Category Archives: Packaging Materials

Zhe Fei pointed to the bright and dark vertical lines running across his computer screen. This nano-image, he explained, shows the waves associated with a half-light, half-matter quasiparticle moving inside a semiconductor.

“These are waves just like water waves,” said Fei, an Iowa State University assistant professor of physics and astronomy and an associate of the U.S. Department of Energy’s Ames Laboratory. “It’s like dropping a rock on the surface of water and seeing waves. But these waves are exciton-polaritons.”

This image shows how researchers launched and studied half-light, half-matter quasiparticles called exciton-polaritons. A laser from the top left shines on the sharp tip of a nano-imaging system aimed at a flat semiconductor. The red circles inside the semiconductor are the waves associated with the quasiparticles. Image courtesy of Zhe Fei/Iowa State University

This image shows how researchers launched and studied half-light, half-matter quasiparticles called exciton-polaritons. A laser from the top left shines on the sharp tip of a nano-imaging system aimed at a flat semiconductor. The red circles inside the semiconductor are the waves associated with the quasiparticles. Image courtesy of Zhe Fei/Iowa State University

Exciton-polaritons are a combination of light and matter. Like all quasiparticles, they’re created within a solid and have physical properties such as energy and momentum. In this study, they were launched by shining a laser on the sharp tip of a nano-imaging system aimed at a thin flake of molybdenum diselenide (MoSe2), a layered semiconductor that supports excitons.

Excitons can form when light is absorbed by a semiconductor. When excitons couple strongly with photons, they create exciton-polaritons.

It’s the first time researchers have made real-space images of exciton-polaritons. Fei said past research projects have used spectroscopic studies to record exciton-polaritons as resonance peaks or dips in optical spectra. Until recent years, most studies have only observed the quasiparticles at extremely cold temperatures – down to about -450 degrees Fahrenheit.

But Fei and his research group worked at room temperature with the scanning near-field optical microscope in his campus lab to take nano-optical images of the quasiparticles.

“We are the first to show a picture of these quasiparticles and how they propagate, interfere and emit,” Fei said.

The researchers, for example, measured a propagation length of more than 12 microns – 12 millionths of a meter – for the exciton-polaritons at room temperature.

Fei said the creation of exciton-polaritons at room temperature and their propagation characteristics are significant for developing future applications for the quasiparticles. One day they could even be used to build nanophotonic circuits to replace electronic circuits for nanoscale energy or information transfer.

Fei said nanophotonic circuits with their large bandwidth could be up to 1 million times faster than current electrical circuits.

A research team led by Fei recently reported its findings in the scientific journal Nature Photonics. The paper’s first author is Fengrui Hu, an Iowa State postdoctoral research associate in physics and astronomy. Additional co-authors are Yilong Luan, an Iowa State doctoral student in physics and astronomy; Marie Scott, a recently graduated undergraduate at the University of Washington; Jiaqiang Yan and David Mandrus of Oak Ridge National Laboratory and the University of Tennessee; and Xiaodong Xu of the University of Washington.

The researchers’ work was supported by funds from Iowa State and the Ames Laboratory to launch Fei’s research program. The W.M. Keck Foundation of Los Angeles also partially supported the nano-optical imaging for the project.

The researchers also learned that by changing the thickness of the MoSe2 semiconductor, they could manipulate the properties of the exciton-polaritons.

Fei, who has been studying quasiparticles in graphene and other 2-D materials since his graduate school days at University of California San Diego, said his earlier work opened the doors for studies of exciton-polaritons.

“We need to explore further the physics of exciton-polaritons and how these quasiparticles can be manipulated,” he said.

That could lead to new devices such as polariton transistors, Fei said. And that could one day lead to breakthroughs in photonic and quantum technologies.

AI is driving the development of 3D TSV and heterogeneous integration technologies. With its new 3D TSV & 2.5D business update report, Yole Développement (Yole), part of Yole Group of Companies investigates the advanced packaging industry and takes a closer look on the AI impact on this market.

“3D integration is clearly offering today unequalled performances suiting exactly the pressing needs of AI applications,” commented Emilie Jolivet, Technology & Market Analyst at Yole.

Initially developed for niche markets including MEMS devices and memories for datacenters, 3D integration is entering in a new era. The world population increase, the exploding smartphones market, the development of new functionalities such as voice/image recognition… all these parameters directly contribute to the development of AI and deep learning solutions, all based on 3D integration technologies. AI is not a concept anymore but a reality that is skyrocketing the development of disruptive advanced packaging technologies.

This year, the “More than Moore” market research and strategy consulting company is moving a step forwards the applications side. Its advanced packaging & semiconductor manufacturing team investigates the industry evolution, taking into account promising sectors such as deep learning, the end-users’ needs and required specifications for final systems. Yole’s analysts combine their advanced packaging expertise and their knowledge of the different industries to perform up-to-date and innovative reports. The 3D TSV & 2.5D business update report is a good example, with a strong focus on the high-performance sector.

Why do we need 3D TSV solutions, especially in high performance applications?

According to Yole, benefits are numerous and are part of the major issues initially identified by the industrial companies. Bandwidth, latency and power consumption are the key words of these innovations… Emilie Jolivet from Yole details some below:

  •  When two chips or more are integrated on an interposer, distance between logic and memory is shortened which enables lower latency and lower power consumption.
•  DRAM, based on a 3D TSV solution, is offering an unequalled bandwidth performance because of the ability of TSV solution to connect several layers of the device.
•  Artificial intelligence and specifically deep learning mostly intensively using memory and computing also need 3D TSV approaches. Both applications are driving the demand of interposer and 3D memory cubes.

AI and deep learning, both part of the high performance applications segment are might be the most impressive applications. However, datacenter networking, AR/VR and autonomous driving are not so far behind. Industrial companies progressively penetrate these market segments by developing dedicated approaches:

  •  Both 3D IC leaders, TSMC and Globalfoundries are involved in the development of new solutions focused on 3D SoC.
•  Samsung introduced its interposer solutions in 2017, SPIL is developing its own 2.5D solutions
•  STMicroelectronics is working on 3D interconnections and interposers for various applications including silicon photonics, data centers.

In addition, companies like Intel, Nvidia are completely re-thinking their growth strategy: “Major IC companies which missed the smartphone business clearly don’t want to miss the AI revolution,” commented Emilie Jolivet from Yole. From their side, investors are part of the playground. Therefore, they all re-align their strategy to have product portfolio for serving AI/deep learning needs. Datacenters, cloud computing, AI, autonomous driving are becoming key words for venture capitalists.

Yole’s analysts are convinced of the added value of 3D integration technologies. AI and deep learning are new applications to consider but not only. AR/VR will be also part of the 3D integration future. And the latest announcement from AMD regarding its new Radeon Pro Vega graphic card dedicated to Apple’s new iMac Pro is another step towards the computing applications™.

A detailed description of the 3D TSV and 2.5D Business Update – Market and Technology Trends 2017 is available on i-micronews.com, advanced packaging reports section.

By Paula Doe, SEMI

The future of contamination control in the next-generation supply chain for beyond 14nm-node semiconductor processes faces stringent challenges. While Moore’s Law is driving scale reduction, the industry is also facing ever-increasing process sensitivity, integration challenges of new materials and the need for unprecedented purity at process maturity.

“The supply chain needs a paradigm shift in thinking about defect control. What was just process variation for previous technology nodes can now be an excursion!” says Dr. Archita Sengupta, Intel senior GSM Technologist, leading the filtration and related supply chain contamination control program, who will discuss these challenges and possible solutions in the session on key materials issues at SEMICON West 2017 on July 11 in San Francisco at Moscone Center.

There are new materials being used for the first time, and even familiar materials need to be treated with new and different specifications. Even if the needed parameters are correctly specified, there may not be an accurate way to measure those parameters under HVM conditions, at least that most material suppliers can afford.  Chemicals, advanced filtration and purification, chemical delivery systems and equipment manufacturing can all be sources of wafer contamination. “The interaction between the tool and the chemicals is also increasingly important,” she notes. “All this is going to add more cost for the industry supply chain for quality control, but it will cost more in the end if we don’t proactively work together throughout the supply chain to figure out what matters to control and how!”

Stability is key

The most important thing material suppliers can do to meet customer quality demands is to maintain absolute stability of everything about their material and manufacturing process, suggests Jim Mulready, VP Global Quality Assurance, JSR Micro, who will also present at SEMICON West. “Traditional quality control, where the QC data at the end of my line only has to meet the customer’s specifications, doesn’t work,” he says, noting that the material supplier doesn’t have the same process tool, the same substrate, or the same process conditions as the customer, so the testing can’t duplicate the customer’s result. Moreover, the process sensitivity is getting tighter at every generation, with the tolerance of defects often being beyond the supplier’s ability to detect them. So, no specification can ever be precise enough to capture everything the customer really needs.  “Often tightening the specs doesn’t solve the problem,” he notes. “There are plenty of examples of material that was well within spec but didn’t function properly. The problem is not inadequate specs, it’s inadequate attention to other quality tools. The spec is necessary, but not sufficient.”

“The systematic (as opposed to technical) root cause of the material problems I faced as fab materials quality manager at Intel almost always came down to a problem in stability,” says Mulready, where there was a change to the material the supplier didn’t think was important, a change in the processing that they didn’t catch, or a change in the incoming raw material that they didn’t detect. “Material suppliers have to accept that the customers’ definition of quality becomes their definition of quality, and the main rule is to make sure that a material that’s working does not change at all. Consistency is the key for the end user, so it must be for us as well.  A spec alone will not measure or ensure that.  It takes robust change control, process control, and incoming raw material control.”

Semiconductor makers meanwhile, need to start paying attention not just to their immediate suppliers, but also to their suppliers’ supply chain; for example, not just the resist but also the resin and even the monomers used to make it. While the material suppliers need to qualify the incoming material, and serve as a kind of safety valve between the chemical industry and the IC makers, it can be difficult for them to control the supply quality when they are a very minor customer for the commodity chemical suppliers.  Those suppliers in turn may have no interest in investing in the tools needed to measure the particular properties of concern, and there may be a need for the IC customer to help inflict some pressure.

For more details on the SEMICON West 2017 Materials program, “Material Supply Challenges for Current and Future Leading-edge Devices,” organized by SEMI’s Chemical & Gas Manufacturers Group (CGMG), see www.semiconwest.org/programs-catalog/material-supply-leading-edge-devices. To see the full SEMICON West agenda, visit www.semiconwest.org/agenda-glance.

Scientists have developed a new method of characterizing graphene’s properties without applying disruptive electrical contacts, allowing them to investigate both the resistance and quantum capacitance of graphene and other two-dimensional materials. Researchers from the Swiss Nanoscience Institute and the University of Basel’s Department of Physics reported their findings in the journal Physical Review Applied.

Graphene consists of a single layer of carbon atoms. It is transparent, harder than diamond and stronger than steel, yet flexible, and a significantly better conductor of electricity than copper. Since graphene was first isolated in 2004, scientists across the world have been researching its properties and the possible applications for the ultrathin material. Other two-dimensional materials with similarly promising fields of application also exist; however, little research has been carried out into their electronic structures.

No need for electrical contacts

Electrical contacts are usually used to characterize the electronic properties of graphene and other two-dimensional materials. However, these can significantly alter the materials’ properties. Professor Christian Schönenberger’s team from the Swiss Nanoscience Institute and the University of Basel’s Department of Physics has now developed a new method of investigating these properties without applying contacts.

To do this, the scientists embedded graphene in the isolator boron nitride, placed it on a superconductor and coupled it with a microwave resonator. Both the electrical resistance and the quantum capacitance of the graphene affect the quality factor and resonance frequency of the resonator. Although these signals are very weak, they can be captured using superconducting resonators.

By comparing the microwave characteristics of resonators with and without encapsulated graphene, the scientists can determine both the electrical resistance and quantum capacitance. “These parameters are important in the determination of graphene’s exact properties and in the identification of limiting factors for its application,” explains Simon Zihlmann, a PhD student in Schönenberger’s group.

Also suitable for other two-dimensional materials

The boron nitride-encapsulated graphene served as a prototype material during the method’s development. Graphene integrated into other materials can be investigated in the same way. In addition, other two-dimensional materials can also be characterized without the use of electrical contacts; for example, the semiconductor molybdenum disulfide, which has applications in solar cells and optics.

By Walt Custer, Custer Consulting Group, and Dan Tracy, SEMI

SEMI’s year-to-date worldwide semiconductor equipment billings year-to-date through March show a 59.6 percent gain to the same period last year.

Understanding volatility in the electronic equipment supply chain can be valuable in forecasting future business activity.  A useful way to compare relevant electronic industry data series is by using 3/12 growth rates.  The 3/12 growth is the ratio of three months of data, compared to the same three months a year earlier.

Chart 1 compares the 3/12 growth rates of four data series:

  • World semiconductor equipment shipments (SEMI; www.semi.org)
  • Taiwan chip foundry sales (company composite maintained by Custer Consulting Group)
  • World semiconductor shipments (SIA, www.semiconductors.org & WSTS, www.wsts.org)
  • World electronic equipment sales (composite of 238 global OEMS maintained by Custer Consulting Group).

supply-chain-dynamics

Highlights

  • Semiconductor capital equipment sales are by far the most volatile of the four series in Chart 1, followed by foundry sales.
  • Foundry sales are a good leading indicator for semiconductor equipment shipments ─ leading SEMI equipment by 3-4 months on a 3/12 growth basis.
  • Foundry growth peaked in November 2016.
  • SEMI equipment growth appears to have peaked in February 2017.
  • Semiconductor shipments may have peaked in March 2017. March semiconductor revenues were up 18.5 percent in 1Q’17 vs 1Q’16 and, although still very strong, their rate of growth appears to have plateaued.

Note that 3/12 values greater than 1.0 indicate growth.  Declining 3/12 values (but greater than 1.0) indicate growth but at a slower rate.  Values below 1.0 indicate contraction.

Based upon Chart 1, semiconductor equipment 3/12 growth will likely reach zero in August or September of this year. Considering the unstable world geopolitical situation, uncertainty clearly exists.

SEMI members can access member-only market data and information at www.semi.org/en/free-market-data-semi-members.

Custer Consulting Group (www.custerconsulting.com) provides market research, business analyses and forecasts for the electronic equipment and solar/photovoltaic supply chains including semiconductors, printed circuit boards & other passive components, photovoltaic cells & modules, EMS, ODM & related assembly activities and materials & process equipment.

Researchers have uncovered the exact mechanism that causes new solar cells to break down in air, paving the way for a solution.

Solar cells harness energy from the Sun and provide an alternative to non-renewable energy sources like fossil fuels. However, they face challenges from costly manufacturing processes and poor efficiency – the amount of sunlight converted to useable energy.

Light-absorbing materials called organic lead halide perovskites are used in a new type of solar cells that have shown great promise, as they are more flexible and cheaper to manufacture than traditional solar cells constructed of silicon.

However, perovskite cells degrade rapidly in natural conditions, greatly decreasing their performance in a matter of days. This is one reason they are not currently widely used.

Previously, a team led by scientists from the Department of Chemistry at Imperial discovered that this breakdown is due to the formation of ‘superoxides’ that attack the perovskite material. These superoxides are formed when light hitting the cells releases electrons, which react with the oxygen in the air.

Now, in a study published in Nature Communications, the team have determined how the superoxides form and how they attack the perovskite material, and have proposed possible solutions.

Working with Dr Christopher Eames and Professor Saiful Islam at the University of Bath, the team found that superoxide formation is helped by spaces in the structure of the perovskite normally taken up by molecules of iodide. Although iodide is a component of the perovskite material itself, there are defects where iodide is missing. These vacant spots are then used in the formation of superoxides.

The team found that dosing the material with extra iodide after manufacturing did improve the stability, but that a more permanent solution could be to engineer the iodide defects out.

Lead author of the new study, Nicholas Aristidou from the Department of Chemistry at Imperial, said: “After identifying the role of iodide defects in generating superoxide, we could successfully improve the material stability by filling the vacancies with additional iodide ions. This open up a new way of optimising the material for enhanced stability by controlling the type and density of defects present.”

Lead researcher Dr Saif Haque from the Department of Chemistry at Imperial added: “We have now provided a pathway to understand this process at the atomic scale and allow the design of devices with improved stability.”

Currently, the only way of protecting perovskite cells from degradation by air and light is to encase them in glass. However, perovskite solar cells are made from flexible material designed to be used in a range of settings, so the glass encasement severely limits their function.

Dr Haque said: “Glass encasement restricts movement and adds weight and cost to the cells. Improving the perovskite cell material itself is the best solution.”

The team hope to next test the stability of the cells in real-world settings. The cells would be exposed to a combination of both oxygen and moisture, testing the cells in more relevant scenarios.

Hafnia dons a new face


May 12, 2017

It’s a material world, and an extremely versatile one at that, considering its most basic building blocks — atoms — can be connected together to form different structures that retain the same composition.

Diamond and graphite, for example, are but two of the many polymorphs of carbon, meaning that both have the same chemical composition and differ only in the manner in which their atoms are connected. But what a world of difference that connectivity makes: The former goes into a ring and costs thousands of dollars, while the latter has to sit content within a humble pencil.

The inorganic compound hafnium dioxide commonly used in optical coatings likewise has several polymorphs, including a tetragonal form with highly attractive properties for computer chips and other optical elements. However, because this form is stable only at temperatures above 3100 degrees Fahrenheit — think blazing inferno — scientists have had to make do with its more limited monoclinic polymorph. Until now.

A team of researchers led by University of Kentucky chemist Beth Guiton and Texas A&M University chemist Sarbajit Banerjee in collaboration with Texas A&M materials science engineer Raymundo Arroyave has found a way to achieve this highly sought-after tetragonal phase at 1100 degrees Fahrenheit — think near-room-temperature and potential holy grail for the computing industry, along with countless other sectors and applications.

The team’s research, published today in Nature Communications, details their observation of this spectacular atom-by-atom transformation, witnessed with the help of incredibly powerful microscopes at Oak Ridge National Laboratory. After first shrinking monoclinic hafnium dioxide particles down to the size of tiny crystal nanorods, they gradually heated them, paying close attention to the barcode-like structure characterizing each nanorod and, in particular, its pair of nanoscale, fault-forming stripes that seem to function as ground zero for the transition.

“In this study we are watching a tiny metal oxide rod transform from one structure, which is the typical material found at room temperature, into a different, related structure not usually stable below 3100 degrees Fahrenheit,” said Guiton, who is an associate professor of chemistry in the UK College of Arts & Sciences. “This is significant because the high-temperature material has amazing properties that make it a candidate to replace silicon dioxide in the semiconductor industry, which is built on silicon.”

Watch through the microscope’s lens as hafnia atoms rearrange themselves at nanoscale levels in this video showing the same raw data seen by the team, courtesy of the UK Guiton Group.

The semiconductor industry has long relied on silicon dioxide as its thin, non-conductive layer of choice in the critical gap between the gate electrode — the valve that turns a transistor on and off — and the silicon transistor. Consistently thinning this non-conductive layer is what allows transistors to become smaller and faster, but Guiton points out there is such a thing as too thin — the point at which electrons start sloshing across the barrier, thereby heating their surroundings and draining power. She says most of us have seen and felt this scenario to some degree (pun intended), for instance, while watching videos on our phones and the battery simultaneously drain as the device in our palm noticeably begins to warm.

As computer chips become smaller, faster and more powerful, their insulating layers must also be much more robust — currently a limiting factor for semiconductor technology. Guiton says this new phase of hafnia is an order of magnitude better at withstanding applied fields.

When it comes to watching hafnia’s structural transition between its traditional monoclinic state and this commercially desirable tetragonal phase at near-room temperature, Banerjee says it’s not unlike popular television — specifically, the “Hall of Faces” in the HBO show “Game of Thrones.”

“In essence, we have been able to watch in real time, on an atom by atom basis, as hafnia is transformed to a new phase, much like Arya Stark donning a new face,” Banerjee said. “The new phase of hafnia has a much higher ‘k’ value representing its ability to store charge, which would allow transistors to work really quickly while merely sipping on power instead of sapping it. The stripes turn out to be really important, since that is where the transition starts as the hafnia loses its stripes.”

Arroyave credits real-time atomic-scale information for enabling the group to figure out that the transformation occurs in a very different way at nanoscale levels than it does within the macroscopic particles that result in hafnia’s monoclinic form. The fact that it is nanoscale in the first place is why he says the transition occurs at, or much closer to, room temperature.

“Through synthesis at the nanoscale, the ‘height’ of the energy barrier separating the two forms has been shrunk, making it possible to observe tetragonal hafnia at much lower temperatures than usual,” Arroyave said. “This points toward strategies that could be used to stabilize a host of useful forms of materials that can enable a wide range of functionalities and associated technologies. This is just one example of the vast possibilities that exist when we start to explore the ‘metastable’ materials space.”

Banerjee says this study suggests one way to stabilize the tetragonal phase at actual room temperature — which he notes that his group previously accomplished via a different method last year — and big implications for fast, low-power-consumption transistors capable of controlling current without drawing power, reducing speed or producing heat.

“The possibilities are endless, including even more powerful laptops that don’t heat up and sip on power from their batteries and smart phones that ‘keep calm and carry on,'” Banerjee said. “We are trying to apply these same tricks to other polymorphs of hafnium dioxide and other materials — isolating other phases that are not readily stabilized at room temperature but may also have strange and desirable properties.”

Soitec, a designer and manufacturer of semiconductor materials for the electronics industry, has appointed Stephen Lin to the newly created position of vice president of strategic business development in China, a key region for the company’s future growth plans. Stephen Lin brings to Soitec nearly 30 years of experience leading semiconductor business operations in China and the U.S.

“Working with our executive team, Stephen is in charge of strengthening Soitec’s business interests within China as well as growing market demand for SOI wafer products,” said Thomas Piliszczuk, Soitec’s executive vice president, Business and Strategic Development. “Stephen will be instrumental in our efforts to continue growing China’s microelectronics ecosystem as he works closely with our customers as well as government agencies, institutions and the financial and investor communities.”

China is home to all key elements of the electronics value chain including semiconductor manufacturers, fabless device designers, and consumer end markets. Soitec is already highly engaged in China, working to expand the semiconductor ecosystem while also driving demand for silicon on insulator (SOI) wafer products with its direct and indirect customers. The company also collaborates closely with its Shanghai-based manufacturing partner Simgui and the National Silicon Industry Group (NSIG), which recently invested in Soitec.

Since beginning his semiconductor career at LSI Logic, Stephen Lin has held senior executive positions within several major electronics companies including NXP Semiconductors, Microsemi, Intel and Siemens. He also has launched start-up companies in China and the U.S. including Mobility Ventures. He earned his master in electrical engineering degree from McGill University in Quebec and his MBA from Santa Clara University in California. He is the author of multiple publications including “The Fabless Semiconductor China Handbook.”

Chemists have tried to synthesize carbon nanobelts for more than 60 years, but none have succeeded until now. A team at Nagoya University reported the first organic synthesis of a carbon nanobelt in Science. Carbon nanobelts are expected to serve as a useful template for building carbon nanotubes and open a new field of nanocarbon science.

The new nanobelt, measuring 0.83 nanometer (nm) in diameter, was developed by researchers at Nagoya University’s JST-ERATO Itami Molecular Nanocarbon Project, and the Institute of Transformative Bio-Molecules (ITbM). Scientists around the world have tried to synthesize carbon nanobelts since the 1950s and Professor Kenichiro Itami’s group has worked on its synthesis for 12 years.

“Nobody knew whether its organic synthesis was even possible or not,” says Segawa, one of the leaders of this study who had been involved in its synthesis for 7 and a half years. “However, I had my mind set on the synthesis of this beautiful molecule.”

Carbon nanobelts are belt-shaped molecules composed of fused benzene rings, which are aromatic rings consisting of six carbon atoms. Carbon nanobelts are a segment of carbon nanotubes, which have various applications in electronics and photonics due to their unique physical characteristics.

Current synthetic methods produce carbon nanotubes with inconsistent diameters and sidewall structures, which changes their electrical and optical properties. This makes it extremely difficult to isolate and purify a single carbon nanotube that has a specific diameter, length and sidewall structure. Therefore, being able to precisely control the synthesis of structurally uniform carbon nanotubes will help develop novel and highly functional materials.

Carbon nanobelts have been identified as a way to build structurally uniform carbon nanotubes. However, synthesizing carbon nanobelts is challenging due to their extremely high strain energies. This is because benzene is stable when flat, but becomes unstable when they are distorted by fusion of the rings.

To overcome this problem, Guillaume Povie, a postdoctoral researcher of the JST-ERATO project, Yasutomo Segawa, a group leader of the JST-ERATO project, and Kenichiro Itami, the director of JST-ERATO project and the center director of ITbM, have succeeded in the first chemical synthesis of a carbon nanobelt from a readily available precursor, p-xylene (a benzene molecule with two methyl groups in the 1,4- (para-) position) in 11 steps.

The key to this success is their synthetic strategy based on the belt-shaped formation from a macrocycle precursor with relatively low ring strain. In their strategy, the team prepared a macrocycle precursor from p-xylene in 10 steps, and formed the belt-shaped aromatic compound by a coupling reaction. Nickel was essential to mediate the coupling process.

“The most difficult part of this research was this key coupling reaction of the macrocycle precursor,” says Povie. “The reaction did not proceed well day after day and it took me three to four months for testing various conditions. I have always believed where there’s a will, there’s a way.”

In 2015, Itami launched a new initiative in his ERATO project to focus particularly on the synthesis of the carbon nanobelt. At the so-called “belt festival,” various new synthetic routes for the carbon nanobelt were proposed and more than 10 researchers were involved in the project. On September 28, 2016, exactly a year after the start of the festival, the carbon nanobelt structure was finally revealed by X-ray crystallography in front of the Itami group members. Everyone held their breath while staring at the screen during X-ray analysis, and cheered when the cylindrical shape image of the carbon nanobelt appeared on the screen. Itami, Segawa and Povie expressed their joy with a high five (movie: https://www.youtube.com/watch?v=cABZla9w0uo).

“It was one of the most exciting moments in my life and I will never forget it,” says Itami. “Since this is the result of a decade-long study, I greatly appreciate all the past and current members of my group for their support and encouragement. Thanks to their skill, toughness, sense and strong will of all members, we achieved this successful result.”

The synthesized carbon nanobelt is a red-colored solid and exhibits deep red fluorescence. Analysis by X-ray crystallography revealed that the carbon nanobelt has a cylindrical shape in the same manner as carbon nanotubes. The researchers also measured its light absorption and emission, electric conductivity and structural rigidity by ultraviolet-visible absorption fluorescence, and Raman spectroscopic studies, as well as theoretical calculations.

“Actually, the synthesis part was finished last August but I could not rest until I was able to confirm the X-ray structure of the carbon nanobelt,” says Povie. “I was really happy when I saw the X-ray structure.”

The carbon nanobelt will be released to the market in the future. “We are looking forward to discovering new properties and functionalities of the carbon nanobelt with researchers from all over the world,” say Segawa and Itami.

Two-dimensional graphene consists of single layers of carbon atoms and exhibits intriguing properties. The transparent material conducts electricity and heat extremely well. It is at the same time flexible and solid. Additionally, the electrical conductivity can be continuously varied between a metal and a semiconductor by, e.g., inserting chemically bound atoms and molecules into the graphene structure – the so-called functional groups. These unique properties offer a wide range of future applications as e.g. for new developments in optoelectronics or ultrafast components in the semiconductor industry. However, a successful use of graphene in the semiconductor industry can only be achieved if properties such as the conductivity, the size and the defects of the graphene structure induced by the functional groups can already be modulated during the synthesis of graphene.

In an international collaboration scientists led by Andreas Hirsch from the Friedrich-Alexander-Universität Erlangen-Nürnberg in close cooperation with Thomas Pichler from the University of Vienna accomplished a crucial breakthrough: using the latter’s newly developed experimental set-up they were able to identify, for the first time, vibrational spectra as the specific fingerprints of step-by-step chemically modified graphene by means of light scattering. This spectral signature, which was also theoretically attested, allows to determine the type and the number of functional groups in a fast and precise way. Among the reactions they examined, was the chemical binding of hydrogen to graphene. This was implemented by a controlled chemical reaction between water and particular compounds in which ions are inserted in graphite, a crystalline form of carbon.

This is a section of a graphene network with chemically bound hydrogen atom: the spectral vibrational signature of the single carbon-carbon bonds adjacent to the bound hydrogen atom is highlighted in different colors. Copyright: Frank Hauke, FAU

This is a section of a graphene network with chemically bound hydrogen atom: the spectral vibrational signature of the single carbon-carbon bonds adjacent to the bound hydrogen atom is highlighted in different colors. Copyright: Frank Hauke, FAU

Additional benefits

“This method of the in-situ Raman spectroscopy is a highly effective technique which allows controlling the function of graphene in a fast, contact-free and extensive way already during the production of the material,” says J. Chacon from Yachay Tech, one of the two lead authors of the study. This enables the production of tailored graphene-based materials with controlled electronic transport properties and their utilisation in semiconductor industry.