Tag Archives: Japan

Smectic liquid crystals

From an April 10, 2015 news release from the Tokyo Institute of Technology,

Researchers at Tokyo Institute of Technology have designed a smectic liquid crystal that overcomes many of the challenges posed by organic field effect transistor materials.

Crystalline organic semiconductors have attracted a lot of interest for convenient low-cost fabrication by printed electronics. However progress has been stymied by the low thermal durability and reproducibility of these materials. Now researchers at Tokyo Institute of Technology and the Japan Science and Technology Agency have designed a liquid crystal molecule that produces high-performance organic field effect transistors (FETs) with good temperature resilience and relatively low device variability in addition to high mobility.

Hiroaki Iino, Takayuki Usui and Jun-ichi Hanna designed a molecule that would incorporate a number of desirable liquid crystal qualities, in particular the smectic E phase. Low ordered liquid crystal phases form droplets at their melting temperature, but the smectic E phase has the advantage of retaining the thin-film shape.

They then fabricated organic FETs by spin coating a solution of their material at 110 °C before allowing it to cool. Comparison of the FET characteristics before and after mild annealing revealed a phase transition. Using atomic force microscopy the researchers identified that at around 120°C in the crystal formed a bilayer crystal phase.

The mobility of a bottom gated FET made from the material was around 12 cm2V-1s-1 comparable to single-crystal devices. “Considering that it could potentially be necessary to fabricate millions of FETs for display applications, polycrystalline OFETs may have an advantage over single-crystal OFETs,” point out the researchers in a report of the work. The devices also exhibited a minimal variability of just 1.2 cm2V-1s-1, which is likely an advantage from the smoothness of the obtained film.

The researchers conclude, “The discovery of a dramatic enhancement of FET mobility up to 13.9cm2V-1s-1, resulting from the phase transition from a monolayer to a bilayer crystal structure in mono-alkylated liquid crystalline molecules may lead to the possibility of designing new materials for the burgeoning field of printed electronics.”

Background

Small-molecule versus polymer FETs

The main issues around organic semiconductor FETs with small molecules are the low thermal durability. The same bonding that makes the molecules soluble for printing fabrication processes also leaves them prone to low melting points, which greatly inhibits the methods available for processing the materials. They also tend to form rough surfaces, which makes it difficult to reproducibly fabricate the devices that have the desired characteristics.

Attempts to use polymers with benzene-like delocalised electron bonding alleviated issues around the thermal durability to a certain extent. However, it exacerbated others, such as reproducible synthesis and purification of the polymers, as well as control of crystallinity and the molecular orientations towards both the substrate surface and the electrodes.

The design of the molecule

The researchers identified specific characteristics to enrol in the design of their molecule. They used a fused ring system of molecules with benzene-like delocalised electron bonding so that the material would readily crystallise. They then added a phenyl group to introduce the kind of disorder required for smectic E phase liquid crystals. A long flexible carbon chain was also added to encourage formation of a liquid crystal.

The molecule was also designed to have a single side chain so that crystallisation on cooling would be lower than that on heating. This is more convenient for fabrication processes with the material.

The phase transition

Studies of the field effect transistors before and after mild annealing revealed an improvement in carrier mobility by over an order of magnitude. The researchers concluded that the material underwent a phase transition between 70 °C and 120 °C. Improvements in device performance plateaued above 120 °C.

Atomic force microscope studies of the materials identified a step structure that changed from monolayer 2.8 nm steps to bilayer 5.7 nm steps following the phase transition. In the absence of a change in grain size or contact resistance, the researchers concluded that  crystal-to-crystal phase change from a monolayer to a bilayer structure was responsible for the improved transistor performance in annealed devices.

Here’s a link to and citation for the paper,

Liquid crystals for organic thin-film transistors by Hiroaki Iino, Takayuki Usui & Jun-ichi Hanna. Nature Communications 6, Article number: 6828 doi:10.1038/ncomms7828 Published 10 April 2015

This is an open access paper.

FibeRio and VF Corporation want their nanofiber technology to lead in apparel and footwear markets

An April 8, 2015 news item on Azonano describes a new business partnership,

FibeRio Technology Corporation, the total nanofiber solutions company, today announced a strategic partnership with VF Corporation, a global leader in branded lifestyle apparel, footwear and accessories, to develop and commercialize next-generation, performance apparel fabrics leveraging FibeRio’s proprietary nanotechnology.

The partnership centers on FibeRio’s Forcespinning® technology platform and its ability to produce unique nanofiber material in high volumes. VF intends to incorporate FibeRio’s capabilities and expertise across its three Global Innovation Centers which focus on advancements in performance apparel, footwear and jeanswear.

An April 8, 2015 FibeRio news release provides more details, including these about the respective companies which help to contextualize the deal,

About FibeRio Technology Corporation
FibeRio is the efficiency and performance layer expert offering composite media improvement services including nanofiber membrane development, pilot production for limited launches and performance layer supply. The Fiber Engine series delivers on the industry’s need for high output, versatile, yet economic nanofiber production solutions. For more information visit www.fiberiotech.com

About VF Corporation
VF Corporation (NYSE: VFC) is a global leader in the design, manufacture, marketing and distribution of branded lifestyle apparel, footwear and accessories. The company’s highly diversified portfolio of 30 powerful brands spans numerous geographies, product categories, consumer demographics and sales channels, giving VF a unique industry position and the ability to create sustainable, long-term growth for our customers and shareholders. The company’s largest brands are The North Face®, Vans®, Timberland®, Wrangler®, Lee® and Nautica®. For more information, visit www.vfc.com.

There are the usual “we’re thrilled and about to do exciting things” quotes along with a dearth of details explaining how nanofibers are going to lead to higher performance,

“VF’s Global Innovation Center strategy is centered on the pursuit of disruptive design and materials that will meaningfully redefine the future of apparel and footwear for our consumers,” said Dan Cherian, Vice President, VF Global Innovation Centers. “Our partnership with FibeRio is a great step toward the co-development of proprietary, high-performance nanofiber materials that will help push the boundaries of performance and explore the creation of new apparel and footwear market categories.”

FibeRio CEO Ellery Buchanan stated, “We are excited to partner with VF Corporation on our Forcespinning-based advanced nanofiber textiles. VF’s long history of brand strength and operational excellence along with our leading commercial scale nanofiber production expertise creates an excellent opportunity to proactively shape the competitive landscape.”

Nanofibers’ higher surface area and smaller pore size improves the characteristics of fibrous material. This enables performance levels in any given application to be materially improved using significantly less material in the end product, which also allows for lighter weight and lower cost. [emphasis mine] FibeRio’s Forcespinning technology is the only technology platform capable of both commercial scale melt and solution spinning nanofibers. This provides a more sustainable method of production because melt spinning does not require solvents. [emphasis mine] Additionally, Forcespinning can be used to solution spin with vastly smaller amounts of solvents than traditional nanofiber production processes such as electrospinning.

Using less material could be considered a good thing, assuming it doesn’t mean that consumers need to purchase the item more frequently. The sustainability aspects such as no solvents or lesser amounts of solvent sound good unless increased demand means that a lesser amount becomes a greater amount.

I look forward to learning more as this partnership develops. One final note, I wonder if these folks are competitive with Teijin-Aramid (a Japanese-Dutch company in the Teijin Group), a company which does a lot of work with nanofibers last mentioned here in a Sept. 24, 2014 posting (scroll down about 60% of the way),

Still talking about textile fibres but on a completely different track, I received a news release this morning (Sept. 25, 2014) from Teijin Aramid about carbon nanotubes and fibres,

Researchers of Teijin Aramid, based in the Netherlands, and Rice University in the USA are awarded with the honorary ‘Paul Schlack Man-Made Fibers Prize’ for corporate-academic partnerships in fiber research. Their new super fibers are now driving innovation in aerospace, healthcare, automotive, and (smart) clothing.

I also found an April 12, 2012 post about Teijin Fibers (another Teijin Group company) and their work with nanofibers and golf gloves and athletic socks.

A city of science in Japan: Kawasaki (Kanagawa)

Happily, I’m getting more nanotechnology (for the most part) information from Japan. Given Japan’s prominence in this field of endeavour I’ve long felt FrogHeart has not adequately represented Japanese contributions. Now that I’m receiving English language translations, I hope to better address the situation.

This morning (March 26, 2015), there were two news releases from Kawasaki INnovation Gateway at SKYFRONT (KING SKYFRONT), Coastal Area International Strategy Office, Kawasaki City, Japan in my mailbox. Before getting on to the news releases, here’s a little about  the city of Kawasaki and about its innovation gateway. From the Kawasaki, Kanagawa entry in Wikipedia (Note: Links have been removed),

Kawasaki (川崎市 Kawasaki-shi?) is a city in Kanagawa Prefecture, Japan, located between Tokyo and Yokohama. It is the 9th most populated city in Japan and one of the main cities forming the Greater Tokyo Area and Keihin Industrial Area.

Kawasaki occupies a belt of land stretching about 30 kilometres (19 mi) along the south bank of the Tama River, which divides it from Tokyo. The eastern end of the belt, centered on JR Kawasaki Station, is flat and largely consists of industrial zones and densely built working-class housing, the Western end mountainous and more suburban. The coastline of Tokyo Bay is occupied by vast heavy industrial complexes built on reclaimed land.

There is a 2014 video about Kawasaki’s innovation gateway, which despite its 14 mins. 39 secs. running time I am embedding here. (Caution: They highlight their animal testing facility at some length.)

Now on to the two news releases. The first concerns research on gold nanoparticles that was published in 2014. From a March 26, 2015 Kawasaki INnovation Gateway news release,

Gold nanoparticles size up to cancer treatment

Incorporating gold nanoparticles helps optimise treatment carrier size and stability to improve delivery of cancer treatment to cells.

Treatments that attack cancer cells through the targeted silencing of cancer genes could be developed using small interfering RNA molecules (siRNA). However delivering the siRNA into the cells intact is a challenge as it is readily degraded by enzymes in the blood and small enough to be eliminated from the blood stream by kidney filtration.  Now Kazunori Kataoka at the University of Tokyo and colleagues at Tokyo Institute of Technology have designed a protective treatment delivery vehicle with optimum stability and size for delivering siRNA to cells.

The researchers formed a polymer complex with a single siRNA molecule. The siRNA-loaded complex was then bonded to a 20 nm gold nanoparticle, which thanks to advances in synthesis techniques can be produced with a reliably low size distribution. The resulting nanoarchitecture had the optimum overall size – small enough to infiltrate cells while large enough to accumulate.

In an assay containing heparin – a biological anti-coagulant with a high negative charge density – the complex was found to release the siRNA due to electrostatic interactions. However when the gold nanoparticle was incorporated the complex remained stable. Instead, release of the siRNA from the complex with the gold nanoparticle could be triggered once inside the cell by the presence of glutathione, which is present in high concentrations in intracellular fluid. The glutathione bonded with the gold nanoparticles and the complex, detaching them from each other and leaving the siRNA prone to release.

The researchers further tested their carrier in a subcutaneous tumour model. The authors concluded that the complex bonded to the gold nanoparticle “enabled the efficient tumor accumulation of siRNA and significant in vivo gene silencing effect in the tumor, demonstrating the potential for siRNA-based cancer therapies.”

The news release provides links to the March 2015 newsletter which highlights this research and to the specific article and video,

March 2015 Issue of Kawasaki SkyFront iNewsletter: http://inewsletter-king-skyfront.jp/en/

Contents

Feature video on Professor Kataoka’s research : http://inewsletter-king-skyfront.jp/en/video_feature/vol_3/feature01/

Research highlights: http://inewsletter-king-skyfront.jp/en/research_highlights/vol_3/research01/

Here’s a link to and a citation for the paper,

Precise Engineering of siRNA Delivery Vehicles to Tumors Using Polyion Complexes and Gold Nanoparticles by Hyun Jin Kim, Hiroyasu Takemoto, Yu Yi, Meng Zheng, Yoshinori Maeda, Hiroyuki Chaya, Kotaro Hayashi, Peng Mi, Frederico Pittella, R. James Christie, Kazuko Toh, Yu Matsumoto, Nobuhiro Nishiyama, Kanjiro Miyata, and Kazunori Kataoka. ACS Nano, 2014, 8 (9), pp 8979–8991 DOI: 10.1021/nn502125h Publication Date (Web): August 18, 2014
Copyright © 2014 American Chemical Society

This article is behind a paywall.

The second March 26, 2015 Kawasaki INnovation Gateway news release concerns a DNA chip and food-borne pathogens,

Rapid and efficient DNA chip technology for testing 14 major types of food borne pathogens

Conventional methods for testing food-borne pathogens is based on the cultivation of pathogens, a process that is complicated and time consuming. So there is demand for alternative methods to test for food-borne pathogens that are simpler, quick and applicable to a wide range of potential applications.

Now Toshiba Ltd and Kawasaki City Institute for Public Health have collaborated in the development of a rapid and efficient automatic abbreviated DNA detection technology that can test for 14 major types of food borne pathogens. The so called ‘DNA chip card’ employs electrochemical DNA chips and overcomes the complicated procedures associated with genetic testing of conventional methods. The ‘DNA chip card’ is expected to find applications in hygiene management in food manufacture, pharmaceuticals, and cosmetics.

Details

The so-called automatic abbreviated DNA detection technology ‘DNA chip card’ was developed by Toshiba Ltd and in a collaboration with Kawasaki City Institute for Public Health, used to simultaneously detect 14 different types of food-borne pathogens in less than 90 minutes. The detection sensitivity depends on the target pathogen and has a range of 1E+01~05 cfu/mL.

Notably, such tests would usually take 4-5 days using conventional methods based on pathogen cultivation. Furthermore, in contrast to conventional DNA protocols that require high levels of skill and expertise, the ‘DNA chip card’ only requires the operator to inject nucleic acid, thereby making the procedure easier to use and without specialized operating skills.

Examples of pathogens associated with food poisoning that were tested with the “DNA chip card”

Enterohemorrhagic Escherichia coli

Salmonella

Campylobacter

Vibrio parahaemolyticus

Shigella

Staphylococcus aureus

Enterotoxigenic Escherichia coli

Enteroaggregative Escherichia coli

Enteropathogenic Escherichia coli

Clostridium perfringens

Bacillus cereus

Yersinia

Listeria

Vibrio cholerae

I think 14 is the highest number of tests I’ve seen for one of these chips. This chip is quite an achievement.

One final bit from the news release about the DNA chip provides a brief description of the gateway and something they call King SkyFront,

About KING SKYFRONT

The Kawasaki INnovation Gateway (KING) SKYFRONT is the flagship science and technology innovation hub of Kawasaki City. KING SKYFRONT is a 40 hectare area located in the Tonomachi area of the Keihin Industrial Region that spans Tokyo and Kanagawa Prefecture and Tokyo International Airport (also often referred to as Haneda Airport).

KING SKYFRONT was launched in 2013 as a base for scholars, industrialists and government administrators to work together to devise real life solutions to global issues in the life sciences and environment.

I find this emphasis on the city interesting. It seems that cities are becoming increasingly important and active where science research and development are concerned. Europe seems to have adopted a biannual event wherein a city is declared a European City of Science in conjunction with the EuroScience Open Forum (ESOF) conferences. The first such city was Dublin in 2012 (I believe the Irish came up with the concept themselves) and was later adopted by Copenhagen for 2014. The latest city to embrace the banner will be Manchester in 2016.

Speeding up the process for converting carbon dioxide into hydrocarbon fuel

This is a personal thrill; it’s the first time in seven years that I’ve received a press release directly from an institution in Asia.

A March 10, 2015 MANA, the International Center for Materials Nanoarchitectonics at NIMS (National Institute for Materials Science) press release announces and describes hydrocarbon fuel research from Japan and China first published online in Nov. 2014 and later in print in January 2015,

A combination of semiconductor catalysts, optimum catalyst shape, gold-copper co-catalyst alloy nanoparticles and hydrous hydrazine reducing agent enables an increase of hydrocarbon generation from CO2 by a factor of ten.

“Solar-energy-driven conversion of CO2 into hydrocarbon fuels can simultaneously generate chemical fuels to meet energy demand and mitigate rising CO2 levels,” explain Jinhua Ye and her colleagues at the International Center for Materials Nanoarchitectonics in their latest report. Now the research team have identified the conditions and catalysts that will maximise the yield of hydrocarbons from CO2, generating ten times previously reported production rates.

Carbon dioxide can be converted into a hydrocarbon by means of ‘reduction reactions’ -a type of reaction that involves reducing the oxygen content of a molecule, increasing the hydrogen content or increasing the electrons. In photocatalytic reduction of CO2 light activates the catalyst for the reaction.

Ye and his team introduced four approaches that each contributed to an increased reaction rate. First, they combined two known semiconductor photocatalysts strontium titanate (STO) and titania [titanium dioxide] (TiO2) – which led to the separation of the charges generated by light and hence a more effective photocatalyst. Second, the high surface area of the nanotubes was made greater by holes in the tube surfaces, which enhances catalysis by increasing the contact between the gases and catalysts. Third, the tubes were decorated with gold-copper (Au3Cu) nanoparticle co-catalysts to further enhance the catalysis, and fourth, they used hydrous hydrazine (N2H4•H2O) as the source of hydrogen.

Although the high hydrogen content of hydrous hydrazine is widely recognised in the context of hydrogen storage there are no previous reports of its use for reduction reactions. The researchers demonstrated that the reducing properties of hydrous hydrazine were so great that oxidation of the co-catalytic nanoparticles – a problem when water or hydrogen are used – was avoided.

The researchers conclude their report, “This opens a feasible route to enhance the photocatalytic efficiency, which also aids the development of photocatalysts and co-catalysts.”

Affiliations

The researchers on this project are associated with the following institutions:

International Center for Materials Nanoarchitectonics (MANA), and the Environmental Remediation Materials Unit,  National Institute for Materials Science (NIMS) 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan

Graduate School of Chemical Science and Engineering, Hokkaido University, Sapporo 060-0814, Japan

TU-NIMS Joint Research Center, School of Material Science and Engineering, Tianjin University 92 Weijin Road, Tianjin,  P.R. China

Here’s a link to and a citation for the paper,

Photocatalytic Reduction of Carbon Dioxide by Hydrous Hydrazine over Au–Cu Alloy Nanoparticles Supported on SrTiO3/TiO2 Coaxial Nanotube Arrays by Dr. Qing Kang, Dr. Tao Wang, Dr. Peng Li, Dr. Lequan Liu, Dr. Kun Chang, Mu Li, and Prof. Jinhua Ye. Angewandte Chemie International Edition Volume 54, Issue 3, pages 841–845, January 12, 2015 DOI: 10.1002/anie.201409183 Article first published online: 24 NOV 2014

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

This research is behind a paywall.

Europe’s search for raw materials and hopes for nanotechnology-enabled solutions

A Feb. 27, 2015 news item on Nanowerk highlights the concerns over the availability of raw materials and European efforts to address those concerns,

Critical raw materials’ are crucial to many European industries but they are vulnerable to scarcity and supply disruption. As such, it is vital that Europe develops strategies for meeting the demand for raw materials. One such strategy is finding methods or substances that can replace the raw materials that we currently use. With this in mind, four EU projects working on substitution in catalysis, electronics and photonics presented their work at the Third Innovation Network Workshop on substitution of Critical Raw Materials hosted by the CRM_INNONET project in Brussels earlier this month [February 2015].

A Feb. 26, 2015 CORDIS press release, which originated the news item, goes on to describe four European Union projects working on nanotechnology-enabled solutions,

NOVACAM

NOVACAM, a coordinated Japan-EU project, aims to develop catalysts using non-critical elements designed to unlock the potential of biomass into a viable energy and chemical feedstock source.

The project is using a ‘catalyst by design’ approach for the development of next generation catalysts (nanoscale inorganic catalysts), as NOVACAM project coordinator Prof. Emiel Hensen from Eindhoven University of Technology in the Netherlands explained. Launched in September 2013, the project is developing catalysts which incorporate non-critical metals to catalyse the conversion of lignocellulose into industrial chemical feedstocks and bio-fuels. The first part of the project has been to develop the principle chemistry while the second part is to demonstrate proof of process. Prof. Hensen predicts that perhaps only two of three concepts will survive to this phase.

The project has already made significant progress in glucose and ethanol conversion, according to Prof. Hensen, and has produced some important scientific publications. The consortium is working with and industrial advisory board comprising Shell in the EU and Nippon Shokubai in Japan.

FREECATS

The FREECATS project, presented by project coordinator Prof. Magnus Rønning from the Norwegian University of Science and Technology, has been working over the past three years to develop new metal-free catalysts. These would be either in the form of bulk nanomaterials or in hierarchically organised structures – both of which would be capable of replacing traditional noble metal-based catalysts in catalytic transformations of strategic importance.

Prof. Magnus Rønning explained that the application of the new materials could eliminate the need for the use for platinum group metals (PGM) and rare earth metals – in both cases Europe is very reliant on other countries for these materials. Over the course of its research, FREECATS targeted three areas in particular – fuel cells, the production of light olefins and water and wastewater purification.

By working to replace the platinum in fuel cells, the project is supporting the EU’s aim of replacing the internal combustion engine by 2050. However, as Prof. Rønning noted, while platinum has been optimized for use over several decades, the materials FREECATS are using are new and thus come with their new challenges which the project is addressing.

HARFIR

Prof. Atsufumi Hirohata of the University of York in the United Kingdom, project coordinator of HARFIR, described how the project aims to discover an antiferromagnetic alloy that does not contain the rare metal Iridium. Iridium is becoming more and more widely used in numerous spin electronic storage devices, including read heads in hard disk drives. The world supply depends on Platinum ore that comes mainly from South Africa. The situation is much worse than for other rare earth elements as the price has been shooting up over recent years, according to Prof. Hirohata.

The HARFIR team, divided between Europe and Japan, aims to replace Iridium alloys with Heusler alloys. The EU team, led by Prof. Hirohata, has been working on the preparation of polycrystalline and epitaxial thin films of Heusler Alloys, with the material design led by theoretical calculations. The Japanese team, led by Prof. Koki Takanashi at Tohoku University, is meanwhile working on the preparation of epitaxial thin films, measurements of fundamental properties and structural/magnetic characterisation by neutron and synchrotron x-ray beams.

One of the biggest challenges has been that Heusler alloys have a relatively complicated atomic structure. In terms of HARFIR’s work, if any atomic disordering at the edge of nanopillar devices, the magnetic properties that are needed are lost. The team is exploring solutions to this challenge.

IRENA

Prof. of Esko Kauppinen Aalto University in Finland closed off the first session of the morning with his presentation of the IRENA project. Launched in September 2013, the project will run until mid 2017 working towards the aim of developing high performance materials, specifically metallic and semiconducting single-walled carbon nanotube (SWCNT) thin films to completely eliminate the use of the critical metals in electron devices. The ultimate aim is to replace Indium in transparent conducting films, and Indium and Gallium as a semiconductor in thin film field effect transistors (TFTs).

The IRENA team is developing an alternative that is flexible, transparent and stretchable so that it can meet the demands of the electronics of the future – including the possibility to print electronics.

IRENA involves three partners from Europe and three from Japan. The team has expertise in nanotube synthesis, thin film manufacturing and flexible device manufacturing, modelling of nanotube growth and thin film charge transport processes, and the project has benefitted from exchanges of team members between institutions. One of the key achievements so far is that the project has succeeded in using a nanotube thin film for the first time as the both the electrode and hole blocking layer in an organic solar cell.

You’ll note that Japan is a partner in all of these projects. In all probability, these initiatives have something to do with rare earths which are used in much of today’s electronics technology and Japan is sorely lacking in those materials. China, by comparison, has dominated the rare earths export industry and here’s an excerpt from my Nov. 1, 2013 posting where I outline the situation (which I suspect hasn’t changed much since),

As for the short supply mentioned in the first line of the news item, the world’s largest exporter of rare earth elements at 90% of the market, China, recently announced a cap according to a Sept. 6, 2013 article by David Stanway for Reuters. The Chinese government appears to be curtailing exports as part of an ongoing, multi-year strategy. Here’s how Cientifica‘s (an emerging technologies consultancy, etc.) white paper (Simply No Substitute?) about critical materials published in 2012 (?), described the situation,

Despite their name, REE are not that rare in the Earth’s crust. What has happened in the past decade is that REE exports from China undercut prices elsewhere, leading to the closure of mines such as the Mountain Pass REE mine in California. Once China had acquired a dominant market position, prices began to rise. But this situation will likely ease. The US will probably begin REE production from the Mountain Pass mine later in 2012, and mines in other countries are expected to start operation soon as well.

Nevertheless, owing to their broad range of uses REE will continue to exert pressures on their supply – especially for countries without notable REE deposits. This highlights two aspects of importance for strategic materials: actual rarity and strategic supply issues such as these seen for REE. Although strategic and diplomatic supply issues may have easier solutions, their consideration for manufacturing industries will almost be the same – a shortage of crucial supply lines.

Furthermore, as the example of REE shows, the identification of long-term supply problems can often be difficult, and not every government has the same strategic foresight that the Chinese demonstrated. And as new technologies emerge, new elements may see an unexpected, sudden demand in supply. (pp. 16-17)

Meanwhile, in response to China’s decision to cap its 2013 REE exports, the Russian government announced a $1B investment to 2018 in rare earth production,, according to a Sept. 10, 2013 article by Polina Devitt for Reuters.

I’m not sure you’ll be able to access Tim Harper’s white paper as he is now an independent, serial entrepreneur. I most recently mentioned him in relation to his articles (on Azonano) about the nanotechnology scene in a Feb. 12, 2015 posting where you’ll also find contact details for him.

Graphene with a pentagonal pattern

Graphene has been viewed, until now, as having an hexgonal (six-sided) pattern. However, researchers have discovered a new graphene pattern according to a Feb. 3, 2015 news item on Nanowerk,

Researchers at Virginia Commonwealth University and universities in China and Japan have discovered a new structural variant of carbon called “penta-graphene” – a very thin sheet of pure carbon that has a unique structure inspired by a pentagonal pattern of tiles found paving the streets of Cairo.

The newly discovered material, called penta-graphene, is a single layer of carbon pentagons that resembles the Cairo tiling, and that appears to be dynamically, thermally and mechanically stable.

A Feb. 3, 2015 Virginia Commonwealth University (VCU) news release by Brian McNeill (also on EurekAlert), which originated the news item, provides more information about the research,

“The three last important forms of carbon that have been discovered were fullerene, the nanotube and graphene. Each one of them has unique structure. Penta-graphene will belong in that category,” said the paper’s senior author, Puru Jena, Ph.D., distinguished professor in the Department of Physics in VCU’s College of Humanities and Sciences.

Qian Wang, Ph.D., a professor at Peking University and an adjunct professor at VCU, was dining in a restaurant in Beijing with her husband when she noticed artwork on the wall depicting pentagon tiles from the streets of Cairo.

“I told my husband, “Come, see! This is a pattern composed only of pentagons,'” she said. “I took a picture and sent it to one of my students, and said, ‘I think we can make this. It might be stable. But you must check it carefully.’ He did, and it turned out that this structure is so beautiful yet also very simple.”

Most forms of carbon are made of hexagonal building blocks, sometimes interspersed with pentagons. Penta-graphene would be a unique two-dimensional carbon allotrope composed exclusively of pentagons.

Along with Jena and Wang, the paper’s authors include Shunhong Zhang, Ph.D candidate, from Peking University; Jian Zhou, Ph.D., a postdoctoral researcher at VCU; Xiaoshuang Chen, Ph.D., from the Chinese Academy of Science in Shanghai; and Yoshiyuki Kawazoe, Ph.D., from Tohoku University in Sendai, Japan.

The researchers simulated the synthesis of penta-graphene using computer modelling. The results suggest that the material might outperform graphene in certain applications, as it would be mechanically stable, possess very high strength, and be capable of withstanding temperatures of up to 1,000 degrees Kelvin.

“You know the saying, diamonds are forever? That’s because it takes a lot of energy to convert diamond back into graphite,” Jena said. “This will be similar.”

Penta-graphene has several interesting and unusual properties, Jena said. For example, penta-graphene is a semiconductor, whereas graphene is a conductor of electricity.

“When you take graphene and roll it up, you make what is called a carbon nanotube which can be metallic or semiconducting,” Jena said. “Penta-graphene, when you roll it up, will also make a nanotube, but it is always semiconducting.”

The way the material stretches is also highly unusual, the researchers said.

“If you stretch graphene, it will expand along the direction it is stretched, but contract along the perpendicular direction.” Wang said. “However, if you stretch penta-graphene, it will expand in both directions.”

The material’s mechanical strength, derived from a rare property known as Negative Poisson’s Ratio, may hold especially interesting applications for technology, the researchers said.

Penta-graphene’s properties suggest that it may have applications in electronics, biomedicine, nanotechnology and more.

The next step, Jena said, is for scientists to synthesize penta-graphene.

“Once you make it, it [will be] very stable. So the question becomes, how do you make it? In this paper, we have some ideas. Right now, the project is theoretical. It’s based on computer modelling, but we believe in this prediction quite strongly. And once you make it, it will open up an entirely new branch of carbon science. Two-dimensional carbon made completely of pentagons has never been known.”

Here’s a graphic representation of the new graphene material,

Caption: The newly discovered material, called penta-graphene, is a single layer of carbon pentagons that resembles the Cairo tiling, and that appears to be dynamically, thermally and mechanically stable. Credit: Virginia Commonwealth University

Caption: The newly discovered material, called penta-graphene, is a single layer of carbon pentagons that resembles the Cairo tiling, and that appears to be dynamically, thermally and mechanically stable.
Credit: Virginia Commonwealth University

Here’s a link to and a citation for the paper,

Penta-graphene: A new carbon allotrope by Shunhong Zhanga, Jian Zhou, Qian Wanga, Xiaoshuang Chen, Yoshiyuki Kawazoe, and Puru Jena. PNAS February 2, 2015 doi: 10.1073/pnas.1416591112 Published online before print February 2, 2015

This paper is behind a paywall.

Nano and stem cell differentiation at Rutgers University (US)

A Nov. 14, 2014 news item on Azonano features a nanoparticle-based platform for differentiating stem cells,

Rutgers University Chemistry Associate Professor Ki-Bum Lee has developed patent-pending technology that may overcome one of the critical barriers to harnessing the full therapeutic potential of stem cells.

A Nov. 1, 2104 Rutgers University news release, which originated the news item, describes the challenge in more detail,

One of the major challenges facing researchers interested in regenerating cells and growing new tissue to treat debilitating injuries and diseases such as Parkinson’s disease, heart disease, and spinal cord trauma, is creating an easy, effective, and non-toxic methodology to control differentiation into specific cell lineages. Lee and colleagues at Rutgers and Kyoto University in Japan have invented a platform they call NanoScript, an important breakthrough for researchers in the area of gene expression. Gene expression is the way information encoded in a gene is used to direct the assembly of a protein molecule, which is integral to the process of tissue development through stem cell therapeutics.

Stem cells hold great promise for a wide range of medical therapeutics as they have the ability to grow tissue throughout the body. In many tissues, stem cells have an almost limitless ability to divide and replenish other cells, serving as an internal repair system.

Transcription factor (TF) proteins are master regulators of gene expression. TF proteins play a pivotal role in regulating stem cell differentiation. Although some have tried to make synthetic molecules that perform the functions of natural transcription factors, NanoScript is the first nanomaterial TF protein that can interact with endogenous DNA. …

“Our motivation was to develop a highly robust, efficient nanoparticle-based platform that can regulate gene expression and eventually stem cell differentiation,” said Lee, who leads a Rutgers research group primarily focused on developing and integrating nanotechnology with chemical biology to modulate signaling pathways in cancer and stem cells. “Because NanoScript is a functional replica of TF proteins and a tunable gene-regulating platform, it has great potential to do exactly that. The field of stem cell biology now has another platform to regulate differentiation while the field of nanotechnology has demonstrated for the first time that we can regulate gene expression at the transcriptional level.”

Here’s an image illustrating NanoScript and gold nanoparticles,

Courtesy Rutgers University

Courtesy Rutgers University

The news release goes on to describe the platform’s use of gold nanoparticles,

NanoScript was constructed by tethering functional peptides and small molecules called synthetic transcription factors, which mimic the individual TF domains, onto gold nanoparticles.

“NanoScript localizes within the nucleus and initiates transcription of a reporter plasmid by up to 30-fold,” said Sahishnu Patel, Rutgers Chemistry graduate student and co-author of the ACS Nano publication. “NanoScript can effectively transcribe targeted genes on endogenous DNA in a nonviral manner.”

Lee said the next step for his research is to study what happens to the gold nanoparticles after NanoScript is utilized, to ensure no toxic effects arise, and to ensure the effectiveness of NanoScript over long periods of time.

“Due to the unique tunable properties of NanoScript, we are highly confident this platform not only will serve as a desirable alternative to conventional gene-regulating methods,” Lee said, “but also has direct employment for applications involving gene manipulation such as stem cell differentiation, cancer therapy, and cellular reprogramming. Our research will continue to evaluate the long-term implications for the technology.”

Lee, originally from South Korea, joined the Rutgers faculty in 2008 and has earned many honors including the NIH Director’s New Innovator Award. Lee received his Ph.D. in Chemistry from Northwestern University where he studied with Professor Chad. A. Mirkin, a pioneer in the coupling of nanotechnology and biomolecules. Lee completed his postdoctoral training at The Scripps Research Institute with Professor Peter G. Schultz. Lee has served as a Visiting Scholar at both Princeton University and UCLA Medical School.

The primary interest of Lee’s group is to develop and integrate nanotechnologies and chemical functional genomics to modulate signaling pathways in mammalian cells towards specific cell lineages or behaviors. He has published more than 50 articles and filed for 17 corresponding patents.

Here’s a link to and a citation for the paper,

NanoScript: A Nanoparticle-Based Artificial Transcription Factor for Effective Gene Regulation by Sahishnu Patel, Dongju Jung, Perry T. Yin, Peter Carlton, Makoto Yamamoto, Toshikazu Bando, Hiroshi Sugiyama, and Ki-Bum Lee. ACS Nano, 2014, 8 (9), pp 8959–8967 DOI: 10.1021/nn501589f Publication Date (Web): August 18, 2014
Copyright © 2014 American Chemical Society

This paper is behind a paywall.

Nestling a two-element atomic chain inside a carbon nanotube

While there doesn’t seem to be a short-term application for this research from Japan, the idea of nestling a chain of two elements inside a carbon nanotube is intriguing, from an Oct. 16, 2014 news item on Nanowerk,

Kazutomo Suenaga of the Nanotube Research Center (NTRC) of the National Institute of Advanced Industrial Science and Technology (AIST) and Ryosuke Senga of the Nano-carbon Characterization Team, NTRC, AIST, have synthesized an atomic chain in which two elements are aligned alternately and have evaluated its physical properties on an atomic level.

An ionic crystalline atomic chain of cesium iodine (CsI) has been synthesized by aligning a cesium ion (Cs+), a cation and an iodine ion (I-), an anion, alternately by encapsulating CsI in the microscopic space inside a carbon nanotube. Furthermore, by using an advanced aberration-corrected electron microscope, the physical phenomena unique to the CsI atomic chain, such as the difference in dynamic behavior of its cations and anions, have been discovered. In addition, from theoretical calculation using density functional theory (DFT), this CsI atomic chain has been found to indicate different optical properties from a three-dimensional CsI crystal, and applications to new optical devices are anticipated.

An Oct. 16, 2014 National Institute of Advanced Industrial Science and Technology (AIST) press release, which originated the news item, situates the research within a social and historical context,

Social Background of Research

In the accelerating and ballooning information society, electronic devices used in computers and smartphones has constantly demanded higher performance and efficiency. The materials currently drawing expectations are low-dimensional materials with a single to few-atom width and thickness. Two-dimensional materials, typified by graphene, indicate unique physical characteristics not found in three-dimensional materials, such as its excellent electrical transport properties, and are being extensively researched.

An atomic chain, which has an even finer structure with a width of only one atom, has been predicted to display excellent electrical transport properties, like two-dimensional materials. Although expectations were higher than for two-dimensional materials from the viewpoint of integration, it had attracted little attention until now. This is because of the technological difficulties faced by the various processes of academic research from synthesis to analysis of atomic chains, and academic understanding has not progressed far (Fig. 1).

Figure 1
Figure 1 : Transition of target materials in material research

History of Research

AIST has been developing element analysis methods on a single-atom level to detect certain special structures including impurities, dopants and defects, that affect the properties of low-dimensional materials such as carbon nanotubes and graphene (AIST press releases on July 6, 2009, January 12, 2010, December 16, 2010 and July 9, 2012). In this research, efforts were made for the synthesis and analysis of the atomic chain, a low-dimensional material, using the accumulated technological expertise. This research has been supported by both the Strategic Basic Research Program of the Japan Science and Technology Agency (FY2012 to FY2016), and the Grants-in-aid for Scientific Research of the Japan Society for the Promotion of Science, “Development of elemental technology for the atomic-scale evaluation and application of low-dimensional materials using nano-space” (FY2014 to FY2016).

The press release also offers more details about the research and future applications,

Details of Research

The developed technology is the technology to expose carbon nanotubes, with a diameter of 1 nm or smaller, to CsI vapor to encapsulate CsI in the microscopic space inside the carbon nanotubes, to synthesize an atomic chain in which two elements, Cs and I, are aligned alternately. Furthermore, by combining aberration-corrected electron microscopy and an electronic spectroscopic technique known as electron energy-loss spectroscopy (EELS) detailed structural analysis of this atomic chain was conducted. In order to identify each atom aligned at a distance of 1 nm or less without destroying them, the accelerating voltage of the electron microscope was significantly lowered to 60 kV to reduce damage to the sample by electron beams, while maintaining sufficient spatial resolution of around 1 nm. Figure 2 indicates the smallest CsI crystal confirmed so far, and the CsI atomic chain synthesized in this research.

Figure 2
Figure 2 : Comparison of CsI atomic chain and CsI crystal
(Top: Actual annular dark-field images, Bottom: Corresponding models)

Figure 3 shows the annular dark-field (ADF) image of the CsI atomic chain and the element mapping for Cs and I, respectively, obtained by EELS. It can be seen that the two elements are aligned alternately. There has not been any report of this simple and ideal structure actually being produced and observed, and it can be said to be a fundamental, important finding in material science.

Normally, in an ADF image, those with larger atomic numbers appear brighter. However, in this CsI atomic chain, I (atomic number 53) appears brighter than Cs (atomic number 55). This is because Cs, being a cation, moves more actively (more accurately, the total amount of electrons scattered by the Cs atom is not very different from those of the I atom, but the electrons scattered by the moving Cs atom generate spatial expansion), indicating a difference in dynamic behavior of the cation and the anion that cannot occur in a large three-dimensional crystal. Locations where single Cs atom or I atom is absent, namely vacancies, were also found (Fig. 3, right).

The unique behavior and structure influence various physical properties. When optical absorption spectra were calculated using DFT, the response of the CsI atomic chain to light differed with the direction of incidence. Furthermore, it was found that in a CsI atomic chain with vacancies, the electron state of vacancy sites where the I atom is absent possess a donor level at which electrons were easily released, while vacancy sites where the Cs atom is absent possess a receptor level at which electrons were easily received. By making use of these physical properties, applications to new electro-optical devices, such as a micro-light source and an optical switch using light emission from a single vacancy in the CsI atomic chain, are conceivable. In addition, further research into combinations of other elements triggered by the present results may lead to the development of new materials and device applications. There are expectations for atomic chains to be the next-generation materials for devices in search of further miniaturization and integration.

Figure 3
Figure 3 : Synthesized CsI atomic chain, encapsulated in double-walled carbon nanotube
(From left: ADF image, element maps for Cs and I, model, ADF image of CsI atomic chains with vacancies)

Future Plans

Since the CsI atomic chain displays optical properties significantly different from large crystals that can be seen by the human eye, there are expectations for its application for new electro-optical devices such as a micro-light source and an optical switch using light emission from a single vacancy in the CsI atomic chain. The researchers will conduct experimental research in its application, focused on detailed study of its various physical properties, starting with its optical properties. In addition to CsI, efforts will also be made in the development of new materials that combine various elements, by applying this technology to other materials.

Furthermore, the mechanism of all adsorbents of radioactive substances (carbon nanotubes, zeolite, Prussian blue, etc.) currently being developed for commercial use are methods of encapsulating radioactive atoms inside microscopic space in the material. The researchers hope to utilize the knowledge of the behavior of the Cs atom in a microscopic space obtained in this research, to improve adsorption performance.

Here’s a link to and a citation for the research paper,

Atomic structure and dynamic behaviour of truly one-dimensional ionic chains inside ​carbon nanotubes by Ryosuke Senga, Hannu-Pekka Komsa, Zheng Liu, Kaori Hirose-Takai, Arkady V. Krasheninnikov, & Kazu Suenaga. Nature Materials (2014) doi:10.1038/nmat4069 Published online 14 September 2014

This paper is behind a paywall.

Replacing copper wire in motors?

Finnish researchers at Lappeenranta University of Technology (LUT) believe it may be possible to replace copper wire used in motors with spun carbon nanotubes. From an Oct. 15, 2014 news item on Azonano,

Lappeenranta University of Technology (LUT) introduces the first electrical motor applying carbon nanotube yarn. The material replaces copper wires in windings. The motor is a step towards lightweight, efficient electric drives. Its output power is 40 W and rotation speed 15000 rpm.

Aiming at upgrading the performance and energy efficiency of electrical machines, higher-conductivity wires are searched for windings. Here, the new technology may revolutionize the industry. The best carbon nanotubes (CNTs) demonstrate conductivities far beyond the best metals; CNT windings may have double the conductivity of copper windings.

”If we keep the design parameters unchanged only replacing copper with carbon nanotube yarns, the Joule losses in windings can be reduced to half of present machine losses. By lighter and more ecological CNT yarn, we can reduce machine dimensions and CO2 emissions in manufacturing and operation. Machines could also be run in higher temperatures,” says Professor Pyrhönen [Juha Pyrhönen], leading the prototype design at LUT.

An Oct. ??, 2014 (?) LUT press release, which originated the news item, further describes the work,

Traditionally, the windings in electrical machines are made of copper, which has the second best conductivity of metals at room temperature. Despite the high conductivity of copper, a large proportion of the electrical machine losses occur in the copper windings. For this reason, the Joule losses are often referred to as copper losses. The carbon nanotube yarn does not have a definite upper limit for conductivity (e.g. values of 100 MS/m have already been measured).

According to Pyrhönen, the electrical machines are so ubiquitous in everyday life that we often forget about their presence. In a single-family house alone there can be tens of electrical machines in various household appliances such as refrigerators, washing machines, hair dryers, and ventilators.

“In the industry, the number of electrical motors is enormous: there can be up to tens of thousands of motors in a single process industry unit. All these use copper in the windings. Consequently, finding a more efficient material to replace the copper conductors would lead to major changes in the industry,” tells Professor Pyrhönen.

There are big plans for this work according to the press release,

The prototype motor uses carbon nanotube yarns spun and converted into an isolated tape by a Japanese-Dutch company Teijin Aramid, which has developed the spinning technology in collaboration with Rice University, the USA. The industrial applications of the new material are still in their infancy; scaling up the production capacity together with improving the yarn performance will facilitate major steps in the future, believes Business Development Manager Dr. Marcin Otto from Teijin Aramid, agreeing with Professor Pyrhönen.

“There is a significant improvement potential in the electrical machines, but we are now facing the limits of material physics set by traditional winding materials. Superconductivity appears not to develop to such a level that it could, in general, be applied to electrical machines. Carbonic materials, however, seem to have a pole position: We expect that in the future, the conductivity of carbon nanotube yarns could be even three times the practical conductivity of copper in electrical machines. In addition, carbon is abundant while copper needs to be mined or recycled by heavy industrial processes.”

The researchers have produced this video about their research,

There’s a reference to some work done at Rice University (Texas, US) with Teijin Armid (Japanese-Dutch company) and Technion Institute (Israel) with spinning carbon nanotubes into threads that look like black cotton (you’ll see the threads in the video). It’s this work that has made the latest research in Finland possible. I have more about the the Rice/Teijin Armid/Technion CNT project in my Jan. 11, 2013 posting, Prima donna of nanomaterials (carbon nanotubes) tamed by scientists at Rice University (Texas, US), Teijin Armid (Dutch/Japanese company), and Technion Institute (based in Israel).

Silver nanoparticles: liquid on the outside, crystal on the inside

Research from the Massachusetts Institute of Technology (MIT) has revealed a new property of metal nanoparticles, in this case, silver. From an Oct. 12, 2014 news item on ScienceDaily,

A surprising phenomenon has been found in metal nanoparticles: They appear, from the outside, to be liquid droplets, wobbling and readily changing shape, while their interiors retain a perfectly stable crystal configuration.

The research team behind the finding, led by MIT professor Ju Li, says the work could have important implications for the design of components in nanotechnology, such as metal contacts for molecular electronic circuits.

The results, published in the journal Nature Materials, come from a combination of laboratory analysis and computer modeling, by an international team that included researchers in China, Japan, and Pittsburgh, as well as at MIT.

An Oct. 12, 2014 MIT news release (also on EurekAlert), which originated the news item, offers both more information about the research and a surprising comparison of nanometers to the width of a human hair,

The experiments were conducted at room temperature, with particles of pure silver less than 10 nanometers across — less than one-thousandth of the width of a human hair. [emphasis mine] But the results should apply to many different metals, says Li, senior author of the paper and the BEA Professor of Nuclear Science and Engineering.

Silver has a relatively high melting point — 962 degrees Celsius, or 1763 degrees Fahrenheit — so observation of any liquidlike behavior in its nanoparticles was “quite unexpected,” Li says. Hints of the new phenomenon had been seen in earlier work with tin, which has a much lower melting point, he says.

The use of nanoparticles in applications ranging from electronics to pharmaceuticals is a lively area of research; generally, Li says, these researchers “want to form shapes, and they want these shapes to be stable, in many cases over a period of years.” So the discovery of these deformations reveals a potentially serious barrier to many such applications: For example, if gold or silver nanoligaments are used in electronic circuits, these deformations could quickly cause electrical connections to fail.

It was a bit surprising to see the reference to 10 nanometers as being less than 1/1,000th (one/one thousandth) of the width of a human hair in a news release from MIT. Generally, a nanometer has been described as being anywhere from less than 1/50,000th to 1/120,000th of the width of a human hair with less than 1/100,000th being one of the most common descriptions. While it’s true that 10 nanometers is less than 1/1,000th of the width of a human hair, it seems a bit misleading when it could be described, in keeping with the more common description, as less than 1/10,000th.

Getting back to the research, the news release offers more details as to how it was conducted,

The researchers’ detailed imaging with a transmission electron microscope and atomistic modeling revealed that while the exterior of the metal nanoparticles appears to move like a liquid, only the outermost layers — one or two atoms thick — actually move at any given time. As these outer layers of atoms move across the surface and redeposit elsewhere, they give the impression of much greater movement — but inside each particle, the atoms stay perfectly lined up, like bricks in a wall.

“The interior is crystalline, so the only mobile atoms are the first one or two monolayers,” Li says. “Everywhere except the first two layers is crystalline.”

By contrast, if the droplets were to melt to a liquid state, the orderliness of the crystal structure would be eliminated entirely — like a wall tumbling into a heap of bricks.

Technically, the particles’ deformation is pseudoelastic, meaning that the material returns to its original shape after the stresses are removed — like a squeezed rubber ball — as opposed to plasticity, as in a deformable lump of clay that retains a new shape.

The phenomenon of plasticity by interfacial diffusion was first proposed by Robert L. Coble, a professor of ceramic engineering at MIT, and is known as “Coble creep.” “What we saw is aptly called Coble pseudoelasticity,” Li says.

Now that the phenomenon has been understood, researchers working on nanocircuits or other nanodevices can quite easily compensate for it, Li says. If the nanoparticles are protected by even a vanishingly thin layer of oxide, the liquidlike behavior is almost completely eliminated, making stable circuits possible.

There are some benefits to this insight (from the news release),

On the other hand, for some applications this phenomenon might be useful: For example, in circuits where electrical contacts need to withstand rotational reconfiguration, particles designed to maximize this effect might prove useful, using noble metals or a reducing atmosphere, where the formation of an oxide layer is destabilized, Li says.

The new finding flies in the face of expectations — in part, because of a well-understood relationship, in most materials, in which mechanical strength increases as size is reduced.

“In general, the smaller the size, the higher the strength,” Li says, but “at very small sizes, a material component can get very much weaker. The transition from ‘smaller is stronger’ to ‘smaller is much weaker’ can be very sharp.”

That crossover, he says, takes place at about 10 nanometers at room temperature — a size that microchip manufacturers are approaching as circuits shrink. When this threshold is reached, Li says, it causes “a very precipitous drop” in a nanocomponent’s strength.

The findings could also help explain a number of anomalous results seen in other research on small particles, Li says.

For more details about the various attempts to create smaller computer chips, you can read my July 11, 2014 posting about IBM and its proposed 7 nanometer chip where you will also find links to announcements and posts about Intel’s smaller chips and HP Labs’ attempt to recreate computers.

As for the research into liquid-like metallic (silver) nanoparticles, here’s a link to and a citation for the paper,

Liquid-like pseudoelasticity of sub-10-nm crystalline ​silver particle by Jun Sun, Longbing He, Yu-Chieh Lo, Tao Xu, Hengchang Bi, Litao Sun, Ze Zhang, Scott X. Mao, & Ju Li. Nature Materials (2014) doi:10.1038/nmat4105 Published online 12 October 2014

This paper is behind a paywall. There is a free preview via ReadCube Access.