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

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.

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

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

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

“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.”