Letters
Nanostraws for Direct Fluidic Intracellular Access
Jules J. VanDersarl - ,
Alexander M. Xu - , and
Nicholas A. Melosh *
Nanomaterials are promising candidates to improve the delivery efficiency and control of active agents such as DNA or drugs directly into cells. Here we demonstrate cell-culture platforms of nanotemplated “nanostraws” that pierce the cell membrane, providing a permanent fluidic pipeline into the cell for direct cytosolic access. Conventional polymeric track-etch cell culture membranes are alumina coated and etched to produce fields of nanostraws with controllable diameter, thickness, and height. Small molecules and ions were successfully transported into the cytosol with 40 and 70% efficiency, respectively, while GFP plasmids were successfully delivered and expressed. These platforms open the way for active, reproducible delivery of a wide variety of species into cells without endocytosis.
Determination of Work Function of Graphene under a Metal Electrode and Its Role in Contact Resistance
Seung Min Song - ,
Jong Kyung Park - ,
One Jae Sul - , and
Byung Jin Cho *
Although the work function of graphene under a given metal electrode is critical information for the realization of high-performance graphene-based electronic devices, relatively little relevant research has been carried out to date. In this work, the work function values of graphene under various metals are accurately measured for the first time through a detailed analysis of the capacitance–voltage (C–V) characteristics of a metal–graphene–oxide–semiconductor (MGOS) capacitor structure. In contrast to the high work function of exposed graphene of 4.89–5.16 eV, the work function of graphene under a metal electrode varies depending on the metal species. With a Cr/Au or Ni contact, the work function of graphene is pinned to that of the contacted metal, whereas with a Pd or Au contact the work function assumes a value of ∼4.62 eV regardless of the work function of the contact metal. A study of the gate voltage dependence on the contact resistance shows that the latter case provides lower contact resistance.
Graphene Induced Surface Reconstruction of Cu
Jifa Tian - ,
Helin Cao - ,
Wei Wu - ,
Qingkai Yu - ,
Nathan P. Guisinger *- , and
Yong P. Chen *
An atomic-scale study utilizing scanning tunneling microscopy (STM) in ultrahigh vacuum (UHV) is performed on large single crystalline graphene grains synthesized on Cu foil by a chemical vapor deposition (CVD) method. After thermal annealing, we observe the presence of periodic surface depressions (stripe patterns) that exhibit long-range order formed in the area of Cu covered by graphene. We suggest that the observed stripe pattern is a Cu surface reconstruction formed by partial dislocations (which appeared to be stair-rod-like) resulting from the strain induced by the graphene overlayer. In addition, these graphene grains are shown to be more decoupled from the Cu substrate compared to previously studied grains that exhibited Moiré patterns.
Graphene Sublattice Symmetry and Isospin Determined by Circular Dichroism in Angle-Resolved Photoemission Spectroscopy
Isabella Gierz *- ,
Matti Lindroos - ,
Hartmut Höchst - ,
Christian R. Ast - , and
Klaus Kern
The Dirac-like electronic structure of graphene originates from the equivalence of the two basis atoms in the honeycomb lattice. We show that the characteristic parameters of the initial state wave function (sublattice symmetry and isospin) can be determined using angle-resolved photoemission spectroscopy (ARPES) with circularly polarized synchrotron radiation. At a photon energy of hν = 52 eV, transition matrix element effects can be neglected allowing us to determine sublattice symmetry and isospin with high accuracy using a simple theoretical model.
Electronic Transport in Two Stacked Graphene Monolayers
Dong-Hun Chae *- ,
Ding Zhang - ,
Xuting Huang - , and
Klaus von Klitzing
We report on interlayer and lateral electronic transport measurements in two stacked graphene monolayers which have separate electrical contacts. The current–voltage characteristic across the two layers shows linear Ohmic behavior at zero magnetic field. At high magnetic fields, sequences of quantum Hall plateaus of the overlap region with filling factors 4, 8, and 12 are observed which can be explained by equilibration of the edge channel potentials of the individual graphene layers. An anomaly is observed at total filling factors ±2 in the overlap region. The I–V characteristic for interlayer transport turns nonlinear, and the Hall signal vanishes, indicating a magnetic field induced electrical decoupling of the two graphene layers.
Mechanical Properties of Thin Glassy Polymer Films Filled with Spherical Polymer-Grafted Nanoparticles
Damien Maillard - ,
Sanat K. Kumar *- ,
Benjamin Fragneaud - ,
Jeffrey W. Kysar - ,
Atri Rungta - ,
Brian C. Benicewicz - ,
Hua Deng - ,
L. Cate Brinson - , and
Jack F. Douglas
It is commonly accepted that the addition of spherical nanoparticles (NPs) cannot simultaneously improve the elastic modulus, the yield stress, and the ductility of an amorphous glassy polymer matrix. In contrast to this conventional wisdom, we show that ductility can be substantially increased, while maintaining gains in the elastic modulus and yield stress, in glassy nanocomposite films composed of spherical silica NPs grafted with polystyrene (PS) chains in a PS matrix. The key to these improvements are (i) uniform NP spatial dispersion and (ii) strong interfacial binding between NPs and the matrix, by making the grafted chains sufficiently long relative to the matrix. Strikingly, the optimal conditions for the mechanical reinforcement of the same nanocomposite material in the melt state is completely different, requiring the presence of spatially extended NP clusters. Evidently, NP spatial dispersions that optimize material properties are crucially sensitive to the state (melt versus glass) of the polymeric material.
Electrically Connected Resonant Optical Antennas
Jord C. Prangsma - ,
Johannes Kern - ,
Alexander G. Knapp - ,
Swen Grossmann - ,
Monika Emmerling - ,
Martin Kamp - , and
Bert Hecht *
Electrically connected resonant optical antennas hold promise for the realization of highly efficient nanoscale electro-plasmonic devices that rely on a combination of electric fields and local near-field intensity enhancement. Here we demonstrate the feasibility of such a concept by attaching leads to the arms of a two-wire antenna at positions of minimal near-field intensity with negligible influence on the antenna resonance. White-light scattering experiments in accordance with simulations show that the optical tunability of connected antennas is fully retained. Analysis of the electric properties demonstrates that in the antenna gaps direct current (DC) electric fields of 108 V/m can consistently be achieved and maintained over extended periods of time without noticeable damage.
Coherent, Mechanical Control of a Single Electronic Spin
Sungkun Hong - ,
Michael S. Grinolds - ,
Patrick Maletinsky - ,
Ronald L. Walsworth - ,
Mikhail D. Lukin - , and
Amir Yacoby *
We demonstrate coherent quantum control of a single spin driven by the motion of a mechanical resonator. The motion of a mechanical resonator is magnetically coupled to the electronic spin of a single nitrogen-vacancy center in diamond. Synchronization of spin-addressing protocols to the motion of the driven oscillator is used to fully exploit the coherence of this hybrid mechanical-spin system. We demonstrate applications of this coherent mechanical spin-control technique to nanoscale scanning magnetometry.
Probing the Nature of Defects in Graphene by Raman Spectroscopy
Axel Eckmann - ,
Alexandre Felten - ,
Artem Mishchenko - ,
Liam Britnell - ,
Ralph Krupke - ,
Kostya S. Novoselov - , and
Cinzia Casiraghi *
Raman spectroscopy is able to probe disorder in graphene through defect-activated peaks. It is of great interest to link these features to the nature of disorder. Here we present a detailed analysis of the Raman spectra of graphene containing different type of defects. We found that the intensity ratio of the D and D′ peak is maximum (∼13) for sp3-defects, it decreases for vacancy-like defects (∼7), and it reaches a minimum for boundaries in graphite (∼3.5). This makes Raman Spectroscopy a powerful tool to fully characterize graphene.
Reversible Chiral Switching of Bis(phthalocyaninato) Terbium(III) on a Metal Surface
Ying-Shuang Fu *- ,
Jörg Schwöbel - ,
Saw-Wai Hla - ,
Andrew Dilullo - ,
Germar Hoffmann - ,
Svetlana Klyatskaya - ,
Mario Ruben - , and
Roland Wiesendanger
We demonstrate a reversible chiral switching of bis(phthalocyaninato) terbium(III) molecules on an Ir(111) surface by low temperature scanning tunneling microscopy. With an azimuthal rotation of its upper phthalocyanine ligand, the molecule can be switched between a chiral and an achiral configuration actuated by respective inelastic electron tunneling and local current heating. Moreover, the molecular chiral configuration can be interchanged between left and right handedness during the switching manipulations, thereby opening up potential nanotechnological applications.
Graphene Reknits Its Holes
Recep Zan - ,
Quentin M. Ramasse *- ,
Ursel Bangert - , and
Konstantin S. Novoselov
Nanoholes, etched under an electron beam at room temperature in single-layer graphene sheets as a result of their interaction with metal impurities, are shown to heal spontaneously by filling up with either nonhexagon, graphene-like, or perfect hexagon 2D structures. Scanning transmission electron microscopy was employed to capture the healing process and study atom-by-atom the regrown structure. A combination of these nanoscale etching and reknitting processes could lead to new graphene tailoring approaches.
Subnanometer Ga2O3 Tunnelling Layer by Atomic Layer Deposition to Achieve 1.1 V Open-Circuit Potential in Dye-Sensitized Solar Cells
Aravind Kumar Chandiran *- ,
Nicolas Tetreault - ,
Robin Humphry-Baker - ,
Florian Kessler - ,
Etienne Baranoff - ,
Chenyi Yi - ,
Mohammad Khaja Nazeeruddin *- , and
Michael Grätzel *
Herein, we present the first use of a gallium oxide tunnelling layer to significantly reduce electron recombination in dye-sensitized solar cells (DSC). The subnanometer coating is achieved using atomic layer deposition (ALD) and leading to a new DSC record open-circuit potential of 1.1 V with state-of-the-art organic D-π-A sensitizer and cobalt redox mediator. After ALD of only a few angstroms of Ga2O3, the electron back reaction is reduced by more than an order of magnitude, while charge collection efficiency and fill factor are increased by 30% and 15%, respectively. The photogenerated exciton separation processes of electron injection into the TiO2 conduction band and the hole injection into the electrolyte are characterized in detail.
Cascading Wafer-Scale Integrated Graphene Complementary Inverters under Ambient Conditions
Laura Giorgia Rizzi - ,
Massimiliano Bianchi - ,
Ashkan Behnam - ,
Enrique Carrion - ,
Erica Guerriero - ,
Laura Polloni - ,
Eric Pop - , and
Roman Sordan *
The fundamental building blocks of digital electronics are logic gates which must be capable of cascading such that more complex logic functions can be realized. Here we demonstrate integrated graphene complementary inverters which operate with the same input and output voltage logic levels, thus allowing cascading. We obtain signal matching under ambient conditions with inverters fabricated from wafer-scale graphene grown by chemical vapor deposition (CVD). Monolayer graphene was incorporated in self-aligned field-effect transistors in which the top gate overlaps with the source and drain contacts. This results in full-channel gating and leads to the highest low-frequency voltage gain reported so far in top-gated CVD graphene devices operating in air ambient, Av ∼ −5. Such gain enabled logic inverters with the same voltage swing of 0.56 V at their input and output. Graphene inverters could find their way in realistic applications where high-speed operation is desired but power dissipation is not a concern, similar to emitter-coupled logic.
Large-Scale Orientation Dependent Heating from a Single Irradiated Gold Nanorod
Haiyan Ma - ,
Poul M. Bendix - , and
Lene B. Oddershede *
We quantify the extreme heating associated with resonant irradiation of individual gold nanorods by using a novel assay based on partitioning of lipophilic dyes between membrane phases. The temperature increase is sensitively dependent on the angle between the laser polarization and the orientation of the nanorod. A dramatic and irreversible decrease in the heating of a nanorod occurs at high-illumination intensities; this effect is attributed to surface melting of the nanorod causing it to restructure into a more spherical shape and lose its extreme photothermal properties.
Magnetically Capped Rolled-up Nanomembranes
Robert Streubel *- ,
Dominic J. Thurmer - ,
Denys Makarov *- ,
Florian Kronast - ,
Tobias Kosub - ,
Volodymyr Kravchuk - ,
Denis D. Sheka - ,
Yuri Gaididei - ,
Rudolf Schäfer - , and
Oliver G. Schmidt
Modifying the curvature in magnetic nanostructures is a novel and elegant way toward tailoring physical phenomena at the nanoscale, allowing one to overcome limitations apparent in planar counterparts. Here, we address curvature-driven changes of static magnetic properties in cylindrically curved magnetic segments with different radii of curvature. The curved architectures are prepared by capping nonmagnetic micrometer- and nanometer-sized rolled-up membranes with a soft-magnetic 20 nm thick permalloy (Ni80Fe20) film. A quantitative comparison between the magnetization reversal processes in caps with different diameters is given. The phase diagrams of magnetic equilibrium domain patterns (diameter versus length) are generated. For this, joint experimental, including X-ray magnetic circular dichroism photoelectron emission microscopy (XMCD-PEEM), and theoretical studies are carried out. The anisotropic magnetostatic interaction in cylindrically curved architectures originating from the thickness gradient reduces substantially the magnetostatic interaction between closely packed curved nanowires. This feature is beneficial for racetrack memory devices, since a much higher areal density might be achieved than possible with planar counterparts.
Toward Plasmonic Polymers
Liane S. Slaughter - ,
Britain A. Willingham - ,
Wei-Shun Chang - ,
Maximilian H. Chester - ,
Nathan Ogden - , and
Stephan Link *
We establish the concept of a plasmonic polymer, whose collective optical properties depend on the repeat unit. Experimental and theoretical analyses of the super- and sub- radiant plasmon response of plasmonic polymers comprising repeat units of single nanoparticles or dimers of gold nanoparticles show that (1) the redshift of the lowest energy coupled mode becomes minimal as the chain approaches the infinite chain limit at a length of ∼10 particles, (2) the presence and energy of the modes are sensitive to the geometries of the constituents, that is, repeat unit, but (3) spatial disorder and nanoparticle heterogeneity have only small effects on the super-radiant mode.
Nano-FTIR Absorption Spectroscopy of Molecular Fingerprints at 20 nm Spatial Resolution
Florian Huth - ,
Alexander Govyadinov - ,
Sergiu Amarie - ,
Wiwat Nuansing - ,
Fritz Keilmann - , and
Rainer Hillenbrand *
We demonstrate Fourier transform infrared nanospectroscopy (nano-FTIR) based on a scattering-type scanning near-field optical microscope (s-SNOM) equipped with a coherent-continuum infrared light source. We show that the method can straightforwardly determine the infrared absorption spectrum of organic samples with a spatial resolution of 20 nm, corresponding to a probed volume as small as 10 zeptoliter (10–20 L). Corroborated by theory, the nano-FTIR absorption spectra correlate well with conventional FTIR absorption spectra, as experimentally demonstrated with poly(methyl methacrylate) (PMMA) samples. Nano-FTIR can thus make use of standard infrared databases of molecular vibrations to identify organic materials in ultrasmall quantities and at ultrahigh spatial resolution. As an application example we demonstrate the identification of a nanoscale PDMS contamination on a PMMA sample.
Ultrashort Channel Silicon Nanowire Transistors with Nickel Silicide Source/Drain Contacts
Wei Tang *- ,
Shadi A. Dayeh *- ,
S. Tom Picraux - ,
Jian Yu Huang - , and
King-Ning Tu
We demonstrate the shortest transistor channel length (17 nm) fabricated on a vapor–liquid–solid (VLS) grown silicon nanowire (NW) by a controlled reaction with Ni leads on an in situ transmission electron microscope (TEM) heating stage at a moderate temperature of 400 °C. NiSi2 is the leading phase, and the silicide–silicon interface is an atomically sharp type-A interface. At such channel lengths, high maximum on-currents of 890 (μA/μm) and a maximum transconductance of 430 (μS/μm) were obtained, which pushes forward the performance of bottom-up Si NW Schottky barrier field-effect transistors (SB-FETs). Through accurate control over the silicidation reaction, we provide a systematic study of channel length dependent carrier transport in a large number of SB-FETs with channel lengths in the range of 17 nm to 3.6 μm. Our device results corroborate with our transport simulations and reveal a characteristic type of short channel effects in SB-FETs, both in on- and off-state, which is different from that in conventional MOSFETs, and that limits transport parameter extraction from SB-FETs using conventional field-effect transconductance measurements.
Large-Area (over 50 cm × 50 cm) Freestanding Films of Colloidal InP/ZnS Quantum Dots
Evren Mutlugun - ,
Pedro Ludwig Hernandez-Martinez - ,
Cuneyt Eroglu - ,
Yasemin Coskun - ,
Talha Erdem - ,
Vijay K. Sharma - ,
Emre Unal - ,
Subhendu K. Panda - ,
Stephen G. Hickey - ,
Nikolai Gaponik - ,
Alexander Eychmüller - , and
Hilmi Volkan Demir *
We propose and demonstrate the fabrication of flexible, freestanding films of InP/ZnS quantum dots (QDs) using fatty acid ligands across very large areas (greater than 50 cm × 50 cm), which have been developed for remote phosphor applications in solid-state lighting. Embedded in a poly(methyl methacrylate) matrix, although the formation of stand–alone films using other QDs commonly capped with trioctylphosphine oxide (TOPO) and oleic acid is not efficient, employing myristic acid as ligand in the synthesis of these QDs, which imparts a strongly hydrophobic character to the thin film, enables film formation and ease of removal even on surprisingly large areas, thereby avoiding the need for ligand exchange. When pumped by a blue LED, these Cd-free QD films allow for high color rendering, warm white light generation with a color rendering index of 89.30 and a correlated color temperature of 2298 K. In the composite film, the temperature-dependent emission kinetics and energy transfer dynamics among different-sized InP/ZnS QDs are investigated and a model is proposed. High levels of energy transfer efficiency (up to 80%) and strong donor lifetime modification (from 18 to 4 ns) are achieved. The suppression of the nonradiative channels is observed when the hybrid film is cooled to cryogenic temperatures. The lifetime changes of the donor and acceptor InP/ZnS QDs in the film as a result of the energy transfer are explained well by our theoretical model based on the exciton–exciton interactions among the dots and are in excellent agreement with the experimental results. The understanding of these excitonic interactions is essential to facilitate improvements in the fabrication of photometrically high quality nanophosphors. The ability to make such large-area, flexible, freestanding Cd-free QD films pave the way for environmentally friendly phosphor applications including flexible, surface-emitting light engines.
Robust Room-Temperature Ferromagnetism with Giant Anisotropy in Nd-Doped ZnO Nanowire Arrays
Dandan Wang - ,
Qian Chen - ,
Guozhong Xing - ,
Jiabao Yi - ,
Saidur Rahman Bakaul - ,
Jun Ding - ,
Jinlan Wang *- , and
Tom Wu *
As an important class of spintronic material, ferromagnetic oxide semiconductors are characterized with both charge and spin degrees of freedom, but they often show weak magnetism and small coercivity, which limit their applications. In this work, we synthesized Nd-doped ZnO nanowire arrays which exhibit stable room temperature ferromagnetism with a large saturation magnetic moment of 4.1 μB/Nd as well as a high coercivity of 780 Oe, indicating giant magnetic anisotropy. First-principles calculations reveal that the remarkable magnetic properties in Nd-doped ZnO nanowires can be ascribed to the intricate interplay between the spin moments and the Nd-derived orbital moments. Our complementary experimental and theoretical results suggest that these magnetic oxide nanowires obtained by the bottom-up synthesis are promising as nanoscale building blocks in spintronic devices.
Engineering Independent Electrostatic Control of Atomic-Scale (∼4 nm) Silicon Double Quantum Dots
Bent Weber - ,
Suddhasatta Mahapatra - ,
Thomas F. Watson - , and
Michelle Y. Simmons *
Scalable quantum computing architectures with electronic spin qubits hosted by arrays of single phosphorus donors in silicon require local electric and magnetic field control of individual qubits separated by ∼10 nm. This daunting task not only requires atomic-scale accuracy of single P donor positioning to control interqubit exchange interaction but also demands precision alignment of control electrodes with careful device design at these small length scales to minimize cross capacitive coupling. Here we demonstrate independent electrostatic control of two Si:P quantum dots, each consisting of ∼15 P donors, in an optimized device design fabricated by scanning tunneling microscope (STM)-based lithography. Despite the atomic-scale dimensions of the quantum dots and control electrodes reducing overall capacitive coupling, the electrostatic behavior of the device shows an excellent match to results of a priori capacitance calculations. These calculations highlight the importance of the interdot angle in achieving independent control at these length-scales. This combination of predictive electrostatic modeling and the atomic-scale fabrication accuracy of STM-lithography, provides a powerful tool for scaling multidonor dots to the single donor limit.
Control of Lateral Dimension in Metal-Catalyzed Germanium Nanowire Growth: Usage of Carbon Sheath
Byung-Sung Kim - ,
Min Jin Kim - ,
Jong Cheol Lee - ,
Sung Woo Hwang *- ,
Byoung Lyong Choi - ,
Eun Kyung Lee - , and
Dongmok Whang *
We report on the catalytic growth of thin carbon sheathed single crystal germanium nanowires (GeNWs), which can solve the obstacles that have disturbed a wide range of applications of GeNWs. Single crystal Ge NW core and amorphous carbon sheath are simultaneously grown via vapor–liquid–solid (VLS) process. The carbon sheath completely blocks unintentional vapor deposition on NW surface, thus ensuring highly uniform diameter, dopant distribution, and electrical conductivity along the entire NW length. Furthermore, the sheath not only inhibits metal diffusion but also improves the chemical stability of GeNWs at even high temperatures.
Highly Flexible MoS2 Thin-Film Transistors with Ion Gel Dielectrics
Jiang Pu - ,
Yohei Yomogida - ,
Keng-Ku Liu - ,
Lain-Jong Li - ,
Yoshihiro Iwasa - , and
Taishi Takenobu
Molybdenum disulfide (MoS2) thin-film transistors were fabricated with ion gel gate dielectrics. These thin-film transistors exhibited excellent band transport with a low threshold voltage (<1 V), high mobility (12.5 cm2/(V·s)) and a high on/off current ratio (105). Furthermore, the MoS2 transistors exhibited remarkably high mechanical flexibility, and no degradation in the electrical characteristics was observed when they were significantly bent to a curvature radius of 0.75 mm. The superior electrical performance and excellent pliability of MoS2 films make them suitable for use in large-area flexible electronics.
Single Step Isolation and Activation of Primary CD3+ T Lymphocytes Using Alcohol-Dispersed Electrospun Magnetic Nanofibers
Kwanghee Kim - ,
Hyo Jin An - ,
Seung-Hyun Jun - ,
Tae-Jin Kim - ,
Seon Ah Lim - ,
Gayoung Park - ,
Hyon Bin Na - ,
Yong Il Park - ,
Taeghwan Hyeon - ,
Cassian Yee - ,
Jeffrey A Bluestone - ,
Jungbae Kim *- , and
Kyung-Mi Lee *
Electrospun polymer nanofibers with entrapped magnetic nanoparticles (magnetic NP–NF) represent a novel scaffold substrate that can be functionalized for single-step isolation and activation of specific lymphocyte subsets. Using a surface-embedded T cell receptor ligand/trigger (anti-CD3 monoclonal antibody), we demonstrate, as proof of principle, the use of magnetic NP–NF to specifically isolate, enrich, and activate CD3+ T cells from a heterogeneous cell mixture, leading to preferential expansion of CD8+CD3+ T cells. The large surface area, adjustable antibody density, and embedded paramagnetic properties of the NP–NF permitted enhanced activation and expansion; its use represents a strategy that is amenable to an efficient selection process for adoptive cellular therapy as well as for the isolation of other cellular subsets for downstream translational applications.
Connecting Dopant Bond Type with Electronic Structure in N-Doped Graphene
Theanne Schiros *- ,
Dennis Nordlund - ,
Lucia Pálová - ,
Deborah Prezzi - ,
Liuyan Zhao - ,
Keun Soo Kim - ,
Ulrich Wurstbauer - ,
Christopher Gutiérrez - ,
Dean Delongchamp - ,
Cherno Jaye - ,
Daniel Fischer - ,
Hirohito Ogasawara - ,
Lars G. M. Pettersson - ,
David R. Reichman - ,
Philip Kim - ,
Mark S. Hybertsen - , and
Abhay N. Pasupathy *
Robust methods to tune the unique electronic properties of graphene by chemical modification are in great demand due to the potential of the two dimensional material to impact a range of device applications. Here we show that carbon and nitrogen core-level resonant X-ray spectroscopy is a sensitive probe of chemical bonding and electronic structure of chemical dopants introduced in single-sheet graphene films. In conjunction with density functional theory based calculations, we are able to obtain a detailed picture of bond types and electronic structure in graphene doped with nitrogen at the sub-percent level. We show that different N-bond types, including graphitic, pyridinic, and nitrilic, can exist in a single, dilutely N-doped graphene sheet. We show that these various bond types have profoundly different effects on the carrier concentration, indicating that control over the dopant bond type is a crucial requirement in advancing graphene electronics.
Diameter-Dependent or Independent: Toward a Mechanistic Understanding of the Vapor–Liquid–Solid Si Nanowire Growth Rate
Y. Y. Lü - ,
H. Cui - ,
G. W. Yang - , and
C. X. Wang *
Si nanowires have received continued increased attention because they keep the promise of monolithic integration of high-performance semiconductors with new functionality into existing silicon technology. Most Si nanowires are grown by vapor–liquid–solid mechanism, and despite many years of study, this growth mechanism remains under lively debate. For instance, contradictory results have been reported on the effect of diameter size on nanowire growth rate. Here, we developed a universal kinetic model of Si nanowire growth based on surface diffusion which takes into account adatom diffusion from the sidewall and substrate surface into the liquid droplet as well as the Gibbs–Thomson effect. Our analysis shows that the diameter independence for Si nanowires is affected by the interplay between the Gibbs–Thomson effect and the surface diffusion, whereas the diameter dependence is mainly influenced by the Gibbs–Thomson effect. The results based on the proposed model are in good agreement with experimental data.
Large Apparent Electric Size of Solid-State Nanopores Due to Spatially Extended Surface Conduction
Choongyeop Lee - ,
Laurent Joly - ,
Alessandro Siria - ,
Anne-Laure Biance - ,
Rémy Fulcrand - , and
Lydéric Bocquet *
Ion transport through nanopores drilled in thin membranes is central to numerous applications, including biosensing and ion selective membranes. This paper reports experiments, numerical calculations, and theoretical predictions demonstrating an unexpectedly large ionic conduction in solid-state nanopores, taking its origin in anomalous entrance effects. In contrast to naive expectations based on analogies with electric circuits, the surface conductance inside the nanopore is shown to perturb the three-dimensional electric current streamlines far outside the nanopore in order to meet charge conservation at the pore entrance. This unexpected contribution to the ionic conductance can be interpreted in terms of an apparent electric size of the solid-state nanopore, which is much larger than its geometric counterpart whenever the number of charges carried by the nanopore surface exceeds its bulk counterpart. This apparent electric size, which can reach hundreds of nanometers, can have a major impact on the electrical detection of translocation events through nanopores, as well as for ionic transport in biological nanopores.
Quantitative Evidence of Crossover toward Partial Dislocation Mediated Plasticity in Copper Single Crystalline Nanowires
Yonghai Yue - ,
Pan Liu - ,
Qingsong Deng - ,
Evan Ma *- ,
Ze Zhang - , and
Xiaodong Han *
In situ tensile tests of Cu single crystalline nanowires in a high-resolution transmission electron microscope reveal a novel effect of sample dimensions on plasticity mechanisms. When the single crystalline nanowire size was reduced to <∼150 nm, the normal full dislocation slip was taken over by partial dislocation mediated plasticity (PDMP). For the first time, we demonstrate this transition in a quantitative manner by assessing the relative contributions to plastic strain from PDMP and full dislocations. The crossover sample size is consistent, well within model predictions. This discovery represents yet another “sample size effect”, beyond other reported influence of sample dimensions on the mechanical behavior of metals, such as dislocation starvation or source truncation, and the “smaller is stronger” trend.
Nanowire Arrays in Multicrystalline Silicon Thin Films on Glass: A Promising Material for Research and Applications in Nanotechnology
Sebastian W. Schmitt - ,
Florian Schechtel - ,
Daniel Amkreutz - ,
Muhammad Bashouti - ,
Sanjay K. Srivastava - ,
Björn Hoffmann - ,
Christel Dieker - ,
Erdmann Spiecker - ,
Bernd Rech - , and
Silke H. Christiansen
Silicon nanowires (SiNW) were formed on large grained, electron-beam crystallized silicon (Si) thin films of only ∼6 μm thickness on glass using nanosphere lithography (NSL) in combination with reactive ion etching (RIE). Electron backscatter diffraction (EBSD) and transmission electron microscopy (TEM) studies revealed outstanding structural properties of this nanomaterial. It could be shown that SiNWs with entirely predetermined shapes including lengths, diameters and spacings and straight side walls form independently of their crystalline orientation and arrange in ordered arrays on glass. Furthermore, for the first time grain boundaries could be observed in individual, straightly etched SiNWs. After heat treatment an electronic grade surface quality of the SiNWs could be shown by X-ray photoelectron spectroscopy (XPS). Integrating sphere measurements show that SiNW patterning of the multicrystalline Si (mc-Si) starting thin film on glass substantially increases absorption and reduces reflection, as being desired for an application in thin film photovoltaics (PV). The multicrystalline SiNWs directly mark a starting point for research not only in PV but also in other areas like nanoelectronics, surface functionalization, and nanomechanics.
Scanning Probe Manipulation of Magnetism at the LaAlO3/SrTiO3 Heterointerface
Beena Kalisky *- ,
Julie A. Bert - ,
Christopher Bell - ,
Yanwu Xie - ,
Hiroki K. Sato - ,
Masayuki Hosoda - ,
Yasuyuki Hikita - ,
Harold Y. Hwang - , and
Kathryn A. Moler
Manipulation of magnetism is a longstanding goal of research in exotic materials. In this work, we demonstrate that the small ferromagnetic patches in LaAlO3/SrTiO3 heterostructures can be dramatically changed by in situ contact of a scanning probe. Our results provide a platform for manipulation of small magnets through either a strong magneto-elastic coupling or sensitivity to surface modification. The ability to locally control magnetism is particularly interesting due to the presence of superconductivity with strong spin–orbit coupling in LaAlO3/SrTiO3.
Separation of Nanoparticles in Aqueous Multiphase Systems through Centrifugation
Ozge Akbulut - ,
Charles R. Mace - ,
Ramses V. Martinez - ,
Ashok A. Kumar - ,
Zhihong Nie - ,
Matthew R. Patton - , and
George M. Whitesides *
This paper demonstrates the use of aqueous multiphase systems (MuPSs) as media for rate-zonal centrifugation to separate nanoparticles of different shapes and sizes. The properties of MuPSs do not change with time or during centrifugation; this stability facilitates sample collection after separation. A three-phase system demonstrates the separation of the reaction products (nanorods, nanospheres, and large particles) of a synthesis of gold nanorods, and enriches the nanorods from 48 to 99% in less than ten minutes using a benchtop centrifuge.
Realization of the Manipulation of Ultracold Atoms with a Reconfigurable Nanomagnetic System of Domain Walls
Adam D. West - ,
Kevin J. Weatherill - ,
Thomas J. Hayward - ,
Paul W. Fry - ,
Thomas Schrefl - ,
Mike R. J. Gibbs - ,
Charles S. Adams - ,
Dan A. Allwood - , and
Ifan G. Hughes *
Planar magnetic nanowires have been vital to the development of spintronic technology. They provide an unparalleled combination of magnetic reconfigurability, controllability, and scalability, which has helped to realize such applications as racetrack memory and novel logic gates. Microfabricated atom optics benefit from all of these properties, and we present the first demonstration of the amalgamation of spintronic technology with ultracold atoms. A magnetic interaction is exhibited through the reflection of a cloud of 87Rb atoms at a temperature of 10 μK, from a 2 mm × 2 mm array of nanomagnetic domain walls. In turn, the incident atoms approach the array at heights of the order of 100 nm and are thus used to probe magnetic fields at this distance.
Plasmonic Light Trapping in Thin-film Silicon Solar Cells with Improved Self-Assembled Silver Nanoparticles
Hairen Tan *- ,
Rudi Santbergen - ,
Arno H. M. Smets - , and
Miro Zeman
Plasmonic metal nanoparticles are of great interest for light trapping in thin-film silicon solar cells. In this Letter, we demonstrate experimentally that a back reflector with plasmonic Ag nanoparticles can provide light-trapping performance comparable to state-of-the-art random textures in n-i-p amorphous silicon solar cells. This conclusion is based on the comparison to high performance n-i-p solar cell and state-of-the-art efficiency p-i-n solar cells deposited on the Asahi VU-type glass. With the plasmonic back reflector a gain of 2 mA/cm2 in short-circuit current density was obtained without any deterioration of open circuit voltage or fill factor compared to the solar cell on a flat back reflector. The excellent light trapping is a result of strong light scattering and low parasitic absorption of self-assembled Ag nanoparticles embedded in the back reflector. The plasmonic back reflector provides a high degree of light trapping with a haze in reflection greater than 80% throughout the wavelength range 520–1100 nm. The high performance of plasmonic back reflector is attributed to improvements in the self-assembly technique, which result in a lower surface coverage and fewer small and irregular nanoparticles.
Selective Supramolecular Fullerene–Porphyrin Interactions and Switching in Surface-Confined C60–Ce(TPP)2 Dyads
Saranyan Vijayaraghavan - ,
David Écija *- ,
Willi Auwärter *- ,
Sushobhan Joshi - ,
Knud Seufert - ,
Ari P. Seitsonen - ,
Kentaro Tashiro - , and
Johannes V. Barth
The control of organic molecules, supramolecular complexes and donor–acceptor systems at interfaces is a key issue in the development of novel hybrid architectures for regulation of charge-carrier transport pathways in nanoelectronics or organic photovoltaics. However, at present little is known regarding the intricate features of stacked molecular nanostructures stabilized by noncovalent interactions. Here we explore at the single molecule level the geometry and electronic properties of model donor–acceptor dyads stabilized by van der Waals interactions on a single crystal Ag(111) support. Our combined scanning tunneling microscopy/spectroscopy (STM/STS) and first-principles computational modeling study reveals site-selective positioning of C60 molecules on Ce(TPP)2 porphyrin double-decker arrays with the fullerene centered on the π-system of the top bowl-shaped tetrapyrrole macrocycle. Three specific orientations of the C60 cage in the van der Waals complex are identified that can be reversibly switched by STM manipulation protocols. Each configuration presents a distinct conductivity, which accounts for a tristable molecular switch and the tunability of the intradyad coupling. In addition, STS data evidence electronic decoupling of the hovering C60 units from the metal substrate, a prerequisite for photophysical applications.
Irradiation Induced Grain Boundary Flow—A New Creep Mechanism at the Nanoscale
Yinon Ashkenazy *- and
Robert S. Averback
A new mechanism of irradiation enhanced creep is proposed for nanocrystalline materials. It derives from local relaxations within the grain boundaries as they absorb point defects produced by irradiation. The process is studied by inserting point defects into the grain boundaries and following the materials response by molecular dynamics. Calculated creep compliances are found in good agreement with those measured in dilute nanocrystalline Cu–W alloys [Tai, K.; Averback, R. S.; Bellon, P.; Ashkenazy Y. Scr. Mater.2011, 65, 163]. The simulations provide a direct link between irradiation induced creep in nanocrystalline materials with radiation-induced viscous flow in amorphous materials, suggesting that grain boundaries in these materials can be treated as an amorphous phase. We provide a simple analytic model based on this assumption that reproduces the main features of the observed creep rates, a linear dependence on stress, inverse dependence of grain size, a weak dependence on temperature, and a reasonable estimate of the absolute creep rate.
Graphene-Enabled Silver Nanoantenna Sensors
Jason C Reed - ,
Hai Zhu - ,
Alexander Y. Zhu - ,
Chen Li - , and
Ertugrul Cubukcu *
Silver is the ideal material for plasmonics because of its low loss at optical frequencies but is often replaced by a more lossy metal, gold. This is because of silver’s tendency to tarnish and roughen, forming Ag2S on its surface, dramatically diminishing optical properties and rendering it unreliable for applications. By passivating the surface of silver nanostructures with monolayer graphene, atmospheric sulfur containing compounds are unable to penetrate the graphene to degrade the surface of the silver. Preventing this sulfidation eliminates the increased material damping and scattering losses originating from the unintentional Ag2S layer. Because it is atomically thin, graphene does not interfere with the ability of localized surface plasmons to interact with the environment in sensing applications. Furthermore, after 30 days graphene-passivated silver (Ag–Gr) nanoantennas exhibit a 2600% higher sensitivity over that of bare Ag nanoantennas and 2 orders of magnitude improvement in peak width endurance. By employing graphene in this manner, the excellent optical properties and large spectral range of silver can be functionally utilized in a variety of nanoscale plasmonic devices and applications.
Direct Identification of Metallic and Semiconducting Single-Walled Carbon Nanotubes in Scanning Electron Microscopy
Jie Li - ,
Yujun He - ,
Yimo Han - ,
Kai Liu - ,
Jiaping Wang - ,
Qunqing Li - ,
Shoushan Fan - , and
Kaili Jiang *
Because of their excellent electrical and optical properties, carbon nanotubes have been regarded as extremely promising candidates for high-performance electronic and optoelectronic applications. However, effective and efficient distinction and separation of metallic and semiconducting single-walled carbon nanotubes are always challenges for their practical applications. Here we show that metallic and semiconducting single-walled carbon nanotubes on SiO2 can have obviously different contrast in scanning electron microscopy due to their conductivity difference and thus can be effectively and efficiently identified. The correlation between conductivity and contrast difference has been confirmed by using voltage-contrast scanning electron microcopy, peak force tunneling atom force microscopy, and field effect transistor testing. This phenomenon can be understood via a proposed mechanism involving the e-beam-induced surface potential of insulators and the conductivity difference between metallic and semiconducting SWCNTs. This method demonstrates great promise to achieve rapid and large-scale distinguishing between metallic and semiconducting single-walled carbon nanotubes, adding a new function to conventional SEM.
Low-Resistivity 10 nm Diameter Magnetic Sensors
Mazin M. Maqableh - ,
Xiaobo Huang - ,
Sang-Yeob Sung - ,
K. Sai Madhukar Reddy - ,
Gregory Norby - ,
R. H. Victora - , and
Bethanie J. H. Stadler *
Resistivities of 5.4 μΩ·cm were measured in 10-nm-diameter metallic wires. Low resistance is important for interconnections of the future to prevent heating, electromigration, high power consumption, and long RC time constants. To demonstrate application of these wires, Co/Cu/Co magnetic sensors were synthesized with 20–30 Ω and 19% magnetoresistance. Compared to conventional lithographically produced magnetic tunnel junction sensors, these structures offer facile fabrication and over 2 orders of magnitude lower resistances due to smooth sidewalls from in situ templated chemical growth.
In Situ Atomic Force Microscopy Tip-Induced Deformations and Raman Spectroscopy Characterization of Single-Wall Carbon Nanotubes
P. T. Araujo - ,
N. M. Barbosa Neto - ,
H. Chacham - ,
S. S. Carara - ,
J. S. Soares - ,
A. D. Souza - ,
L. G. Cançado - ,
A. B. de Oliveira - ,
R. J. C. Batista - ,
E. Joselevich - ,
M. S. Dresselhaus - , and
A. Jorio *
In this work, an atomic force microscope (AFM) is combined with a confocal Raman spectroscopy setup to follow in situ the evolution of the G-band feature of isolated single-wall carbon nanotubes (SWNTs) under transverse deformation. The SWNTs are pressed by a gold AFM tip against the substrate where they are sitting. From eight deformed SWNTs, five exhibit an overall decrease in the Raman signal intensity, while three exhibit vibrational changes related to the circumferential symmetry breaking. Our results reveal chirality dependent effects, which are averaged out in SWNT bundle measurements, including a previously elusive mode symmetry breaking that is here explored using molecular dynamics calculations.
Assessing Graphene Nanopores for Sequencing DNA
David B. Wells - ,
Maxim Belkin - ,
Jeffrey Comer - , and
Aleksei Aksimentiev *
Using all-atom molecular dynamics and atomic-resolution Brownian dynamics, we simulate the translocation of single-stranded DNA through graphene nanopores and characterize the ionic current blockades produced by DNA nucleotides. We find that transport of single DNA strands through graphene nanopores may occur in single nucleotide steps. For certain pore geometries, hydrophobic interactions with the graphene membrane lead to a dramatic reduction in the conformational fluctuations of the nucleotides in the nanopores. Furthermore, we show that ionic current blockades produced by different DNA nucleotides are, in general, indicative of the nucleotide type, but very sensitive to the orientation of the nucleotides in the nanopore. Taken together, our simulations suggest that strand sequencing of DNA by measuring the ionic current blockades in graphene nanopores may be possible, given that the conformation of DNA nucleotides in the nanopore can be controlled through precise engineering of the nanopore surface.
Conductive Rigid Skeleton Supported Silicon as High-Performance Li-Ion Battery Anodes
Xilin Chen - ,
Xiaolin Li - ,
Fei Ding - ,
Wu Xu - ,
Jie Xiao - ,
Yuliang Cao - ,
Praveen Meduri - ,
Jun Liu *- ,
Gordon L. Graff - , and
Ji-Guang Zhang *
A cost-effective and scalable method is developed to prepare a core–shell structured Si/B4C composite with graphite coating with high efficiency, exceptional rate performance, and long-term stability. In this material, conductive B4C with a high Mohs hardness serves not only as micro/nano-millers in the ball-milling process to break down micron-sized Si but also as the conductive rigid skeleton to support the in situ formed sub-10 nm Si particles to alleviate the volume expansion during charge/discharge. The Si/B4C composite is coated with a few graphitic layers to further improve the conductivity and stability of the composite. The Si/B4C/graphite (SBG) composite anode shows excellent cyclability with a specific capacity of ∼822 mAh·g–1 (based on the weight of the entire electrode, including binder and conductive carbon) and ∼94% capacity retention over 100 cycles at 0.3 C rate. This new structure has the potential to provide adequate storage capacity and stability for practical applications and a good opportunity for large-scale manufacturing using commercially available materials and technologies.
Tracking Mesenchymal Stem Cells with Iron Oxide Nanoparticle Loaded Poly(lactide-co-glycolide) Microparticles
Chenjie Xu - ,
David Miranda-Nieves - ,
James A. Ankrum - ,
Mads Emil Matthiesen - ,
Joseph A. Phillips - ,
Isaac Roes - ,
Gregory R. Wojtkiewicz - ,
Vikram Juneja - ,
Jens Roat Kultima - ,
Weian Zhao - ,
Praveen Kumar Vemula - ,
Charles P. Lin - ,
Matthias Nahrendorf - , and
Jeffrey M. Karp *
Monitoring the location, distribution and long-term engraftment of administered cells is critical for demonstrating the success of a cell therapy. Among available imaging-based cell tracking tools, magnetic resonance imaging (MRI) is advantageous due to its noninvasiveness, deep penetration, and high spatial resolution. While tracking cells in preclinical models via internalized MRI contrast agents (iron oxide nanoparticles, IO-NPs) is a widely used method, IO-NPs suffer from low iron content per particle, low uptake in nonphagocytotic cell types (e.g., mesenchymal stem cells, MSCs), weak negative contrast, and decreased MRI signal due to cell proliferation and cellular exocytosis. Herein, we demonstrate that internalization of IO-NP (10 nm) loaded biodegradable poly(lactide-co-glycolide) microparticles (IO/PLGA-MPs, 0.4–3 μm) in MSCs enhances MR parameters such as the r2 relaxivity (5-fold), residence time inside the cells (3-fold) and R2 signal (2-fold) compared to IO-NPs alone. Intriguingly, in vitro and in vivo experiments demonstrate that internalization of IO/PLGA-MPs in MSCs does not compromise inherent cell properties such as viability, proliferation, migration and their ability to home to sites of inflammation.
Self-Aligned, Extremely High Frequency III–V Metal-Oxide-Semiconductor Field-Effect Transistors on Rigid and Flexible Substrates
Chuan Wang - ,
Jun-Chau Chien - ,
Hui Fang - ,
Kuniharu Takei - ,
Junghyo Nah - ,
E. Plis - ,
Sanjay Krishna - ,
Ali M. Niknejad - , and
Ali Javey *
This paper reports the radio frequency (RF) performance of InAs nanomembrane transistors on both mechanically rigid and flexible substrates. We have employed a self-aligned device architecture by using a T-shaped gate structure to fabricate high performance InAs metal-oxide-semiconductor field-effect transistors (MOSFETs) with channel lengths down to 75 nm. RF measurements reveal that the InAs devices made on a silicon substrate exhibit a cutoff frequency (ft) of ∼165 GHz, which is one of the best results achieved in III–V MOSFETs on silicon. Similarly, the devices fabricated on a bendable polyimide substrate provide a ft of ∼105 GHz, representing the best performance achieved for transistors fabricated directly on mechanically flexible substrates. The results demonstrate the potential of III–V-on-insulator platform for extremely high-frequency (EHF) electronics on both conventional silicon and flexible substrates.
Glancing Angle Deposition of Copper Iodide Nanocrystals for Efficient Organic Photovoltaics
Ying Zhou *- ,
Tetsuya Taima *- ,
Tetsuhiko Miyadera - ,
Toshihiro Yamanari - ,
Michinori Kitamura - ,
Kazuhiro Nakatsu - , and
Yuji Yoshida
We report a simple method to achieve efficient nanostructured organic photovoltaics via patterning copper iodide (CuI) nanocrystals on indium tin oxide by glancing angle deposition. The strong interfacial interaction between zinc phthalocyanine (ZnPc) and CuI leads to the formation of nanopillar arrays with lying-down molecular order, which greatly improve light absorption and surface roughness for exciton dissociation. Optimized ZnPc/C60 bilayer cell has a power conversion efficiency of 4.0 ± 0.1%, which is about 3-fold larger than that of conventional planar cell.
Bismuth-Catalyzed and Doped Silicon Nanowires for One-Pump-Down Fabrication of Radial Junction Solar Cells
Linwei Yu - ,
Franck Fortuna - ,
Benedict O’Donnell - ,
Taewoo Jeon - ,
Martin Foldyna - ,
Gennaro Picardi - , and
Pere Roca i Cabarrocas
Silicon nanowires (SiNWs) are becoming a popular choice to develop a new generation of radial junction solar cells. We here explore a bismuth- (Bi-) catalyzed growth and doping of SiNWs, via vapor–liquid–solid (VLS) mode, to fabricate amorphous Si radial n–i–p junction solar cells in a one-pump-down and low-temperature process in a single chamber plasma deposition system. We provide the first evidence that catalyst doping in the SiNW cores, caused by incorporating Bi catalyst atoms as n-type dopant, can be utilized to fabricate radial junction solar cells, with a record open circuit voltage of Voc = 0.76 V and an enhanced light trapping effect that boosts the short circuit current to Jsc = 11.23 mA/cm2. More importantly, this bi-catalyzed SiNW growth and doping strategy exempts the use of extremely toxic phosphine gas, leading to significant procedure simplification and cost reduction for building radial junction thin film solar cells.
Measurement of the Docking Time of a DNA Molecule onto a Solid-State Nanopore
Stefan W. Kowalczyk - and
Cees Dekker *
We present measurements of the change in ionic conductance due to double-stranded (ds) DNA translocation through small (6 nm diameter) nanopores at low salt (100 mM KCl). At both low (<200 mV) and high (>600 mV) voltages we observe a current enhancement during DNA translocation, similar to earlier reports. Intriguingly, however, in the intermediate voltage range, we observe a new type of composite events, where within each single event the current first decreases and then increases. From the voltage dependence of the magnitude and timing of these current changes, we conclude that the current decrease is caused by the docking of the DNA random coil onto the nanopore. Unexpectedly, we find that the docking time is exponentially dependent on voltage (t ∝ e–V/V0). We discuss a physical picture where the docking time is set by the time that a DNA end needs to move from a random location within the DNA coil to the nanopore. Upon entrance of the pore, the current subsequently increases due to enhanced flow of counterions along the DNA. Interestingly, these composite events thus allow to independently measure the actual translocation time as well as the docking time before translocation.
Simple Monitoring of Cancer Cells Using Nanoparticles
Marisa Maltez-da Costa - ,
Alfredo de la Escosura-Muñiz - ,
Carme Nogués - ,
Lleonard Barrios - ,
Elena Ibáñez - , and
Arben Merkoçi *
Here we present a new strategy for a simple and fast detection of cancer circulating cells (CTCs) using nanoparticles. The human colon adenocarcinoma cell line (Caco2) was chosen as a model CTC. Similarly to other adenocarcinomas, colon adenocarcinoma cells have a strong expression of EpCAM, and for this reason this glycoprotein was used as the capture target. We combine the capturing capability of anti-EpCAM functionalized magnetic beads (MBs) and the specific labeling through antibody-modified gold nanoparticles (AuNPs), with the sensitivity of the AuNPs-electrocatalyzed hydrogen evolution reaction (HER) detection technique. The fully optimized process was used for the electrochemical detection of Caco2 cells in the presence of monocytes (THP-1), other circulating cells that could interfere in real blood samples. Therefore we obtained a novel and simple in situ-like sensing format that we applied for the rapid quantification of AuNPs-labeled CTCs in the presence of other human cells.
Plasmon Spectroscopy and Imaging of Individual Gold Nanodecahedra: A Combined Optical Microscopy, Cathodoluminescence, and Electron Energy-Loss Spectroscopy Study
Viktor Myroshnychenko *- ,
Jaysen Nelayah - ,
Giorgio Adamo - ,
Nicolas Geuquet - ,
Jessica Rodríguez-Fernández - ,
Isabel Pastoriza-Santos - ,
Kevin F. MacDonald - ,
Luc Henrard - ,
Luis M. Liz-Marzán - ,
Nikolay I. Zheludev - ,
Mathieu Kociak - , and
F. Javier García de Abajo *
Imaging localized plasmon modes in noble-metal nanoparticles is of fundamental importance for applications such as ultrasensitive molecular detection. Here, we demonstrate the combined use of optical dark-field microscopy (DFM), cathodoluminescence (CL), and electron energy-loss spectroscopy (EELS) to study localized surface plasmons on individual gold nanodecahedra. By exciting surface plasmons with either external light or an electron beam, we experimentally resolve a prominent dipole-active plasmon band in the far-field radiation acquired via DFM and CL, whereas EELS reveals an additional plasmon mode associated with a weak dipole moment. We present measured spectra and intensity maps of plasmon modes in individual nanodecahedra in excellent agreement with boundary-element method simulations, including the effect of the substrate. A simple tight-binding model is formulated to successfully explain the rich plasmon structure in these particles encompasing bright and dark modes, which we predict to be fully observable in less lossy silver decahedra. Our work provides useful insight into the complex nature of plasmon resonances in nanoparticles with pentagonal symmetry.
One-Volt Operation of High-Current Vertical Channel Polymer Semiconductor Field-Effect Transistors
Danvers E. Johnston - ,
Kevin G. Yager - ,
Chang-Yong Nam - ,
Benjamin M. Ocko - , and
Charles T. Black *
We realize a vertical channel polymer semiconductor field effect transistor architecture by confining the organic material within gratings of interdigitated trenches. The geometric space savings of a perpendicular channel orientation results in devices sourcing areal current densities in excess of 40 mA/cm2, using a one-volt supply voltage, and maintaining near-ideal device operating characteristics. Vertical channel transistors have a similar electronic mobility to that of planar devices using the same polymer semiconductor, consistent with a molecular reorientation within confining trenches we understand through X-ray scattering measurements.
Pulsed Laser Deposition of CdSe Quantum Dots on Zn2SnO4 Nanowires and Their Photovoltaic Applications
Qilin Dai - ,
Jiajun Chen - ,
Liyou Lu - ,
Jinke Tang - , and
Wenyong Wang *
In this work we report a physical deposition-based, one-step quantum dot (QD) synthesis and assembly on ternary metal oxide nanowires for photovoltaic applications. Typical solution-based synthesis of colloidal QDs for QD sensitized solar cells involves nontrivial ligand exchange processing and toxic wet chemicals, and the effect of the ligands on carrier transport has not been fully understood. In this research using pulsed laser deposition, CdSe QDs were coated on Zn2SnO4 nanowires without ligand molecules, and the coverage could be controlled by adjusting the laser fluence. Growth of QDs in dense nanowire network structures was also achieved, and photovoltaic cells fabricated using this method exhibited promising device performance. This approach could be further applied for the assembly of QDs where ligand exchange is difficult and could possibly lead to reduced fabrication cost and improved device performance.
Single Crystalline β-Ag2Te Nanowire as a New Topological Insulator
Sunghun Lee - ,
Juneho In - ,
Youngdong Yoo - ,
Younghun Jo - ,
Yun Chang Park - ,
Hyung-jun Kim - ,
Hyun Cheol Koo *- ,
Jinhee Kim *- ,
Bongsoo Kim *- , and
Kang L. Wang
A recent theoretical study suggested that Ag2Te is a topological insulator with a highly anisotropic Dirac cone. Novel physics in the topological insulators with an anisotropic Dirac cone is anticipated due to the violation of rotational invariance. From magnetoresistance (MR) measurements of Ag2Te nanowires (NWs), we have observed Aharanov–Bohm (AB) oscillation, which is attributed to the quantum interference of electron phase around the perimeter of the NW. Angle and temperature dependences of the AB oscillation indicate the existence of conducting surface states in the NWs, confirming that Ag2Te is a topological insulator. For Ag2Te nanoplates (NPLs), we have observed high carrier mobility exceeding 22 000 cm2/(V s) and pronounced Shubnikov–de Haas (SdH) oscillation. From the SdH oscillation, we have obtained Fermi state parameters of the Ag2Te NPLs, which can provide valuable information on Ag2Te. Understanding the basic physics of the topological insulator with an anisotropic Dirac cone could lead to new applications in nanoelectronics and spintronics.
On the Origin of Photoluminescence in Silicon Nanocrystals: Pressure-Dependent Structural and Optical Studies
Daniel C. Hannah - ,
Jihua Yang - ,
Paul Podsiadlo - ,
Maria K.Y. Chan - ,
Arnaud Demortière - ,
David J. Gosztola - ,
Vitali B. Prakapenka - ,
George C. Schatz - ,
Uwe Kortshagen - , and
Richard D. Schaller *
A lack of consensus persists regarding the origin of photoluminescence in silicon nanocrystals. Here we report pressure-dependences of X-ray diffraction and photoluminescence from alkane-terminated colloidal particles. We determine the diamond-phase bulk modulus, observe multiple phase transitions, and importantly find a systematic photoluminescence red shift that matches the Xconduction-to-Γvalence transition of bulk crystalline silicon. These results, reinforced by calculations, suggest that the efficient photoluminescence, frequently attributed to defects, arises instead from core-states that remain highly indirect despite quantum confinement.
Synergistic Effects from Graphene and Carbon Nanotubes Enable Flexible and Robust Electrodes for High-Performance Supercapacitors
Yingwen Cheng - ,
Songtao Lu - ,
Hongbo Zhang - ,
Chakrapani V. Varanasi - , and
Jie Liu *
Flexible and lightweight energy storage systems have received tremendous interest recently due to their potential applications in wearable electronics, roll-up displays, and other devices. To manufacture such systems, flexible electrodes with desired mechanical and electrochemical properties are critical. Herein we present a novel method to fabricate conductive, highly flexible, and robust film supercapacitor electrodes based on graphene/MnO2/CNTs nanocomposites. The synergistic effects from graphene, CNTs, and MnO2 deliver outstanding mechanical properties (tensile strength of 48 MPa) and superior electrochemical activity that were not achieved by any of these components alone. These flexible electrodes allow highly active material loading (71 wt % MnO2), areal density (8.80 mg/cm2), and high specific capacitance (372 F/g) with excellent rate capability for supercapacitors without the need of current collectors and binders. The film can also be wound around 0.5 mm diameter rods for fabricating full cells with high performance, showing significant potential in flexible energy storage devices.
Engineering Graphene Mechanical Systems
Maxim K. Zalalutdinov - ,
Jeremy T. Robinson *- ,
Chad E. Junkermeier - ,
James C. Culbertson - ,
Thomas L. Reinecke - ,
Rory Stine - ,
Paul E. Sheehan - ,
Brian H. Houston - , and
Eric S. Snow
We report a method to introduce direct bonding between graphene platelets that enables the transformation of a multilayer chemically modified graphene (CMG) film from a “paper mache-like” structure into a stiff, high strength material. On the basis of chemical/defect manipulation and recrystallization, this technique allows wide-range engineering of mechanical properties (stiffness, strength, density, and built-in stress) in ultrathin CMG films. A dramatic increase in the Young’s modulus (up to 800 GPa) and enhanced strength (sustainable stress ≥1 GPa) due to cross-linking, in combination with high tensile stress, produced high-performance (quality factor of 31 000 at room temperature) radio frequency nanomechanical resonators. The ability to fine-tune intraplatelet mechanical properties through chemical modification and to locally activate direct carbon–carbon bonding within carbon-based nanomaterials will transform these systems into true “materials-by-design” for nanomechanics.
Cooperative Vaccinia Infection Demonstrated at the Single-Cell Level Using FluidFM
Philipp Stiefel - ,
Florian I. Schmidt - ,
Pablo Dörig - ,
Pascal Behr - ,
Tomaso Zambelli *- ,
Julia A. Vorholt - , and
Jason Mercer *
The mechanisms used by viruses to enter and replicate within host cells are subjects of intense investigation. These studies are ultimately aimed at development of new drugs that interfere with these processes. Virus entry and infection are generally monitored by dispensing bulk virus suspensions on layers of cells without accounting for the fate of each virion. Here, we take advantage of the recently developed FluidFM to deposit single vaccinia virions onto individual cells in a controlled manner. While the majority of virions were blocked prior to early gene expression, infection of individual cells increased in a nondeterministic fashion with respect to the number of viruses placed. Microscopic analyses of several stages of the virus lifecycle indicated that this was the result of cooperativity between virions during early stages of infection. These findings highlight the importance of performing controlled virus infection experiments at the single cell level.
Color Matrix Refractive Index Sensors Using Coupled Vertical Silicon Nanowire Arrays
M. Khorasaninejad - ,
N. Abedzadeh - ,
J. Walia - ,
S. Patchett - , and
S. S. Saini *
Vivid colors are demonstrated in silicon nanowires with diameters ranging from 105 to 346 nm. The nanowires are vertically arranged in a square lattice with a pitch of 400 nm and are electromagnetically coupled to each other, resulting in frequency-dependent reflection spectra. Since the coupling is dependent on the refractive index of the medium surrounding the nanowires, the arrays can be used for sensing. A simple sensor is demonstrated by observing the change in the reflected color with changing refractive index of the surrounding medium. A refractive index resolution of 5 × 10–5 is achieved by analyzing bright-field images captured with an optical microscope equipped with a charge coupled device camera.
Multiple Exciton Generation and Dissociation in PbS Quantum Dot-Electron Acceptor Complexes
Ye Yang - ,
William Rodríguez-Córdoba - , and
Tianquan Lian *
Multiple exciton generation (MEG) in quantum dots (QDs), a process by which one absorbed photon generates multiple electron–hole pairs, has provided exciting possibilities for improving the energy conversion efficiency of photovoltaic and photocatalytic devices. However, implementing MEG in practical devices requires the extraction of multiple charge carriers before exciton–exciton annihilation and the development of materials with improved MEG efficiency. In this report, using PbS QD/methylene blue complexes as a QD/electron acceptor model system, we demonstrate that the presence of electron acceptors does not affect the MEG efficiency of QDs and all generated excitons can be dissociated by electron transfer to the acceptor, achieving MEG and multiple exciton dissociation efficiencies of 112%. We further demonstrate that these efficiencies are not affected by the charging of QDs.
Metal Oxide Nanoparticle Mediated Enhanced Raman Scattering and Its Use in Direct Monitoring of Interfacial Chemical Reactions
Li Li - ,
Tanya Hutter - ,
Alexander S. Finnemore - ,
Fu Min Huang - ,
Jeremy J. Baumberg - ,
Stephen R. Elliott - ,
Ullrich Steiner - , and
Sumeet Mahajan *
Metal oxide nanoparticles (MONPs) have widespread usage across many disciplines, but monitoring molecular processes at their surfaces in situ has not been possible. Here we demonstrate that MONPs give highly enhanced (×104) Raman scattering signals from molecules at the interface permitting direct monitoring of their reactions, when placed on top of flat metallic surfaces. Experiments with different metal oxide materials and molecules indicate that the enhancement is generic and operates at the single nanoparticle level. Simulations confirm that the amplification is principally electromagnetic and is a result of optical modulation of the underlying plasmonic metallic surface by MONPs, which act as scattering antennae and couple light into the confined region sandwiched by the underlying surface. Because of additional functionalities of metal oxides as magnetic, photoelectrochemical and catalytic materials, enhanced Raman scattering mediated by MONPs opens up significant opportunities in fundamental science, allowing direct tracking and understanding of application-specific transformations at such interfaces. We show a first example by monitoring the MONP-assisted photocatalytic decomposition reaction of an organic dye by individual nanoparticles.
Bipolar Resistive Switching of Single Gold-in-Ga2O3 Nanowire
Chia-Wei Hsu - and
Li-Jen Chou *
We have fabricated single nanowire chips on gold-in-Ga2O3 core–shell nanowires using the electron-beam lithography techniques and realized bipolar resistive switching characteristics having invariable set and reset voltages. We attribute the unique property of invariance to the built-in conduction path of gold core. This invariance allows us to fabricate many resistive switching cells with the same operating voltage by simple depositing repetitive metal electrodes along a single nanowire. Other characteristics of these core–shell resistive switching nanowires include comparable driving electric field with other thin film and nanowire devices and a remarkable on/off ratio more than 3 orders of magnitude at a low driving voltage of 2 V. A smaller but still impressive on/off ratio of 10 can be obtained at an even lower bias of 0.2 V. These characteristics of gold-in-Ga2O3 core–shell nanowires make fabrication of future high-density resistive memory devices possible.
A DNA Nanostructure Platform for Directed Assembly of Synthetic Vaccines
Xiaowei Liu - ,
Yang Xu - ,
Tao Yu - ,
Craig Clifford - ,
Yan Liu - ,
Hao Yan *- , and
Yung Chang *
Safe and effective vaccines offer the best intervention for disease control. One strategy to maximize vaccine immunogenicity without compromising safety is to rationally design molecular complexes that mimic the natural structure of immunogenic microbes but without the disease-causing components. Here we use highly programmable DNA nanostructures as platforms to assemble a model antigen and CpG adjuvants together into nanoscale complexes with precise control of the valency and spatial arrangement of each element. Our results from immunized mice show that compared to a mixture of antigen and CpG molecules, the assembled antigen-adjuvant-DNA complexes induce strong and long-lasting antibody responses against the antigen without stimulating a reaction to the DNA nanostructure itself. This result demonstrates the potential of DNA nanostructures to serve as general platforms for the rational design and construction of a variety of vaccines.
Exciton–Plasmon Interactions in Quantum Dot–Gold Nanoparticle Structures
Eyal Cohen-Hoshen *- ,
Garnett W. Bryant - ,
Iddo Pinkas - ,
Joseph Sperling - , and
Israel Bar-Joseph
We present a self-assembly method to construct CdSe/ZnS quantum dot–gold nanoparticle complexes. This method allows us to form complexes with relatively good control of the composition and structure that can be used for detailed study of the exciton–plasmon interactions. We determine the contribution of the polarization-dependent near-field enhancement, which may enhance the absorption by nearly two orders of magnitude and that of the exciton coupling to plasmon modes, which modifies the exciton decay rate.
Synthesis of PtPd Bimetal Nanocrystals with Controllable Shape, Composition, and Their Tunable Catalytic Properties
Xiaoqing Huang - ,
Yujing Li - ,
Yongjia Li - ,
Hailong Zhou - ,
Xiangfeng Duan - , and
Yu Huang *
We report a facile synthetic strategy to single-crystalline PtPd nanocrystals with controllable shapes and tunable compositions. In the developed synthesis, the molar ratio of the starting precursors determines the composition in the final PtPd nanocrystals, while the halides function as the shape-directing agent to induce the formation of PtPd nanocrystals with cubic or octahedral/tetrahedral morphology. These obtained PtPd nanocrystals exhibit high activity in the hydrogenation of nitrobenzene, and their performance is highly shape- and composition-dependent with Pt in ∼50% showing the optimum activity and the {100}-facet-enclosed PtPd nanocrystals demonstrating a higher activity than the {111}-facet-bounded PtPd nanocrystals.
Negligible Particle-Specific Antibacterial Activity of Silver Nanoparticles
Zong-ming Xiu - ,
Qing-bo Zhang - ,
Hema L. Puppala - ,
Vicki L. Colvin - , and
Pedro J. J. Alvarez *
For nearly a decade, researchers have debated the mechanisms by which AgNPs exert toxicity to bacteria and other organisms. The most elusive question has been whether the AgNPs exert direct “particle-specific” effects beyond the known antimicrobial activity of released silver ions (Ag+). Here, we infer that Ag+ is the definitive molecular toxicant. We rule out direct particle-specific biological effects by showing the lack of toxicity of AgNPs when synthesized and tested under strictly anaerobic conditions that preclude Ag(0) oxidation and Ag+ release. Furthermore, we demonstrate that the toxicity of various AgNPs (PEG- or PVP- coated, of three different sizes each) accurately follows the dose–response pattern of E. coli exposed to Ag+ (added as AgNO3). Surprisingly, E. coli survival was stimulated by relatively low (sublethal) concentration of all tested AgNPs and AgNO3 (at 3–8 μg/L Ag+, or 12–31% of the minimum lethal concentration (MLC)), suggesting a hormetic response that would be counterproductive to antimicrobial applications. Overall, this work suggests that AgNP morphological properties known to affect antimicrobial activity are indirect effectors that primarily influence Ag+ release. Accordingly, antibacterial activity could be controlled (and environmental impacts could be mitigated) by modulating Ag+ release, possibly through manipulation of oxygen availability, particle size, shape, and/or type of coating.
Stabilization of Ferromagnetic Order in La0.7Sr0.3MnO3–SrRuO3 Superlattices
M. Ziese *- ,
F. Bern - ,
E. Pippel - ,
D. Hesse - , and
I. Vrejoiu *
The study of spatially confined complex oxides is of wide interest, since correlated electrons at interfaces might form exotic phases. Here La0.7Sr0.3MnO3/SrRuO3 superlattices with coherently grown interfaces were studied by structural techniques, magnetization, and magnetotransport measurements. Magnetization measurements showed that ferromagnetic order in ultrathin La0.7Sr0.3MnO3 layers is stabilized in the superlattices down to layer thicknesses of at least two unit cells. This stabilization is destroyed, if the ferromagnetic layers are separated by two unit cell thick SrTiO3 layers. The resistivity of the superlattices showed metallic behavior and was dominated by the conducting SrRuO3 layers, the off-diagonal resistivity showed an anomalous Hall effect from both SrRuO3 and La0.7Sr0.3MnO3 layers. This shows that the La0.7Sr0.3MnO3 layers are not only ferromagnetic but also highly conducting; probably a conducting hole gas is induced at the interfaces that stabilizes the ferromagnetic order. This result opens up an alternative route for the fabrication of two-dimensional systems with long-range ferromagnetic order.
Focused Orientation and Position Imaging (FOPI) of Single Anisotropic Plasmonic Nanoparticles by Total Internal Reflection Scattering Microscopy
Ji Won Ha - ,
Kyle Marchuk - , and
Ning Fang *
The defocused orientation and position imaging (DOPI) and polarization-based in-focus imaging techniques have been widely used for detecting rotational motions with anisotropic gold nanorods (AuNRs) as orientation probes. However, these techniques have a number of significant limitations, such as the greatly reduced signal intensity and relatively low spatial and temporal resolutions for out-of-focus AuNRs and the angular degeneracy for in-focus AuNRs. Herein, we present a total internal reflection (TIR) scattering-based focused orientation and position imaging (FOPI) of AuNRs supported on a 50 nm thick gold film, which enables us to overcome the aforementioned limitations. Imaging AuNRs under the TIR scattering microscope provides excellent signal-to-noise ratio and results in no deteriorating images. The scattering patterns of AuNRs on the gold substrate are affected by the strong interaction of the excited dipole in the AuNR with the image dipole in the gold substrate. The doughnut-shaped scattering field distribution allows for high-throughput determination of the three-dimensional spatial orientation of in-focus AuNRs within a single frame without angular degeneracy. Therefore, the TIR scattering-based FOPI method is demonstrated to be an outstanding candidate for studying dynamics of functionalized nanoparticles on a large variety of functional surfaces.
Pt–Au Alloying at the Nanoscale
Valeri Petkov *- ,
Bridgid N. Wanjala - ,
Rameshwori Loukrakpam - ,
Jin Luo - ,
Lefu Yang - ,
Chuan-Jian Zhong - , and
Sarvjit Shastri
The formation of nanosized alloys between a pair of elements, which are largely immiscible in bulk, is examined in the archetypical case of Pt and Au. Element specific resonant high-energy X-ray diffraction experiments coupled to atomic pair distribution functions analysis and computer simulations prove the formation of Pt–Au alloys in particles less than 10 nm in size. In the alloys, Au–Au and Pt–Pt bond lengths differing in 0.1 Å are present leading to extra structural distortions as compared to pure Pt and Au particles. The alloys are found to be stable over a wide range of Pt–Au compositions and temperatures contrary to what current theory predicts. The alloy-type structure of Pt–Au nanoparticles comes along with a high catalytic activity for electrooxidation of methanol making an excellent example of the synergistic effect of alloying at the nanoscale on functional properties.
Screening-Engineered Field-Effect Solar Cells
William Regan - ,
Steven Byrnes - ,
Will Gannett - ,
Onur Ergen - ,
Oscar Vazquez-Mena - ,
Feng Wang - , and
Alex Zettl *
Photovoltaics (PV) are a promising source of clean renewable energy, but current technologies face a cost-to-efficiency trade-off that has slowed widespread implementation.(1, 2) We have developed a PV architecture—screening-engineered field-effect photovoltaics (SFPV)—that in principle enables fabrication of low-cost, high efficiency PV from virtually any semiconductor, including the promising but hard-to-dope metal oxides, sulfides, and phosphides.(3) Prototype SFPV devices have been constructed and are found to operate successfully in accord with model predictions.
Interface Driven Energy Filtering of Thermoelectric Power in Spark Plasma Sintered Bi2Te2.7Se0.3 Nanoplatelet Composites
Ajay Soni - ,
Yiqiang Shen - ,
Ming Yin - ,
Yanyuan Zhao - ,
Ligen Yu - ,
Xiao Hu - ,
Zhili Dong - ,
Khiam Aik Khor - ,
Mildred S. Dresselhaus - , and
Qihua Xiong *
Control of competing parameters such as thermoelectric (TE) power and electrical and thermal conductivities is essential for the high performance of thermoelectric materials. Bulk-nanocomposite materials have shown a promising improvement in the TE performance due to poor thermal conductivity and charge carrier filtering by interfaces and grain boundaries. Consequently, it has become pressingly important to understand the formation mechanisms, stability of interfaces and grain boundaries along with subsequent effects on the physical properties. We report here the effects of the thermodynamic environment during spark plasma sintering (SPS) on the TE performance of bulk-nanocomposites of chemically synthesized Bi2Te2.7Se0.3 nanoplatelets. Four pellets of nanoplatelets powder synthesized in the same batch have been made by SPS at different temperatures of 230, 250, 280, and 350 °C. The X-ray diffraction, transmission electron microscopy, thermoelectric, and thermal transport measurements illustrate that the pellet sintered at 250 °C shows a minimum grain growth and an optimal number of interfaces for efficient TE figure of merit, ZT∼0.55. For the high temperature (350 °C) pelletized nanoplatelet composites, the concurrent rise in electrical and thermal conductivities with a deleterious decrease in thermoelectric power have been observed, which results because of the grain growth and rearrangements of the interfaces and grain boundaries. Cross section electron microscopy investigations indeed show significant grain growth. Our study highlights an optimized temperature range for the pelletization of the nanoplatelet composites for TE applications. The results provide a subtle understanding of the grain growth mechanism and the filtering of low energy electrons and phonons with thermoelectric interfaces.
Extremely High Tunability and Low Loss in Nanoscaffold Ferroelectric Films
OonJew Lee - ,
Sophie A. Harrington - ,
Ahmed Kursumovic - ,
Emmanuel Defay - ,
Haiyan Wang - ,
Zhenxing Bi - ,
Chen-Fong Tsai - ,
Li Yan - ,
Quanxi Jia - , and
Judith L. MacManus-Driscoll *
There are numerous radio frequency and microwave device applications which require materials with high electrical tunability and low dielectric loss. For phased array antenna applications there is also a need for materials which can operate above room temperature and which have a low temperature coefficient of capacitance. We have created a nanoscaffold composite ferroelectric material containing Ba0.6Sr0.4TiO3 and Sm2O3 which has a very high tunability which scales inversely with loss. This behavior is opposite to what has been demonstrated in any previous report. Furthermore, the materials operate from room temperature to above 150 °C, while maintaining high tunability and low temperature coefficient of tunability. This new paradigm in dielectric property control comes about because of a vertical strain control mechanism which leads to high tetragonality (c/a ratio of 1.0126) in the BSTO. Tunability values of 75% (200 kV/cm field) were achieved at room temperature in micrometer thick films, the value remaining to >50% at 160 °C. Low dielectric loss values of <0.01 were also achieved, significantly lower than reference pure films.
Ferroelectricity in Simple Binary ZrO2 and HfO2
Johannes Müller *- ,
Tim S. Böscke - ,
Uwe Schröder - ,
Stefan Mueller - ,
Dennis Bräuhaus - ,
Ulrich Böttger - ,
Lothar Frey - , and
Thomas Mikolajick
The transition metal oxides ZrO2 and HfO2 as well as their solid solution are widely researched and, like most binary oxides, are expected to exhibit centrosymmetric crystal structure and therewith linear dielectric characteristics. For this reason, those oxides, even though successfully introduced into microelectronics, were never considered to be more than simple dielectrics possessing limited functionality. Here we report the discovery of a field-driven ferroelectric phase transition in pure, sub 10 nm ZrO2 thin films and a composition- and temperature-dependent transition to a stable ferroelectric phase in the HfO2–ZrO2 mixed oxide. These unusual findings are attributed to a size-driven tetragonal to orthorhombic phase transition that in thin films, similar to the anticipated tetragonal to monoclinic transition, is lowered to room temperature. A structural investigation revealed the orthorhombic phase to be of space group Pbc21, whose noncentrosymmetric nature is deemed responsible for the spontaneous polarization in this novel, nanoscale ferroelectrics.
Liquid Plasmonics: Manipulating Surface Plasmon Polaritons via Phase Transitions
S. R. C. Vivekchand - ,
Clifford J. Engel - ,
Steven M. Lubin - ,
Martin G. Blaber - ,
Wei Zhou - ,
Jae Yong Suh - ,
George C. Schatz - , and
Teri W. Odom *
This paper reports the manipulation of surface plasmon polaritons (SPPs) in a liquid plasmonic metal by changing its physical phase. Dynamic properties were controlled by solid-to-liquid phase transitions in 1D Ga gratings that were fabricated using a simple molding process. Solid and liquid phases were found to exhibit different plasmonic properties, where light coupled to SPPs more efficiently in the liquid phase. We exploited the supercooling characteristics of Ga to access plasmonic properties associated with the liquid phase over a wider temperature range (up to 30 °C below the melting point of bulk Ga). Ab initio density functional theory–molecular dynamic calculations showed that the broadening of the solid-state electronic band structure was responsible for the superior plasmonic properties of the liquid metal.
Brownian Motion in a Designer Force Field: Dynamical Effects of Negative Refraction on Nanoparticles
A. Cuche - ,
B. Stein - ,
A. Canaguier-Durand - ,
E. Devaux - ,
C. Genet *- , and
T. W. Ebbesen
Photonic crystals (PC) have demonstrated unique features that have renewed the fields of classical and quantum optics. Although holding great promises, associated mechanical effects have proven challenging to observe. We demonstrate for the first time that one of the most salient properties of PC, namely negative refraction, can induce specific forces on metal nanoparticles. By integrating a periodically patterned metal film in a fluidic cell, we show that near-field optical forces associated with negatively refracted surface plasmons are capable of controlling particle trajectories. Coupling particle motions to PC band structures draws new approaches and strategies for parallel and high resolution all-optical control of particle flows with applications for micro- and nanofluidic systems.
A Transmission Electron Microscopy Study of the Electrochemical Process of Lithium–Oxygen Cells
Hun-Gi Jung - ,
Hee-Soo Kim - ,
Jin-Bum Park - ,
In-Hwan Oh - ,
Jusef Hassoun - ,
Chong Seung Yoon *- ,
Bruno Scrosati *- , and
Yang-Kook Sun *
The electrochemical reaction of a lithium–oxygen cell using a tetraethylene glycol dimethyl ether-lithium triflate, TEGDME-LiCF3SO3 electrolyte, is investigated by a detailed transmission electron microscopy analysis. The results confirm the reversibility of the process by showing the formation–dissolution of lithium peroxide, Li2O2, upon repeating cell charge and discharge cycles.
Intersublevel Spectroscopy on Single InAs-Quantum Dots by Terahertz Near-Field Microscopy
Rainer Jacob - ,
Stephan Winnerl *- ,
Markus Fehrenbacher - ,
Jayeeta Bhattacharyya - ,
Harald Schneider - ,
Marc Tobias Wenzel - ,
Hans-Georg von Ribbeck - ,
Lukas M. Eng - ,
Paola Atkinson - ,
Oliver G. Schmidt - , and
Manfred Helm
Using scattering-type near-field infrared microscopy in combination with a free-electron laser, intersublevel transitions in buried single InAs quantum dots are investigated. The experiments are performed at room temperature on doped self-assembled quantum dots capped with a 70 nm GaAs layer. Clear near-field contrast of single dots is observed when the photon energy of the incident beam matches intersublevel transition energies, namely the p-d and s-d transition of conduction band electrons confined in the dots. The observed room-temperature line width of 5–8 meV of these resonances in the mid-infrared range is significantly below the inhomogeneously broadened spectral lines of quantum dot ensembles. The experiment highlights the strength of near-field microspectroscopy by demonstrating signals from bound-to-bound transitions of single electrons in a probe volume of the order of (100 nm)3.
Crystallinity Control of Ferromagnetic Contacts in Stressed Nanowire Templates and the Magnetic Domain Anisotropy
Yung-Chen Lin - ,
Yu Chen - ,
Renjie Chen - ,
Kaushik Ghosh - ,
Qihua Xiong - , and
Yu Huang *
We report the controlled growth of single-crystalline ferromagnetic contacts through solid state reaction at nanoscale. Single-crystal Mn5Si3 and Fe5Ge3 contacts were grown within stressed Si and Ge nanowire templates, where oxide-shells were used to exert compressive stress on the silicide or germanide. Compared to polycrystalline silicide and germanide structures observed within bare nanowires, the built-in high strain in the oxide-shelled nanostructures alters the nucleation behavior of the ferromagnetic materials, leading to single crystal growth in the transverse/radial direction. Interestingly, the compressive stress is also found to affect the magnetic anisotropy of the ferromagnetic contacts. In-plane and out-of-plane magnetization were observed in Fe5Ge3 for different crystal orientations, showing distinctly preferred domain orientations. These interesting results display the capability to control both the crystallinity and the magnetic anisotropy of ferromagnetic contacts in engineered nanostructures.
Plasmonic Color Filters for CMOS Image Sensor Applications
Sozo Yokogawa - ,
Stanley P. Burgos - , and
Harry A. Atwater *
We report on the optical properties of plasmonic hole arrays as they apply to requirements for plasmonic color filters designed for state-of-the-art Si CMOS image sensors. The hole arrays are composed of hexagonally packed subwavelength sized holes on a 150 nm Al film designed to operate at the primary colors of red, green, and blue. Hole array plasmonic filters show peak transmission in the 40–50% range for large (>5 × 5 μm2) size filters and maintain their filtering function for pixel sizes as small as ∼1 × 1 μm2, albeit at a cost in transmission efficiency. Hole array filters are found to robust with respect to spatial crosstalk between pixel within our detection limit and preserve their filtering function in arrays containing random defects. Analysis of hole array filter transmittance and crosstalk suggests that nearest neighbor hole–hole interactions rather than long-range interactions play the dominant role in the transmission properties of plasmonic hole array filters. We verify this via a simple nearest neighbor model that correctly predicts the hole array transmission efficiency as a function of the number of holes.
Effects of Magnetic Doping on Weak Antilocalization in Narrow Bi2Se3 Nanoribbons
Judy J. Cha - ,
Martin Claassen - ,
Desheng Kong - ,
Seung Sae Hong - ,
Kristie J. Koski - ,
Xiao-Liang Qi - , and
Yi Cui *
We report low-temperature, magnetotransport measurements of ferrocene-doped Bi2Se3 nanoribbons grown by vapor–liquid–solid method. The Kondo effect, a saturating resistance upturn at low temperatures, is observed in these ribbons to indicate presence of localized impurity spins. Magnetoconductances of the ferrocene-doped ribbons display both weak localization and weak antilocalization, which is in contrast with those of undoped ribbons that show only weak antilocalization. We show that the observed magnetoconductances are governed by a one-dimensional localization theory that includes spin orbit coupling and magnetic impurity scattering, yielding various scattering and dephasing lengths for Bi2Se3. The power law decay of the dephasing length on temperature also reflects one-dimensional localization regime in these narrow Bi2Se3 nanoribbons. The emergence of weak localization in ferrocene-doped Bi2Se3 nanoribbons presents ferrocene as an effective magnetic dopant source.
High Carrier Mobility in Single Ultrathin Colloidal Lead Selenide Nanowire Field Effect Transistors
Rion Graham - and
Dong Yu *
Ultrathin colloidal lead selenide (PbSe) nanowires with continuous charge transport channels and tunable bandgap provide potential building blocks for solar cells and photodetectors. Here, we demonstrate a room-temperature hole mobility as high as 490 cm2/(V s) in field effect transistors incorporating single colloidal PbSe nanowires with diameters of 6–15 nm, coated with ammonium thiocyanate and a thin SiO2 layer. A long carrier diffusion length of 4.5 μm is obtained from scanning photocurrent microscopy (SPCM). The mobility is increased further at lower temperature, reaching 740 cm2/(V s) at 139 K.
Independent Control of Bulk and Interfacial Morphologies of Small Molecular Weight Organic Heterojunction Solar Cells
Jeramy D. Zimmerman - ,
Xin Xiao - ,
Christopher Kyle Renshaw - ,
Siyi Wang - ,
Vyacheslav V. Diev - ,
Mark E. Thompson - , and
Stephen R. Forrest
We demonstrate that solvent vapor annealing of small molecular weight organic heterojunctions can be used to independently control the interface and bulk thin-film morphologies, thereby modifying charge transport and exciton dissociation in these structures. As an example, we anneal diphenyl-functionalized squaraine (DPSQ)/C60 heterojunctions before or after the deposition of C60. Solvent vapor annealing of DPSQ before C60 deposition results in molecular order at the heterointerface. Organic photovoltaics based on this process have reduced open circuit voltages and power conversion efficiencies relative to as-cast devices. In contrast, annealing following C60 deposition locks in interface disorder found in unannealed junctions while improving order in the thin-film bulk. This results in an increase in short circuit current by >30% while maintaining the open circuit voltage of the as-cast heterojunction device. These results are analyzed in terms of recombination dynamics at excitonic heterojunctions and demonstrate that the optimal organic photovoltaic morphology is characterized by interfacial disorder to minimize polaron-pair recombination, while improved crystallinity in the bulk increases exciton and charge transport efficiency in the active region.
Tuning Radiative Recombination in Cu-Doped Nanocrystals via Electrochemical Control of Surface Trapping
Sergio Brovelli - ,
Christophe Galland - ,
Ranjani Viswanatha - , and
Victor I. Klimov *
The incorporation of copper dopants into II–VI colloidal nanocrystals (NCs) leads to the introduction of intragap electronic states and the development of a new emission feature due to an optical transition which couples the NC conduction band to the Cu-ion state. The mechanism underlying Cu-related emission and specifically the factors that control the branching between the intrinsic and impurity-related emission channels remain unclear. Here, we address this problem by conducting spectro-electrochemical measurements on Cu-doped core/shell ZnSe/CdSe NCs. These measurements indicate that the distribution of photoluminescence (PL) intensity between the intrinsic and the impurity bands as well as the overall PL efficiency can be controlled by varying the occupancy of surface defect sites. Specifically, by activating hole traps under negative electrochemical potential (the Fermi level is raised), we can enhance the Cu band at the expense of band-edge emission, which is consistent with the predominant Cu2+ character of the dopant ions. Furthermore, we observe an overall PL “brightening” under negative potential and “dimming” under positive potential, which we attribute to changes in the occupancy of the electron trap sites (that is, the degree of their electronic passivation) that control nonradiative losses due to electron surface trapping.
Steric Hindrance Induces crosslike Self-Assembly of Gold Nanodumbbells
Marek Grzelczak *- ,
Ana Sánchez-Iglesias - ,
Hamed Heidari Mezerji - ,
Sara Bals - ,
Jorge Pérez-Juste - , and
Luis M. Liz-Marzán *
In the formation of colloidal molecules, directional interactions are crucial for controlling the spatial distribution of the building blocks. Anisotropic nanoparticles facilitate directional clustering via steric constraints imposed by each specific shape, thereby restricting assembly along certain directions. We show in this Letter that the combination of patchiness (attraction) and shape (steric hindrance) allows assembling gold nanodumbbell building blocks into crosslike dimers with well-controlled interparticle distance and relative orientation. Steric hindrance between interacting dumbbell-like particles opens up a new synthetic approach toward low-symmetry plasmonic clusters, which may significantly contribute to understand complex plasmonic phenomena.
Luminescence Quantum Yield of Single Gold Nanorods
Mustafa Yorulmaz - ,
Saumyakanti Khatua - ,
Peter Zijlstra - ,
Alexander Gaiduk - , and
Michel Orrit *
We study the luminescence quantum yield (QY) of single gold nanorods with different aspect ratios and volumes. Compared to gold nanospheres, we observe an increase of QY by about an order of magnitude for particles with a plasmon resonance >650 nm. The observed trend in QY is further confirmed by controlled reshaping of a single gold nanorod to a spherelike shape. Moreover, we identify two spectral components, one around 500 nm originating from a combination of interband transitions and the transverse plasmon and one coinciding with the longitudinal plasmon band. These components are analyzed by correlating scattering and luminescence spectra of single nanorods and performing polarization sensitive measurements. Our study contributes to the understanding of luminescence from gold nanorods. The enhanced QY we report can benefit applications in biological and soft matter studies.
Periodic Bicontinuous Composites for High Specific Energy Absorption
Jae-Hwang Lee - ,
Lifeng Wang - ,
Mary C. Boyce - , and
Edwin L. Thomas *
We report on the mechanical behavior of an interpenetrating carbon/epoxy periodic submicrometer-scale bicontinuous composite material fabricated following the design principles deduced from biological composites. Using microscopic uniaxial compressive tests, the specific energy absorption is quantitatively evaluated and compared with the epoxy/air and carbon/air precursors. The carbon/epoxy material demonstrates extremely high specific energy absorption up to 720 kJ/kg and shear-dominant interphase interactions from the interlocked hard (carbon) and soft (epoxy) phases. Such bicontinuous nanocomposites are a new type of structural metamaterial with designed cell topology and mechanical anisotropy. Their inherent small length scale can play a critical role in prohibiting segregated mechanical responses leading to flaw tolerance.
Reactive Flow in Silicon Electrodes Assisted by the Insertion of Lithium
Kejie Zhao - ,
Georgios A. Tritsaris - ,
Matt Pharr - ,
Wei L. Wang - ,
Onyekwelu Okeke - ,
Zhigang Suo - ,
Joost J. Vlassak - , and
Efthimios Kaxiras *
In the search for high-energy density materials for Li-ion batteries, silicon has emerged as a promising candidate for anodes due to its ability to absorb a large number of Li atoms. Lithiation of Si leads to large deformation and concurrent changes in its mechanical properties, from a brittle material in its pure form to a material that can sustain large inelastic deformation in the lithiated form. These remarkable changes in behavior pose a challenge to theoretical treatment of the material properties. Here, we provide a detailed picture of the origin of changes in the mechanical properties, based on first-principles calculations of the atomic-scale structural and electronic properties in a model amorphous silicon (a-Si) structure. We regard the reactive flow of lithiated silicon as a nonequilibrium process consisting of concurrent Li insertion driven by unbalanced chemical potential and flow driven by deviatoric stress. The reaction enables the material to flow at a lower level of stress. Our theoretical model is in excellent quantitative agreement with experimental measurements of lithiation-induced stress on a Si thin film.
Nanopatterned Electrically Conductive Films of Semiconductor Nanocrystals
Tamar S. Mentzel *- ,
Darcy D. Wanger - ,
Nirat Ray - ,
Brian J. Walker - ,
David Strasfeld - ,
Moungi G. Bawendi - , and
Marc A. Kastner
We present the first semiconductor nanocrystal films of nanoscale dimensions that are electrically conductive and crack-free. These films make it possible to study the electrical properties intrinsic to the nanocrystals unimpeded by defects such as cracking and clustering that typically exist in larger-scale films. We find that the electrical conductivity of the nanoscale films is 180 times higher than that of drop-cast, microscopic films made of the same type of nanocrystal. Our technique for forming the nanoscale films is based on electron-beam lithography and a lift-off process. The patterns have dimensions as small as 30 nm and are positioned on a surface with 30 nm precision. The method is flexible in the choice of nanocrystal core–shell materials and ligands. We demonstrate patterns with PbS, PbSe, and CdSe cores and Zn0.5Cd0.5Se–Zn0.5Cd0.5S core–shell nanocrystals with a variety of ligands. We achieve unprecedented versatility in integrating semiconductor nanocrystal films into device structures both for studying the intrinsic electrical properties of the nanocrystals and for nanoscale optoelectronic applications.
Tilted Face-Centered-Cubic Supercrystals of PbS Nanocubes
Zewei Quan - ,
Welley Siu Loc - ,
Cuikun Lin - ,
Zhiping Luo - ,
Kaikun Yang - ,
Yuxuan Wang - ,
Howard Wang - ,
Zhongwu Wang *- , and
Jiye Fang *
We demonstrate a direct fabrication of PbS nanocube supercrystals without size-selection pretreatment on the building blocks. Electron microscopic and synchrotron small angle X-ray scattering analyses confirm that nanocubes pack through a tilted face-centered-cubic (fcc) arrangement, that is, face-to-face along the ⟨110⟩super direction, resulting in a real packing efficiency of as high as ∼83%. This new type of superstructure consisting of nanocubes as building blocks, reported here for the first time, is considered the most stable surfactant-capped nanocube superstructure determined by far.
Additions and Corrections
Correction to Induction of Malaria Parasite Migration by Synthetically Tunable Microenvironments
Nadine Perschmann - ,
Janina Kristin Hellmann - ,
Friedrich Frischknecht - , and
Joachim P. Spatz
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Correction to Dynamic Fluctuations in Ultrasmall Nanocrystals Induce White Light Emission
Timothy J. Pennycook - ,
James R. McBride - ,
Sandra J. Rosenthal - ,
Stephen J. Pennycook - , and
Sokrates T. Pantelides
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Correction to Anomalous Pseudocapacitive Behavior of a Nanostructured, Mixed-Valent Manganese Oxide Film for Electrical Energy Storage
Min-Kyu Song - ,
Shuang Cheng - ,
Haiyan Chen - ,
Wentao Qin - ,
Kyung-Wan Nam - ,
Shucheng Xu - ,
Xiao-Qing Yang - ,
Angelo Bongiorno - ,
Jangsoo Lee - ,
Jianming Bai - ,
Trevor A. Tyson - ,
Jaephil Cho - , and
Meilin Liu
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