Materials Science and NanoEngineering

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https://hdl.handle.net/1911/76491

In Fall 2013, the Materials Science faculty separated from the MEMS Department and formed the new department of Materials Science and NanoEngineering.

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Photonic density of states of two-dimensional quasicrystalline photonic structures
(American Physical Society, 2011) Jia, Lin; Bita, Ion; Thomas, Edwin L.
A large photonic band gap (PBG) is highly favorable for photonic crystal devices. One of the most important goals of PBG materials research is identifying structural design strategies for maximizing the gap size. We provide a comprehensive analysis of the PBG properties of two-dimensional (2D) quasicrystals (QCs), where rotational symmetry, dielectric fill factor, and structural morphology were varied systematically in order to identify correlations between structure and PBG width at a given dielectric contrast (13:1, Si:air). The transverse electric (TE) and transverse magnetic (TM) PBGs of 12 types of QCs are investigated (588 structures). We discovered a 12mm QC with a 56.5% TE PBG, the largest reported TE PBG for an aperiodic crystal to date. We also report here a QC morphology comprising “throwing star”-like dielectric domains, with near-circular air cores and interconnecting veins emanating radially around the core. This interesting morphology leads to a complete PBG of ∼20% , which is the largest reported complete PBG for aperiodic crystals.
Impact of Geometry on the TM Photonic Band Gaps of Photonic Crystals and Quasicrystals
(American Physical Society, 2011) Jia, Lin; Bita, Ion; Thomas, Edwin L.
Here we demonstrate a novel quantitative procedure to pursue statistical studies on the geometric properties of photonic crystals and photonic quasicrystals (PQCs) which consist of separate dielectric particles. The geometric properties are quantified and correlated to the size of the photonic band gap (PBG) for wide permittivity range using three characteristic parameters: shape anisotropy, size distribution, and feature-feature distribution. Our concept brings statistical analysis to the photonic crystal research and offers the possibility to predict the PBG from a morphological analysis.
Two-pattern compound photonic crystals with a large complete photonic band gap
(American Physical Society, 2011) Jia, Lin; Thomas, Edwin L.
We present a set of two-dimensional aperiodic structures with a large complete photonic band gap (PBG), which are named two-pattern photonic crystals. By superposing two substructures without regard to registration, we designed six new aperiodic PBG structures having a complete PBG larger than 15% for ɛ2/ɛ1=11.4. The rod-honeycomb two-pattern photonic crystal provides the largest complete PBG to date. An aperiodic structure becomes the champion structure with the largest PBG. Surprisingly, the TM and TE gaps of a two-pattern photonic crystal are much less interdependent than the PBGs of conventional photonic crystals proposed before, affording interesting capabilities for us to tune the TM and TE PBGs separately. By altering the respective substructures, optical devices for different polarizations (TE, TM, or both) can readily be designed.
Optical forces and optical torques on various materials arising from optical lattices in the Lorentz-Mie regime
(American Physical Society, 2011) Jia, Lin; Thomas, Edwin L.
By combining the Maxwell stress tensor with the finite-difference time-domain (FDTD) method, we calculate the optical force and optical torque on particles from optical lattices. We compare our method to the two-component method and the electrostatic approximation (ESA). We also discuss how particle's refractive index, shape, size, and the morphology of an optical lattice influence optical forces and the condition to form stable optical trapping wells. In addition to optical forces, optical torque from one dimensional (1D) optical lattice is discussed for particles having anisotropic shapes; metastable and stable equilibrium orientation states are found. A detailed understanding of the optical force and torque from optical lattices has significant implications for optical trapping, micromanipulation, and sorting of particles.
Enhancement of the Electron Spin Resonance of Single-Walled Carbon Nanotubes by Oxygen Removal
(American Chemical Society, 2012) Rice, William D.; Weber, Ralph T.; Leonard, Ashley D.; Tour, James M.; Nikolaev, Pavel; Arepalli, Sivaram; Berka, Vladimir; Tsai, Ah-Lim; Kono, Junichiro
We have observed a nearly 4-fold increase in the electron spin resonance (ESR) signal from an ensemble of single-walled carbon nanotubes (SWCNTs) due to oxygen desorption. By performing temperature-dependent ESR spectroscopy both before and after thermal annealing, we found that the ESR in SWCNTs can be reversibly altered via the molecular oxygen content in the samples. Independent of the presence of adsorbed oxygen, a Curie law (spin susceptibility ∝ 1/T) is seen from ∼4 to 300 K, indicating that the probed spins are finite-level species. For both the pre-annealed and post-annealed sample conditions, the ESR line width decreased as the temperature was increased, a phenomenon we identify as motional narrowing. From the temperature dependence of the line width, we extracted an estimate of the intertube hopping energy; for both sample conditions, we found this hopping energy to be ∼1.2 meV. Since the spin hopping energy changes only slightly when oxygen is desorbed, we conclude that only the spin susceptibility, not spin transport, is affected by the presence of physisorbed molecular oxygen in SWCNT ensembles. Surprisingly, no line width change is observed when the amount of oxygen in the SWCNT sample is altered, contrary to other carbonaceous systems and certain 1D conducting polymers. We hypothesize that physisorbed molecular oxygen acts as an acceptor (p-type), compensating the donor-like (n-type) defects that are responsible for the ESR signal in bulk SWCNTs.
Dynamic response of exchange bias in graphene nanoribbons
(American Institute of Physics, 2012) Jammalamadaka, S. Narayana; Rao, S.S.; Vanacken, J.; Moshchalkov, V.V.; Lu, Wei; Tour, J.M.; Smalley Institute for Nanoscale Science and Technology
The dynamics of magnetic hysteresis, including the training effect and the field sweep rate dependence of the exchange bias, is experimentally investigated in exchange-coupled potassium split graphenenanoribbons (GNRs). We find that, at low field sweep rate, the pronounced absolute training effect is present over a large number of cycles. This is reflected in a gradual decrease of the exchange bias with the sequential field cycling. However, at high field sweep rate above 0.5 T/min, the training effect is not prominent. With the increase in field sweep rate, the average value of exchange bias field grows and is found to follow power-law behavior. The response of the exchange bias field to the field sweep rate variation is linked to the difference in the time it takes to perform a hysteresis loop measurement compared with the relaxation time of the anti-ferromagnetically aligned spins. The present results may broaden our current understanding of magnetism of GNRs and would be helpful in establishing the GNRs-based spintronic devices.
Enhancement of the Electron Spin Resonance of Single-Walled Carbon Nanotubes by Oxygen Removal
(American Chemical Society, 2012) Rice, William D.; Weber, Ralph T.; Leonard, Ashley D.; Tour, James M.; Nikolaev, Pavel; Arepalli, Sivaram; Berka, Vladimir; Tsai, Ah-Lim; Kono, Junichiro
We have observed a nearly 4-fold increase in the electron spin resonance (ESR) signal from an ensemble of single-walled carbon nanotubes (SWCNTs) due to oxygen desorption. By performing temperature-dependent ESR spectroscopy both before and after thermal annealing, we found that the ESR in SWCNTs can be reversibly altered via the molecular oxygen content in the samples. Independent of the presence of adsorbed oxygen, a Curie law (spin susceptibility ∝ 1/T) is seen from ∼4 to 300 K, indicating that the probed spins are finite-level species. For both the pre-annealed and post-annealed sample conditions, the ESR line width decreased as the temperature was increased, a phenomenon we identify as motional narrowing. From the temperature dependence of the line width, we extracted an estimate of the intertube hopping energy; for both sample conditions, we found this hopping energy to be ∼1.2 meV. Since the spin hopping energy changes only slightly when oxygen is desorbed, we conclude that only the spin susceptibility, not spin transport, is affected by the presence of physisorbed molecular oxygen in SWCNT ensembles. Surprisingly, no line width change is observed when the amount of oxygen in the SWCNT sample is altered, contrary to other carbonaceous systems and certain 1D conducting polymers. We hypothesize that physisorbed molecular oxygen acts as an acceptor (p-type), compensating the donor-like (n-type) defects that are responsible for the ESR signal in bulk SWCNTs.
Ferromagnetism in Graphene Nanoribbons: Split versus Oxidative Unzipped Ribbons
(American Chemical Society, 2012) Rao, S.S.; Jammalamadaka, S. Narayana; Stesmans, A.; Moshchalkov, V.V.; van Tol, J.; Kosynkin, D.V.; Higginbotham, A.; Tour, J.M.; Smalley Institute for Nanoscale Science and Technology
Two types of graphene nanoribbons: (a) potassium-split graphene nanoribbons (GNRs), and (b) oxidative unzipped and chemically converted graphene nanoribbons (CCGNRs) were investigated for their magnetic properties using the combination of static magnetization and electron spin resonance measurements. The two types of ribbons possess remarkably different magnetic properties. While a low-temperature ferromagnet-like feature is observed in both types of ribbons, such room-temperature feature persists only in potassium-split ribbons. The GNRs show negative exchange bias, but the CCGNRs exhibit a ﾓpositive exchange biasﾔ. Electron spin resonance measurements suggest that the carbon-related defects may be responsible for the observed magnetic behavior in both types of ribbons. Furthermore, information on the proton hyperfine coupling strength has been obtained from hyperfine sublevel correlation experiments performed on the GNRs. Electron spin resonance finds no evidence for the presence of potassium (cluster) related signals, pointing to the intrinsic magnetic nature of the ribbons. Our combined experimental results may indicate the coexistence of ferromagnetic clusters with antiferromagnetic regions leading to disordered magnetic phase. We discuss the possible origin of the observed contrast in the magnetic behaviors of the two types of ribbons studied.
Transparent, flexible supercapacitors from nano-engineered carbon films
(Nature Publishing Group, 2012) Jung, Hyun Young; Karimi, Majid B.; Hahm, Myung Gwan; Ajayan, Pulickel M.; Jung, Yung Joon
Here we construct mechanically flexible and optically transparent thin film solid state supercapacitors by assembling nano-engineered carbon electrodes, prepared in porous templates, with morphology of interconnected arrays of complex shapes and porosity. The highly textured graphitic films act as electrode and current collector and integrated with solid polymer electrolyte, function as thin film supercapacitors. The nanostructured electrode morphology and the conformal electrolyte packaging provide enough energy and power density for the devices in addition to excellent mechanical flexibility and optical transparency, making it a unique design in various power delivery applications.
Graphene as an atomically thin interface for growth of vertically aligned carbon nanotubes
(Macmillan Publishers Limited, 2013) Rao, Rahul; Chen, Gugang; Arava, Leela Mohana Reddy; Kalaga, Kaushik; Ishigami, Masahiro; Heinz, Tony F.; Ajayan, Pulickel M.; Harutyunyan, Avetik R.
Growth of vertically aligned carbon nanotube (CNT) forests is highly sensitive to the nature of the substrate. This constraint narrows the range of available materials to just a few oxide-based dielectrics and presents a major obstacle for applications. Using a suspended monolayer, we show here that graphene is an excellent conductive substrate for CNT forest growth. Furthermore, graphene is shown to intermediate growth on key substrates, such as Cu, Pt, and diamond, which had not previously been compatible with nanotube forest growth. We find that growth depends on the degree of crystallinity of graphene and is best on mono- or few-layer graphene. The synergistic effects of graphene are revealed by its endurance after CNT growth and low contact resistances between the nanotubes and Cu. Our results establish graphene as a unique interface that extends the class of substrate materials for CNT growth and opens up important new prospects for applications.
Intrinsic carrier mobility of multi-layered MoS2 field-effect transistors on SiO2
(American Institute of Physics, 2013) Pradhan, N.R.; Rhodes, D.; Zhang, Q.; Talapatra, S.; Terrones, M.; Ajayan, P.M.; Balicas, L.
Host-Guest Self-assembly in Block Copolymer Blends
(Springer Nature, 2013) Park, Woon Ik; Kim, YongJoo; Jeong, Jae Won; Kim, Kyungho; Yoo, Jung-Keun; Hur, Yoon Hyung; Kim, Jong Min; Thomas, Edwin L.; Alexander-Katz, Alfredo; Jung, Yeon Sik
Ultrafine, uniform nanostructures with excellent functionalities can be formed by self-assembly of block copolymer (BCP) thin films. However, extension of their geometric variability is not straightforward due to their limited thin film morphologies. Here, we report that unusual and spontaneous positioning between host and guest BCP microdomains, even in the absence of H-bond linkages, can create hybridized morphologies that cannot be formed from a neat BCP. Our self-consistent field theory (SCFT) simulation results theoretically support that the precise registration of a spherical BCP microdomain (guest, B-b-C) at the center of a perforated lamellar BCP nanostructure (host, A-b-B) can energetically stabilize the blended morphology. As an exemplary application of the hybrid nanotemplate, a nanoring-type Ge2Sb2Te5 (GST) phase-change memory device with an extremely low switching current is demonstrated. These results suggest the possibility of a new pathway to construct more diverse and complex nanostructures using controlled blending of various BCPs.
Cytotoxicity and variant cellular internalization behavior of water-soluble sulfonated nanographene sheets in liver cancer cells
(Springer, 2013) Corr, Stuart J.; Raoof, Mustafa; Cisneros, Brandon T.; Kuznetsov, Oleksandr; Massey, Katheryn; Kaluarachchi, Warna D.; Cheney, Matthew A.; Billups, Edward W.; Wilson, Lon J.; Curley, Steven A.; Richard E. Smalley Institute for Nanoscale Science and Technology
Highly exfoliated sulfonated graphene sheets (SGSs), an alternative to graphene oxide and graphene derivatives, were synthesized, characterized, and applied to liver cancer cells in vitro. Cytotoxicity profiles were obtained using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide, WST-1[2-(4-iodophenyl)-3-(4-nitrophenyl)-5-(2,4-disulfophenyl)-2H-tetrazolium, and lactate dehydrogenase release colorimetric assays. These particles were found to be non-toxic across the concentration range of 0.1 to 10 μg/ml. Internalization of SGSs was also studied by means of optical and electron microscopy. Although not conclusive, high-resolution transmission and scanning electron microscopy revealed variant internalization behaviors where some of the SGS became folded and compartmentalized into tight bundles within cellular organelles. The ability for liver cancer cells to internalize, fold, and compartmentalize graphene structures is a phenomenon not previously documented for graphene cell biology and should be further investigated.
Volcano-shape glycerol oxidation activity of palladium-decorated gold nanoparticles
(Royal Society of Chemistry, 2014) Zhao, Zhun; Arentz, Joni; Pretzer, Lori A.; Limpornpipat, Pongsak; Clomburg, James M.; Gonzalez, Ramon; Schweitzer, Neil M.; Wu, Tianpin; Miller, Jeffrey T.; Wong, Michael S.
Bimetallic PdAu catalysts are more active than monometallic ones for the selective oxidation of alcohols, but the reasons for improvement remain insufficiently detailed. A metal-on-metal material can probe the structure–catalysis relationship more clearly than conventionally prepared bimetallics. In this study, Pd-on-Au nanoparticles with variable Pd surface coverages (sc%) ranging from 10 to 300 sc% were synthesized and immobilized onto carbon (Pd-on-Au/C). Tested for glycerol oxidation at 60 °C, pH 13.5, and 1 atm under flowing oxygen, the series of Pd-on-Au/C materials showed volcano-shape catalytic activity dependence on Pd surface coverage. Increasing surface coverage led to higher catalytic activity, such that initial turnover frequency (TOF) reached a maximum of ̴6000 h−1 at 80 sc%. Activity decreased above 80 sc% mostly due to catalyst deactivation. Pd-on-Au/C at 80 sc% was >10 times more active than monometallic Au/C and Pd/C, with both exhibiting TOF values less than [similar]500 h−1. Glyceric acid was the dominant primary reaction product for all compositions, with its zero-conversion selectivity varying monotonically as a function of Pd surface coverage. Glyceric acid yield from Pd-on-Au/C (80 sc%) was 42%, almost double the yields from Au/C and Pd/C (16% and 22%, respectively). Ex situ X-ray absorption near edge structure analysis of two Pd-on-Au/C materials with comparable activities (60 sc% and 150 sc%) showed that the former had less oxidized Pd ensembles than the latter, and that both catalysts were less oxidized compared to Pd/C. That Au stabilizes the metallic state of surface Pd atoms may be responsible for activity enhancement observed in other PdAu-catalyzed oxidation reactions. Decorating a Au surface with Pd generates a catalyst that has the deactivation resistance of Au, the higher glyceric acid selectivity of Pd, and the synergistically higher activities that neither metal has.
Nanocrystalline materials: recent advances in crystallographic characterization techniques
(International Union of Crystallography, 2014) Ringe, Emilie
Most properties of nanocrystalline materials are shape-dependent, providing their exquisite tunability in optical, mechanical, electronic and catalytic properties. An example of the former is localized surface plasmon resonance (LSPR), the coherent oscillation of conduction electrons in metals that can be excited by the electric field of light; this resonance frequency is highly dependent on both the size and shape of a nanocrystal. An example of the latter is the marked difference in catalytic activity observed for different Pd nanoparticles. Such examples highlight the importance of particle shape in nanocrystalline materials and their practical applications. However, one may ask ‘how are nanoshapes created?’, ‘how does the shape relate to the atomic packing and crystallography of the material?’, ‘how can we control and characterize the external shape and crystal structure of such small nanocrystals?’. This feature article aims to give the reader an overview of important techniques, concepts and recent advances related to these questions. Nucleation, growth and how seed crystallography influences the final synthesis product are discussed, followed by shape prediction models based on seed crystallography and thermodynamic or kinetic parameters. The crystallographic implications of epitaxy and orientation in multilayered, core-shell nanoparticles are overviewed, and, finally, the development and implications of novel, spatially resolved analysis tools are discussed.
Imaging molecular adsorption and desorption dynamics on graphene using terahertz emission spectroscopy
(Nature Publishing Group, 2014) Ajayan, P.M.; Kono, J.; Tonouchi, M.
Being an atomically thin material, graphene is known to be extremely susceptible to its environment, including defects and phonons in the substrate on which it is placed as well as gas molecules that surround it. Thus, any device design using graphene has to take into consideration all surrounding components, and device performance needs to be evaluated in terms of environmental influence. However, no methods have been established to date to readily measure the density and distribution of external perturbations in a quantitative and non-destructive manner. Here, we present a rapid and non-contact method for visualizing the distribution of molecular adsorbates on graphene semi-quantitatively using terahertz time-domain spectroscopy and imaging. We found that the waveform of terahertz bursts emitted from graphene-coated InP sensitively changes with the type of atmospheric gas, laser irradiation time, and ultraviolet light illumination. The terahertz waveform change is explained through band structure modifications in the InP surface depletion layer due to the presence of localized electric dipoles induced by adsorbed oxygen. These results demonstrate that terahertz emission serves as a local probe for monitoring adsorption and desorption processes on graphene films and devices, suggesting a novel two-dimensional sensor for detecting local chemical reactions.
Assessing Carbon-Based Anodes for Lithium-Ion Batteries: A Universal Description of Charge-Transfer Binding
(American Physical Society, 2014) Liu, Yuanyue; Wang, Y. Morris; Yakobson, Boris I.; Wood, Brandon C.; Smalley Institute for Nanoscale Science and Technology
Many key performance characteristics of carbon-based lithium-ion battery anodes are largely determined by the strength of binding between lithium (Li) and sp2 carbon (C), which can vary significantly with subtle changes in substrate structure, chemistry, and morphology. Here, we use density functional theory calculations to investigate the interactions of Li with a wide variety of sp2 C substrates, including pristine, defective, and strained graphene, planar C clusters, nanotubes, C edges, and multilayer stacks. In almost all cases, we find a universal linear relation between the Li-C binding energy and the work required to fill previously unoccupied electronic states within the substrate. This suggests that Li capacity is predominantly determined by two key factors?namely, intrinsic quantum capacitance limitations and the absolute placement of the Fermi level. This simple descriptor allows for straightforward prediction of the Li-C binding energy and related battery characteristics in candidate C materials based solely on the substrate electronic structure. It further suggests specific guidelines for designing more effective C-based anodes. The method should be broadly applicable to charge-transfer adsorption on planar substrates, and provides a phenomenological connection to established principles in supercapacitor and catalyst design.
Plasmon and compositional mapping of plasmonic nanostructures
(SPIE, 2014) Ringe, Emilie; Collins, Sean M.; DeSantis, Christopher J.; Skrabalak, Sara E.; Midgley, Paul A.
Recently, co-reduction of Au and Pd has allowed the synthesis of complex Au core/AuPd shell nanoparticles with elongated tips and cubic-like symmetry. Optical studies have shown strong plasmonic behavior and high refractive index sensitivities. In this paper, we describe the composition and the near-field plasmonic behavior of those complex structures. Monochromated STEM-EELS, Cathodoluminescence, and EDS mapping reveals the different resonant modes in these particles, and shows that Pd, a poor plasmonic metal, does not prevent strong resonances and could actually be extremely helpful for plasmon-enhanced catalysis.
Efficient Modulation of 1.55 μm Radiation with Gated Graphene on a Silicon Microring Resonator
(American Chemical Society, 2014) Qiu, Ciyuan; Gao, Weilu; Vajtai, Robert; Ajayan, Pulickel M.; Kono, Junichiro; Xu, Qianfan
The gate-controllability of the Fermi-edge onset of interband absorption in graphene can be utilized to modulate near-infrared radiation in the telecommunication band. However, a high modulation efficiency has not been demonstrated to date, because of the small amount of light absorption in graphene. Here, we demonstrate a ~40% amplitude modulation of 1.55 μm radiation with gated single-layer graphene that is coupled with a silicon microring resonator. Both the quality factor and resonance wavelength of the silicon microring resonator were strongly modulated through gate tuning of the Fermi level in graphene. These results promise an efficient electro-optic modulator, ideal for applications in large-scale on-chip optical interconnects that are compatible with complementary metal-oxide-semiconductor technology
3D Macroporous Solids from Chemically Cross-linked Carbon Nanotubes
(Wiley, 2014) Ozden, Sehmus; Narayanan, Tharangattu N.; Tiwary, Chandra S.; Dong, Pei; Hart, Amelia H.C.; Vajtai, Robert; Ajayan, Pulickel M.
Suzuki reaction for covalently interconnected 3D carbon nanotube (CNT) architectures is reported. The synthesis of 3D macroscopic solids made of CNTs covalently connected via Suzuki cross-coupling, a well-known carbon-carbon covalent bond forming reaction in organic chemistry, is scalable. The resulting solid has a highly porous, interconnected structure of chemically cross-linked CNTs. Its use for the removal of oil from contaminated water is demonstrated.

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