable,” said Hans Bechtel an ALS scientist. “You could use this for many types of material — the only limitation is that it has to be relatively flat” so that the tip of the atomic force microscope can move across its peaks and valleys.

Markus Raschke, a CU-Boulder professor who developed the imaging technique with Eric Muller, a postdoctoral researcher in his group, said, “If you know the molecular composition and orientation in these organic materials then you can optimize their properties in a much more straightforward way.

“This work is informing materials design. The sensitivity of this technique is going from an average of millions of molecules to a few hundred, and the imaging resolution is going from the micron scale (millionths of an inch) to the nanoscale (billionths of an inch),” he said.

The infrared light of the synchrotron provided the essential wide band of the infrared spectrum, which makes it sensitive to many different chemicals’ bonds at the same time and also provides the sample’s molecular orientation. The conventional infrared laser, with its high power yet narrow range of infrared light, meanwhile, allowed researchers to zoom in on specific bonds to obtain very detailed imaging.

“Neither the ALS synchrotron nor the laser alone would have given us this level of microscopic insight,” Raschke said, while the combination of the two provided a powerful probe “greater than the sum of its parts.”

Raschke a decade ago first explored synchrotron-based infrared nano-spectroscopy using the BESSY synchrotron in Berlin. With his help and that of ALS scientists Michael Martin and Bechtel, the ALS in 2014 became the first synchrotron to offer nanoscale infrared imaging to visiting scientists.

The technique is particularly useful for the study and understanding of so-called “functional materials” that possess special photonic, electronic, or energy-conversion or energy-storage properties, he noted.

In principle, he added, the new advance in determining molecular orientation could be adapted to biological studies of proteins. “Molecular orientation is critical in determining biological function,” Raschke said. The orientation of molecules determines how energy and charge flows across from cell membranes to molecular solar energy conversion materials.

Bechtel said the infrared technique permits imaging resolution down to about 10-20 nanometers, which can resolve features up to 50,000 times smaller than a grain of sand.

The imaging technique used in these experiments, known as “scattering-type scanning near-field optical microscopy,” or s-SNOM, essentially uses the atomic force microscope tip as an ultrasensitive antenna, which transmits and receives focused infrared light in the region of the tip apex. Scattered light, captured from the tip as it moves over the sample, is recorded by a detector to produce high-resolution images.

“It’s non-invasive, and it provides information about molecular vibrations,” as the microscope’s tip moves over the sample, Bechtel said. Researchers used the technique to study the crystalline features of an organic semiconductor material known as PTCDA (perylenetetracarboxylic dianhydride).

Researchers reported that they observed defects in the orientation of the material’s crystal structure that provide a new understanding of the crystals’ growth mechanism and could aid in the design molecular devices using this material.

The new imaging capability sets the stage for a new National Science Foundation Center, announced in late September, that links CU-Boulder with Berkeley Lab, UC Berkeley, Florida International University, UC Irvine, and Fort Lewis College in Durango, Colo. The center will combine a range of microscopic imaging methods, including those that use electrons, X-rays, and light, across a broad range of disciplines.

This center, dubbed STROBE for Science and Technology Center on Real-Time Functional Imaging, will be led by Margaret Murnane, a distinguished professor at CU-Boulder, with Raschke serving as a co-lead.

At Berkeley Lab, STROBE will be served by a range of ALS capabilities, including the infrared beamlines managed by Bechtel and Martin and a new beamline dubbed COSMIC (for “coherent scattering and microscopy”). It will also benefit from Berkeley Lab-developed data analysis tools.

A team of Shanghai Jiao Tong University researchers has used the shape of cicada wings as a template to create antireflective structures fabricated with one of the most intriguing semiconductor materials, titanium dioxide (TiO2). The antireflective structures they produced are capable of suppressing visible light — 450 to 750 nanometers — at different angles of incidence.

I. Photograph and scanning electron microscope characterizations of a black cicada wing (Cryptympana atrata Fabricius). II. Synthesis process of biomorphic TiO2 with ordered nano-nipple array structures. III. Counter map angle-dependent antireflection of biomorphic TiO2 and non-templated TiO2, respectively. Credit: Shanghai Jiao Tong University

I. Photograph and scanning electron microscope characterizations of a black cicada wing (Cryptympana atrata Fabricius). II. Synthesis process of biomorphic TiO2 with ordered nano-nipple array structures. III. Counter map angle-dependent antireflection of biomorphic TiO2 and non-templated TiO2, respectively. Credit: Shanghai Jiao Tong University

Why cicada wings? The surfaces of the insect’s wings are composed of highly ordered, tiny vertical “nano-nipple” arrays, according to the researchers. As they report this week in Applied Physics Letters, from AIP Publishing, the resulting biomorphic TiO2 surface they created with antireflective structures shows a significant decrease in reflectivity.

“This can be attributed to an optimally graded refractive index profile between air and the TiO2 via antireflective structures on the surface,” explained Wang Zhang, associate professor at State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University in China.

Small spaces between the ordered nano-antireflective structures “can be thought of as a light-transfer path that let incident light rays into the interior surface of the biomorphic TiO2 — allowing the incident light rays to completely enter the structure,” Zhang continued. “The multiple reflective and scattering effects of the antireflective structures prevented the incident light from returning to the outside atmosphere.”

Significantly, the team’s work relies on “a simple and low-cost sol-gel (wet chemical) method to fabricate biomorphic TiO2 with precise subwavelength antireflective surfaces,” Zhang pointed out. “The TiO2 was a purely anatase phase (a mineral form of TiO2), which has unique antireflective surfaces. This led to an optimally graded refractive index and, ultimately, to angle-dependent antireflective properties within the visible light range.”

In terms of applications, the team’s biomorphic TiO2 antireflective structures “show great potential for photovoltaic devices such as solar cells,” Zhang said. “We expect our work to inspire and motivate engineers to develop antireflective surfaces with unique structures for various practical applications.”

Even after high calcination at 500 C, the antireflective structures retain their morphology and high-performance antireflection properties. These qualities should enable the coatings to withstand harsh environments and make them suitable for long-term applications.

In the future, the team plans “to reduce the optical losses in solar cells by using materials with a higher refractive index such as tantalum pentoxide or any other semiconductor materials,” Zhang said.

Scientists with the Energy Department’s National Renewable Energy Laboratory (NREL) for the first time discovered how to make perovskite solar cells out of quantum dots and used the new material to convert sunlight to electricity with 10.77 percent efficiency.

The research, Quantum dot-induced phase stabilization of a-CsPbI3 perovskite for high-efficiency photovoltaics, appears in the journal Science. The authors are Abhishek Swarnkar, Ashley Marshall, Erin Sanehira, Boris Chernomordik, David Moore, Jeffrey Christians, and Joseph Luther from NREL. Tamoghna Chakrabarti from the Colorado School of Mines also is a co-author.

In addition to developing quantum dot perovskite solar cells, the researchers discovered a method to stabilize a crystal structure in an all-inorganic perovskite material at room temperature that was previously only favorable at high temperatures. The crystal phase of the inorganic material is more stable in quantum dots.

Most research into perovskites has centered on a hybrid organic-inorganic structure. Since research into perovskites for photovoltaics began in 2009, their efficiency of converting sunlight into electricity has climbed steadily and now shows greater than 22 percent power conversion efficiency. However, the organic component hasn’t been durable enough for the long-term use of perovskites as a solar cell.

NREL scientists turned to quantum dots-which are essentially nanocrystals-of cesium lead iodide (CsPbI3) to remove the unstable organic component and open the door to high-efficiency quantum dot optoelectronics that can be used in LED lights and photovoltaics.

The nanocrystals of CsPbI3 were synthesized through the addition of a Cs-oleate solution to a flask containing PbI2 precursor. The NREL researchers purified the nanocrystals using methyl acetate as an anti-solvent that removed excess unreacted precursors. This step turned out to be critical to increasing their stability.

Contrary to the bulk version of CsPbI3, the nanocrystals were found to be stable not only at temperatures exceeding 600 degrees Fahrenheit but also at room temperatures and at hundreds of degrees below zero. The bulk version of this material is unstable at room temperature, where photovoltaics normally operate and convert very quickly to an undesired crystal structure.

NREL scientists were able to transform the nanocrystals into a thin film by repeatedly dipping them into a methyl acetate solution, yielding a thickness between 100 and 400 nanometers. Used in a solar cell, the CsPbI3 nanocrystal film proved efficient at converting 10.77 percent of sunlight into electricity at an extraordinary high open circuit voltage. The efficiency is similar to record quantum dot solar cells of other materials and surpasses other reported all-inorganic perovskite solar cells.

The research was funded in part by the Energy Department’s Office of Science and by the SunShot Initiative.

NREL is the U.S. Department of Energy’s primary national laboratory for renewable energy and energy efficiency research and development. NREL is operated for the Energy Department by The Alliance for Sustainable Energy, LLC.

The SunShot Initiative is a collaborative national effort that aggressively drives innovation to make solar energy fully cost-competitive with traditional energy sources before the end of the decade. Through SunShot, the Energy Department supports efforts by private companies, universities, and national laboratories to drive down the cost of solar electricity to $0.06 per kilowatt-hour. Learn more at energy.gov/sunshot.

Dual-ion batteries (DIBs) are a new type of battery developed in recent years, typically using graphite as both the cathode and anode material. DIBs can operate across a wider voltage window with safer performance, and are cheaper than conventional lithium ion batteries.

Schematic structure of the DIB. Credit: TANG Yongbing

Schematic structure of the DIB. Credit: TANG Yongbing

Prof. TANG Yongbing and colleagues from the Shenzhen Institutes of Advanced Technology, Chinese Academy of Sciences, had previously developed a novel and low-cost aluminum-graphite DIB (AGDIB) using Al foil as both the anode and current collector. Although the AGDIB exhibits high energy density, it is far from a practical application due to poor stability caused by the crack and pulverization problem of Al foil during cycling.

To solve this problem, Prof. TANG and his colleagues designed a 3D porous Al foil coated with a uniform carbon layer (pAl/C) both as the anode and the current collector for the DIB. The 3D porous structure of Al alleviates the mechanical stress caused by the volume change of Al during electrochemical cycling, and shortens the ion diffusion length as well. The carbon layer helps buffer the Al volume change, and alleviates undesirable surface reactions through SEI film formation.

Therefore, owing to the synergistic effect of the porous and conductive structure of the pAl/C anode, the DIB exhibits an excellent long-term cycling stability of over 1000 cycles with 89.4% retention of capacity at 2C current rate (charging/discharging within 30 minutes). It’s worth noting that the energy density of this DIB is estimated to be 204 Wh kg-1 at a high power density of 3084 W kg-1 (charging/discharging within 4 minutes), which is two times larger than best commercial lithium ion batteries and the best performance of any reported DIBs.

Prof. TANG and colleagues believe that this novel DIB, characterized by low cost, high rate, high energy density and long-term cycling capabilities, shows great potential for industrial applications in the energy field such as portable electronics and electric vehicles.

This research was supported by the Guangdong Innovation Team and the National Natural Science Foundation of China and published online in Advanced Materials.

Researchers have designed a device that uses light to manipulate its mechanical properties. The device, which was fabricated using a plasmomechanical metamaterial, operates through a unique mechanism that couples its optical and mechanical resonances, enabling it to oscillate indefinitely using energy absorbed from light.

This is an optically-driven mechanical oscillator fabricated using a plasmomechanical metamaterial. Credit: UC San Diego Jacobs School of Engineering

This is an optically-driven mechanical oscillator fabricated using a plasmomechanical metamaterial. Credit: UC San Diego Jacobs School of Engineering

This work demonstrates a metamaterial-based approach to develop an optically-driven mechanical oscillator. The device can potentially be used as a new frequency reference to accurately keep time in GPS, computers, wristwatches and other devices, researchers said. Other potential applications that could be derived from this metamaterial-based platform include high precision sensors and quantum transducers. The research was published Oct. 10 in the journal Nature Photonics.

Researchers engineered the metamaterial-based device by integrating tiny light absorbing nanoantennas onto nanomechanical oscillators. The study was led by Ertugrul Cubukcu, a professor of nanoengineering and electrical engineering at the University of California San Diego. The work, which Cubukcu started as a faculty member at the University of Pennsylvania and is continuing at the Jacobs School of Engineering at UC San Diego, demonstrates how efficient light-matter interactions can be utilized for applications in novel nanoscale devices.

Metamaterials are artificial materials that are engineered to exhibit exotic properties not found in nature. For example, metamaterials can be designed to manipulate light, sound and heat waves in ways that can’t typically be done with conventional materials.

Metamaterials are generally considered “lossy” because their metal components absorb light very efficiently. “The lossy trait of metamaterials is considered a nuisance in photonics applications and telecommunications systems, where you have to transmit a lot of power. We’re presenting a unique metamaterials approach by taking advantage of this lossy feature,” Cubukcu said.

The device in this study resembles a tiny capacitor–roughly the size of a quarter–consisting of two square plates measuring 500 microns by 500 microns. The top plate is a bilayer gold/silicon nitride membrane containing an array of cross-shaped slits–the nanoantennas–etched into the gold layer. The bottom plate is a metal reflector that is separated from the gold/silicon nitride bilayer by a three-micron-wide air gap.

When light is shined upon the device, the nanoantennas absorb all of the incoming radiation from light and convert that optical energy into heat. In response, the gold/silicon nitride bilayer bends because gold expands more than silicon nitride when heated. The bending of the bilayer alters the width of the air gap separating it from the metal reflector. This change in spacing causes the bilayer to absorb less light and as a result, the bilayer bends back to its original position. The bilayer can once again absorb all of the incoming light and the cycle repeats over and over again.

The device relies on a unique hybrid optical resonance known as the Fano resonance, which emerges as a result of the coupling between two distinct optical resonances of the metamaterial. The optical resonance can be tuned “at will” by applying a voltage.

The researchers also point out that because the plasmomechanical metamaterial can efficiently absorb light, it can function under a broad optical resonance. That means this metamaterial can potentially respond to a light source like an LED and won’t need a strong laser to provide the energy.

“Using plasmonic metamaterials, we were able to design and fabricate a device that can utilize light to amplify or dampen microscopic mechanical motion more powerfully than other devices that demonstrate these effects. Even a non-laser light source could still work on this device,” said Hai Zhu, a former graduate student in Cubukcu’s lab and first author of the study.

“Optical metamaterials enable the chip-level integration of functionalities such as light-focusing, spectral selectivity and polarization control that are usually performed by conventional optical components such as lenses, optical filters and polarizers. Our particular metamaterial-based approach can extend these effects across the electromagnetic spectrum,” said Fei Yi, a postdoctoral researcher who worked in Cubukcu’s lab.

Dr. Lingkui Meng, Dr. Yasutomo Segawa, Professor Kenichiro Itami of the JST-ERATO Itami Molecular Nanocarbon Project, Institute of Transformative Bio-Molecules (ITbM) of Nagoya University and Integrated Research Consortium on Chemical Sciences, and their colleagues have reported in the Journal of the American Chemical Society, on the development of a simple and effective method for the synthesis of thiophene-fused PAHs.

Thiophene-fused PAHs are organic molecules composed of multiple aromatic rings including thiophene. Thiophene is a five-membered aromatic ring containing four carbon atoms and a sulfur atom. Thiophene-fused PAHs are known to be one of the most common organic semiconductors and are used in various electronic materials, such as in transistors, organic thin-film solar cells, organic electro-luminescent diodes and electronic devices. More recently, they have found use in wearable devices due to their lightweight and flexibility.

Yellow and gray colors on the molecule represent sulfur and carbon atoms respectively. Thiophene-fused PAHs have found uses as transistors. Credit: ITbM, Nagoya University

Yellow and gray colors on the molecule represent sulfur and carbon atoms respectively. Thiophene-fused PAHs have found uses as transistors. Credit: ITbM, Nagoya University

Thienannulation (thiophene-annulation) reactions, a transformation that makes new thiophene rings via cyclization, leads to various thiophene-fused PAHs. Most conventional thienannulation methods require the introduction of two functional groups adjacent to each other to form two reactive sites on PAHs before the cyclization can take place. Thus, multiple steps are required for the preparation of the substrates. As a consequence, a more simple method to access thiophene-fused PAHs is desirable.

A team led by Yasutomo Segawa, a group leader of the JST-ERATO project, and Kenichiro Itami, the director of the JST-ERATO project and the center director of ITbM, has succeeded in developing a simple and effective method for the formation of various thiophene-fused PAHs. They have managed to start from PAHs that have only one functional group, which saves the effort of installing another functional group, and have performed the thienannulation reactions using elemental sulfur, a readily available low cost reagent. The reactions can be carried out on a multigram scale and can be conducted in a one-pot two-step reaction sequence starting from an unfunctionalized PAH. This new approach can also generate multiple thiophene moieties in a single reaction. Hence, this method has the advantage of offering a significant reduction in the number of required steps and in the reagent costs for thiophene-fused PAH synthesis compared to conventional methods.

The researchers have shown that upon heating and stirring the dimethylformamide solution of arylethynyl group-substituted PAHs and elemental sulfur in air, they were able to obtain the corresponding thiophene-fused PAHs. The arylethynyl group consists of an alkyne (a moiety with a carbon-carbon triple bond) bonded to an aromatic ring. The reaction proceeds via a carbon-hydrogen (C-H) bond cleavage at the position next to the arylethynyl group (called the ortho-position) on PAHs, in the presence of sulfur. As the ortho-C-H bond on the PAH can be cleaved under the reaction conditions, prior functionalization (installation of a functional group) becomes unnecessary.

Arylethynyl-substituted PAHs are readily accessible by the Sonogashira coupling, which is a cross-coupling reaction to form carbon-carbon bonds between an alkyne and a halogen-substituted aromatic compound. The synthesis of thiophene-fused PAHs can also be carried out in one-pot, in which PAHs are subjected to a Sonogashira coupling to form arylethynyl-substituted PAHs, followed by direct treatment of the alkyne with elemental sulfur to induce thienannulation.

“Actually, we coincidentally discovered this reaction when we were testing different chemical reactions to synthesize a new molecule for the Itami ERATO project,” says Yasutomo Segawa, one of the leaders of this study. “At first, most members including myself felt that the reaction may have already been reported because it is indeed a very simple reaction. Therefore, the most difficult part of this research was to clarify the novelty of this reaction. We put in a significant amount of effort to investigate previous reports, including textbooks from more than 50 years ago as well as various Internet sources, to make sure that our reaction conditions had not been disclosed before,” he continues.

The team succeeded in synthesizing more than 20 thiophene-fused PAHs. They also revealed that multiple formations of thiophene rings of PAHs substituted with multiple arylethynyl groups could be carried out all at once. Multiple thiophene-fused PAHs were generated from three-fold and five-fold thienannulations, which generated triple thia[5]helicene (containing three thiophenes) and pentathienocorannulene (containing five thiophenes), respectively. The pentathienocorannulene was an unprecedented molecule that was synthesized for the first time.

“I was extremely happy when I was able to obtain the propeller-shaped triple thia[5]helicene and hat-shaped pentathienocorannulene, because I have always been aiming to synthesize exciting new molecules since I joined Professor Itami’s group,” says Lingkui Meng, a postdoctoral researcher who mainly conducted the experiments. “We had some problems in purifying the compounds but we were delighted when we obtained the crystal structures of the thiophene compounds, which proved that the desired reactions had taken place.”

“The best part of this research for me is to discover that our C-H functionalization strategy on PAHs could be applied to synthesize structurally beautiful molecules with high functionalities,” says Segawa. “The successful synthesis of a known high-performance organic semiconductive molecule, (2,6-bis(4-n-octylphenyl)- dithieno[3,2-b:2?,3?-d]thiophene, from a relatively cheap substrate opens doors to access useful thiophene compounds in a rapid and cost-effective manner.”

“We hope that ongoing advances in our method may lead to the development of new organic electronic devices, including semiconductor and luminescent materials,” say Segawa and Itami. “We are considering the possibilities to make this reaction applicable for making useful thiophene-fused PAHs, which would lead to the rapid discovery and optimization of key molecules that would advance the field of materials science.”

Researchers at North Carolina State University have created a high voltage and high frequency silicon carbide (SiC) power switch that could cost much less than similarly rated SiC power switches. The findings could lead to early applications in the power industry, especially in power converters like medium voltage drives, solid state transformers and high voltage transmissions and circuit breakers.

A new NC State high-power switch has the potential to work more efficiently and cost less than conventional solutions. Credit: Xiaoqing Song, NC State University

A new NC State high-power switch has the potential to work more efficiently and cost less than conventional solutions. Credit: Xiaoqing Song, NC State University

Wide bandgap semiconductors, such as SiC, show tremendous potential for use in medium- and high-voltage power devices because of their capability to work more efficiently at higher voltages. Currently though, their high cost impedes their widespread adoption over the prevailing workhorse and industry standard – insulated-gate bipolar transistors (IGBT) made from silicon – which generally work well but incur large energy losses when they are turned on and off.

The new SiC power switch, however, could cost approximately one-half the estimated cost of conventional high voltage SiC solutions, say Alex Huang and Xiaoqing Song, researchers at NC State’s FREEDM Systems Center, a National Science Foundation-funded engineering research center. Besides the lower cost, the high-power switch maintains the SiC device’s high efficiency and high switching speed characteristics. In other words, it doesn’t lose as much energy when it is turned on or off.

The power switch, called the FREEDM Super-Cascode, combines 12 smaller SiC power devices in series to reach a power rating of 15 kilovolts (kV) and 40 amps (A). It requires only one gate signal to turn it on and off, making it simple to implement and less complicated than IGBT series connection-based solutions. The power switch is also able to operate over a wide range of temperatures and frequencies due to its proficiency in heat dissipation, a critical factor in power devices.

“Today, there is no high voltage SiC device commercially available at voltage higher than 1.7 kV,” said Huang, Progress Energy Distinguished Professor and the founding director of the FREEDM Systems Center. “The FREEDM Super-Cascode solution paves the way for power switches to be developed in large quantities with breakdown voltages from 2.4 kV to 15 kV.”

The FREEDM Super-Cascode switch was presented by Xiaoqing Song, a Ph.D. candidate at the FREEDM Systems Center under Huang’s supervision, at the IEEE Energy Conversion Congress & Exposition (ECCE 2016) held in Milwaukee from Sept. 18-22, 2016.

A team led by Cory Dean, assistant professor of physics at Columbia University, Avik Ghosh, professor of electrical and computer engineering at the University of Virginia, and James Hone, Wang Fong-Jen Professor of Mechanical Engineering at Columbia Engineering, has directly observed–for the first time–negative refraction for electrons passing across a boundary between two regions in a conducting material. First predicted in 2007, this effect has been difficult to confirm experimentally. The researchers were able to observe the effect in graphene, demonstrating that electrons in the atomically thin material behave like light rays, which can be manipulated by such optical devices as lenses and prisms. The findings, which are published in the September 30 edition of Science, could lead to the development of new types of electron switches, based on the principles of optics rather than electronics.

Illustration of refraction through a normal optical medium versus what it would look like for a medium capable of negative refraction. Credit: Cory Dean, Columbia University

Illustration of refraction through a normal optical medium versus what it would look like for a medium capable of negative refraction. Credit: Cory Dean, Columbia University

“The ability to manipulate electrons in a conducting material like light rays opens up entirely new ways of thinking about electronics,” says Dean. “For example, the switches that make up computer chips operate by turning the entire device on or off, and this consumes significant power. Using lensing to steer an electron ‘beam’ between electrodes could be dramatically more efficient, solving one of the critical bottlenecks to achieving faster and more energy efficient electronics.”

Dean adds, “These findings could also enable new experimental probes. For example, electron lensing could enable on-chip versions of an electron microscope, with the ability to perform atomic scale imageing and diagnostics. Other components inspired by optics, such as beam splitters and interferometers, could additionally enable new studies of the quantum nature of electrons in the solid state.”

While graphene has been widely explored for supporting high electron speed, it is notoriously hard to turn off the electrons without hurting their mobility. Ghosh says, “The natural follow-up is to see if we can achieve a strong current turn-off in graphene with multiple angled junctions. If that works to our satisfaction, we’ll have on our hands a low-power, ultra-high-speed switching device for both analog (RF) and digital (CMOS) electronics, potentially mitigating many of the challenges we face with the high energy cost and thermal budget of present day electronics.”

Light changes direction – or refracts – when passing from one material to another, a process that allows us to use lenses and prisms to focus and steer light. A quantity known as the index of refraction determines the degree of bending at the boundary, and is positive for conventional materials such as glass. However, through clever engineering, it is also possible to create optical “metamaterials” with a negative index, in which the angle of refraction is also negative. “This can have unusual and dramatic consequences,” Hone notes. “Optical metamaterials are enabling exotic and important new technologies such as super lenses, which can focus beyond the diffraction limit, and optical cloaks, which make objects invisible by bending light around them.”

Electrons travelling through very pure conductors can travel in straight lines like light rays, enabling optics-like phenomena to emerge. In materials, the electron density plays a similar role to the index of refraction, and electrons refract when they pass from a region of one density to another. Moreover, current carriers in materials can either behave like they are negatively charged (electrons) or positively charged (holes), depending on whether they inhabit the conduction or the valence band. In fact, boundaries between hole-type and electron-type conductors, known as p-n junctions (“p” positive, “n” negative), form the building blocks of electrical devices such as diodes and transistors.

“Unlike in optical materials”, says Hone, “where creating a negative index metamaterial is a significant engineering challenge, negative electron refraction occurs naturally in solid state materials at any p-n junction.”

The development of two-dimensional conducting layers in high-purity semiconductors such as GaAs (Gallium arsenide) in the 1980s and 1990s allowed researchers to first demonstrate electron optics including the effects of both refraction and lensing. However, in these materials, electrons travel without scattering only at very low temperatures, limiting technological applications. Furthermore, the presence of an energy gap between the conduction and valence band scatters electrons at interfaces and prevents observation of negative refraction in semiconductor p-n junctions. In this study, the researchers’ use of graphene, a 2D material with unsurpassed performance at room temperature and no energy gap, overcame both of these limitations.

The possibility of negative refraction at graphene p-n junctions was first proposed in 2007 by theorists working at both the University of Lancaster and Columbia University. However, observation of this effect requires extremely clean devices, such that the electrons can travel ballistically, without scattering, over long distances. Over the past decade, a multidisciplinary team at Columbia – including Hone and Dean, along with Kenneth Shepard, Lau Family Professor of Electrical Engineering and professor of biomedical engineering, Abhay Pasupathy, associate professor of physics, and Philip Kim, professor of physic at the time (now at Harvard) – has worked to develop new techniques to construct extremely clean graphene devices. This effort culminated in the 2013 demonstration of ballistic transport over a length scale in excess of 20 microns. Since then, they have been attempting to develop a Veselago lens, which focuses electrons to a single point using negative refraction. But they were unable to observe such an effect and found their results puzzling.

In 2015, a group at Pohang University of Science and Technology in South Korea reported the first evidence focusing in a Veselago-type device. However, the response was weak, appearing in the signal derivative. The Columbia team decided that to fully understand why the effect was so elusive, they needed to isolate and map the flow of electrons across the junction. They utilized a well-developed technique called “magnetic focusing” to inject electrons onto the p-n junction. By measuring transmission between electrodes on opposite sides of the junction as a function of carrier density they could map the trajectory of electrons on both sides of the p-n junction as the incident angle was changed by tuning the magnetic field.

Crucial to the Columbia effort was the theoretical support provided by Ghosh’s group at the University of Virginia, who developed detailed simulation techniques to model the Columbia team’s measured response. This involved calculating the flow of electrons in graphene under the various electric and magnetic fields, accounting for multiple bounces at edges, and quantum mechanical tunneling at the junction. The theoretical analysis also shed light on why it has been so difficult to measure the predicted Veselago lensing in a robust way, and the group is developing new multi-junction device architectures based on this study. Together the experimental data and theoretical simulation gave the researchers a visual map of the refraction, and enabled them to be the first to quantitatively confirm the relationship between the incident and refracted angles (known as Snell’s Law in optics), as well as confirmation of the magnitude of the transmitted intensity as a function of angle (known as the Fresnel coefficients in optics).

“In many ways, this intensity of transmission is a more crucial parameter,” says Ghosh, “since it determines the probability that electrons actually make it past the barrier, rather than just their refracted angles. The transmission ultimately determines many of the performance metrics for devices based on these effects, such as the on-off ratio in a switch, for example.”