RESEARCH INSTITUTES AND LABS

The Graphene Research Centre Singapore

Antonio H. Castro Neto
Director, Graphene Research Centre, National University of Singapore

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Graphene and its relatives

Human progress and development has always been marked by breakthroughs in the control of materials. Since prehistoric times, through the stone, bronze, and iron ages, humans have exploited their environment for materials that can be either used directly or can be modified for their benefit, to make their life more comfortable, productive, or to gain military advantage. One age replaces another when the material that is the basis for its sustainability runs its course and is replaced by another material which presents more qualities or functionalities. In the 20th century the advancements in material science have been so profound that the process of material raise and fall has accelerated tremendously. This process has shaped in such a strong way our lives that it is very hard to imagine how the world looked like before jet planes, computers, and the global unification that the internet has created. This revolution in the way we interact with the world has its origin in the advances made in the beginning of the 20th century with the advent of the quantum theory. Quantum physics and chemistry are the cornerstones for the understanding on how materials behave electronically and structurally, and hence, the basis for essentially everything that surround us. Since quantum mechanics was firmly established theoretically and experimentally, a plethora of new materials, which today make our way of life, have been created: plastics, rubbers, glasses, metallic alloys, semiconductors, superconductors, and magnets, just to mention some. Graphene, an atomically thin crystal made out of pure carbon, is another material that is making its mark in history. While fullerenes were discovered in the 1980s and nanotubes in the 1990s, graphene was only discovered in 2004 by physicists from Manchester University in England.
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Amazingly, graphene was discovered by exfoliation (or peeling) of graphite using what nowadays is called scotch tape technique. Since this discovery the field has evolved significantly to the production of graphene via more controlled techniques such as epitaxial growth and chemical vapor deposition (CVD). Nowadays graphene wafers can be produced routinely. Although graphene is one atom thick, it can be seen with an ordinary optical microscope when placed on top of a properly chosen substrates. It has the properties of a good metal, although its electronic properties do not fit the standard theory of metals. Graphene is also resistant against extrinsic impurities because its chemical bonding is very specific. Consequently graphene conducts electricity better, with less energy loss, than any other semiconductor, including Si, and even Cu. Moreover, graphene is one of the strongest materials ever measured. The only other material that is comparable in strength is diamond, another

Fig. 1. 3D materials made out 2D crystals.

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carbon allotrope. Nevertheless it is one of softest and the only example of a metallic membrane. It can be used as an ultra-sensitive nano-mechanical resonator besides being highly impermeable. Hence it is not surprising that so many industries are interested in developing graphene-based devices for a plethora of applications, from high-frequency transistors to surface coating. However, there are still major challenges that have to be surmounted before graphene can play an important industrial role. With the advent of graphene a new field of research and technology was created, the field of two-dimensional crystals (2DC) and atomically thin films (ATF). Graphene is only one example of a large class of materials where the atoms bind strongly in-plane, forming 2D structures. These 2D crystals interact weakly with each other to form 3D bulk materials. Transition metal dichalcogenides and oxides, for instance, are layered materials with unique properties such as magnetism and superconductivity, and that can be exfoliated or synthesized artificially into 2DC.

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Graphene and Singapore

The Graphene Research Centre (GRC) at the National University of Singapore (NUS) was established in August of 2010 under the directorship of Prof. Antonio H. Castro Neto, with the following objectives: Become a world leader in the synthesis, electronic and structural characterization, chemical functionalization, and theoretical and computer modeling of a new class of ATF, and 2DC such as Graphene; Attract and retain world-class investigators to perform high quality and high impact research in Singapore; Enhance graduate education and train high quality manpower for Singapore; Produce intellectual property (IP), generate spin-offs, and interactions with the industry;
Fig. 3. Materials characterization in the GRCs clean room.

Fig. 2. Graphene synthesis in the clean room of GRC.

Create new knowledge in a selected area of focus which is of strategic relevance to Singapores economy. With a generous start-up funding from NUS, and approximately 3,000 m2 of space for its facilities, the GRC is quickly becoming a worldwide reference in the study of ATFs. Today, GRC counts with several laboratories with the state of the art tools for the growth and study of new materials and development of new devices that have the potential to disrupt several different industrial sectors, from the electronics industry to composite materials manufacturing. In June 2012, GRC inaugurated its Micro and NanoFabrication Facility which is the first of its kind, allowing for the synthesis, characterization, and device fabrication in a closed, controlled, clean room environment which guarantees the best possible device performance. GRC also counts with a large computer cluster (800 nodes) for the simulation and modeling of new materials and devices. In fact, GRC was planned to be a fully self-contained institute where experiment, theory and applications are developed simultaneously and harmoniously. GRC has also been supported by the National Research Foundation (NRF) of Singapore. GRC has been able to secure funding for its many projects through competitive grant applications. In 2011, Prof. Castro Neto was awarded
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a Competitive Research Programme (CRP) grant to study Novel 2D materials with tailored properties: beyond graphene and a Campus for Research Excellence and Technological Enterprise (CREATE), jointly with University of California at Berkeley and Nanyang Technological University (NTU), for the creation of the Singapore-Berkeley Research Institute for Sustainable Energy. In 2012, GRC, through his principal investigators (PI), has been able to secure other two CRP grants: Plasmonics-electronics: new generation of devices to bypass electronic limitations under Prof. Christian Nijhuis and Towards commercialization of graphene under Prof. Barbaros Oezyilmaz. GRC is a truly interdisciplinary institute. It counts with 22 faculty from different departments across NUS: Chemistry, Electrical and Bio Engineering, and Physics. Out of those, 7 have been awarded the prestigious NRF Fellowship. This is the largest concentration of NRF fellows in a single research institution in Singapore. GRC also counts with two distinguished scientific advisors: Prof. Konstantin Novoselov and Prof. Andre Geim, both from Manchester University, UK. Prof. Novoselov and Prof. Geim shared the 2010 Nobel Prize Physics prize for breakthrough experiments in the novel 2D material, graphene. Prof. Novoselov and Geim have participated directly in the foundation of GRC. Prof. Novoselov is a regular visitor to GRC and has participated directly in the project and construction of GRCs Micro and NanoFabrication Facility. Prof. Geim is a Distinguished Visiting Professor at NUS and spends 1 to 2 months a year in the GRC. South Korea in 2011, and in 2012 it took place in Beijing, China. In 2013, it will take place in Tokyo, Japan and in 2014 it will be organized in Taipei, Taiwan. Although GRC is still in its infancy, it has already written its name in some of the most important scientific journals and magazines. We highlight three recent publications that are having impact in the area of nanotechnology. In a recent article published in the journal Science (Science 2012; 335, 947) in collaboration with researchers from University of Manchester, GRC PIs have worked on a new class of electronic devices called vertical field-effect tunneling transistors (see Figure). These devices are created using graphene as the conducting electrode and atomically thin films of Boron-Nitride or MoS2 as the semiconductor component. Being atomically thin, these new transistors can replace ordinary transistors with large gain in miniaturization and performance. Moreover, because these devices are also transparent and flexible, they can lead to a new class of applications that can be rolled, folded, wrapped, and glued to glass or transparent ceramics for use in vehicles and airplanes.

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GRC goes global

GRC is an international research centre with a network of collaborators in several continents. GRC has memorandum of understanding (MoU) for collaborations and exchange of expertise and personnel with Manchester University (UK), Boston University (USA), Sungkyunkwan University (South Korea), and Mackenzie Presbyterian University (Brazil). GRC organizes one of the most important graphene conference in the world, Recent Progress in Graphene Research (RPGR). RPGR was created with the objective of bringing together the most important Asian researchers in the area of 2DC research, so that they can discuss their latest theoretical and experimental findings. RPGR also rotates among Asian countries in order to promote dissemination of knowledge, and promote collaboration and cooperation among Asian researchers. It was inaugurated in Seoul, South Korea, in 2009, followed by Singapore in 2010, Suwon in
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Fig. 4. Vertical eld-effect transistor.

In a publication in the journal Nature (Nature, 2012; 487, 82) GRC researchers, in collaboration with scientists from University of California San Diego, made their mark in the rapidly developing field of graphene plasmonics (see Figure). Plasmons are collective electron oscillations in metals or semiconductors that enable confinement and control of electromagnetic energy at sub-wavelength scales. Using infrared nano-imaging, it was shown that common graphene/SiO2/Si back-gated structures support propagating surface plasmons. The wavelength of graphene plasmons is of the order of 200nanometers at technologically relevant infrared frequencies, and they can propagate several times

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postdoctoral fellows, and PhD students work at the GRC facilities. Among the many projects developed at GRC, we can highlight: Atomically thin, wafer size, crystal growth; Characterization of materials using Raman spectroscopy, atomic force microscopy (AFM), scanning electron microscopy (SEM), scanning tunneling microscopy (STM), single electron transistor (SET) probes, magnetotransport, angle resolved photoemission (ARPES), optics, among others. Flexible electronics; Strain engineering; Mechanics of ATFs; Chemical functionalization of ATFs (polymer and molecular doping); Nano-scale patterning and device development; Three-dimensional architectures based on atomically thin films; Contactless, non-invasive, optical methods to measure stress in composite materials; Spintronics and valleytronics; Atomically thin electrodes for photovoltaic and organic light emitting diode applications; Atomically thin gas barriers and electrodes for energy/ charge transfer and storage (batteries, water splitting, fuel cells, etc); Solution-processed atomically thin films; Atomically thin films as optical components in fiber lasers; Atomically thin film platforms for bio-sensing and cell growth; Atomically thin film platforms for sol-gel, organic, and electro-chemistry; Graphene-ferroelectric memories, graphene spin torque transistors; Computational modeling of new atomically thin materials and complex architectures. In the area of ATF synthesis and growth, GRC currently has capability to produce 8 inch graphene wafers using the inductive couple plasma chemical vapor deposition (ICP-CVD) growth. GRC researchers are also developing solution processed graphene for structural materials, thermal management, and printed electronics.

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Fig. 5. Injecting light into graphene via graphene plasmons.

this distance. It is possible to alter both the amplitude and the wavelength of the plasmons by varying the gate voltage. Using plasmon interferometry, we have investigated the electromagnetic losses in graphene by exploring real-space profiles of plasmon standing waves formed between the tip of a nano-probe and the edges of the samples. Plasmon dissipation quantified through this analysis is linked to the exotic electrodynamics of graphene, which resembles the electrodynamics of massless particles propagating at the speed of light, the so-called Dirac particles. Standard plasmonic figures of merit of these tunable graphene devices surpass those of common metal-based structures. The concept of strain engineering is based on the modifications of the electronic properties of a material by application of stress, shear, or pressure. In a publication in the journal Nature Communications (Nature Communications 2012; 3, 823), Prof. Loh Kian Ping and collaborators at GRC have shown that graphene can be controllably transformed from a semi-metal to a semiconductor by chemically delaminating it from a substrate and producing nano-bubbles that behave as quantum dots with large electronic gaps. These nano-bubbles can be used in a large number of different applications in nanotechnology since they, unlike unstrained graphene, have a large on-off electrical current ratio and can be used in digital applications. The journal Nature (Nature 2012; 488, 140) has recently pointed out that NUS is one of the world leader in publications in the area of graphene, surpassing universities in the United States and Europe.

Money makes the world go around

Forward looking

Currently, approximately 100 researchers, including PIs,

Graphene is a multi-purpose, multi-functional, material and the industrial possibilities for its use are only limited by our imagination. The interest in the industrial use of graphene and other 2DC has been tremendous. Several market
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Applications 2011-2011: Technologies, Players and Opportunities projects a market of US$ 35 Billion, with applications as diverse as conductive inks and logic/memory devices. The figures of merit in this technological area are the transparency of film and its electrical conductivity. In the figure below we show how different applications can be obtained by controlling these two parameters. At GRC we are exploring this parameter space and looking for new technologies that can be developed from this class of ATFs. Nevertheless, the research at GRC is not limited to electronics. GRC PIs are working on projects that cover many important markets. For instance, we are investigating the use of graphene for composite materials that are flexible and highly resistant. In the field of Bio-Medical applications, we have been working on coatings for medical equipment, such as stents, and the use of graphene as a substrate for cell growth (skin, stem, neurons, etc).

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Fig. 6. Graphene nano-bubbles that are 5nm in diameter and 0.5nm in height.

research reports have pointed out the enormous potential of graphene for a large number of applications: electronic circuits, flexible electronics, fuel cells, infrared filters, photo sensors, solar cells, organic electronics (organic light emitting diodes and organic solar cells), supercapacitors and batteries, chemical and bio sensors, electro actuators, among others. Graphene-based companies are springing around the world in the expectation of big profits in just a few years time. For instance, for solution processed graphene alone, the projected marked for 2020 is of approximately US$ 675 Million according to the BCC, Market Research Report (1-59623-715-5). For flexible electronics the projected numbers are actually much higher. The IDTechEx 2011 Market Research Report Carbon Nanotubes and Graphene for Electronics

Fig. 7. ICP-CVD system at the clean room of GRC.

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and Fuji Electric, and is also currently in discussions about possible JDAs with Samsung, Bosch, Infineon, Rusnano, and LG Electronics. GRC has signed MoUs with IBM (USA), ST Kinetics (Singapore), and the Office of Naval Research (USA) for collaborations in several aspects of graphene applications.

Graphene Island
In technology, the best way to predict the future is to create it. At GRC, we are exploring science at its frontiers and creating new disruptive technologies that can have direct impact in our society by creating new markets and job opportunities. The path that we are following, that is, investigating materials that will lead to progress and prosperity, is no different from what our ancestors have been doing for many millennia. This time, however, we have on our side the knowledge of quantum physics and the recent developments in materials science, nano-science, and nano-technology, and the discovery of 2D crystals, to lead the way. This field is still in its infancy but we are moving fast. In the same way that in the 20th century the silicon technology created the Silicon Valley in the USA, we are working hard and diligently so that, one day in the 21st century, Singapore will be called the Graphene Island.

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Fig. 8: Figures of merit in exible and transparent thin lm technology: transparency versus electrical resistance.

In its two and one half years of existence, GRC PIs have generated more than 40 patent applications. One of its patents have been licensed for a spin-off company called Graphite Zero that has the target of producing industrial quantities of graphene flakes by chemical exfoliation. This company has attracted already US$ 1 M of foreign investment. GRC is also in the process of signing joint development agreements (JDA) with several large companies such as BASF

Fig. 9

graphene.nus.edu.sg

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