Electro-thermal actuation in percolative ferroelectric polymer nanocomposites.

The interconversion between electrical and mechanical energies is pivotal to ferroelectrics to enable their applications in transducers, actuators and sensors. Ferroelectric polymers exhibit a giant electric-field-induced strain (>4.0%), markedly exceeding the actuation strain (≤1.

Relaxor ferroelectric polymer exhibits ultrahigh electromechanical coupling at low electric field.

Electromechanical (EM) coupling-the conversion of energy between electric and mechanical forms-in ferroelectrics has been used for a broad range of applications. Ferroelectric polymers have weak EM coupling that severely limits their usefulness for applications. We introduced a small amount of fluorinated alkyne (FA) monomers (<2 mol %) in relaxor ferroelectric poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) (PVDF-TrFE-CFE) terpolymer that markedly enhances the polarization change with strong EM coupling while suppressing other polarization changes that do not contribute to it.

On-surface cyclodehydrogenation reaction pathway determined by selective molecular deuterations.

Understanding the reaction mechanisms of dehydrogenative C-C coupling is the key to directed formation of π-extended polycyclic aromatic hydrocarbons. Here we utilize isotopic labeling to identify the exact pathway of cyclodehydrogenation reaction in the on-surface synthesis of model atomically precise graphene nanoribbons (GNRs). Using selectively deuterated molecular precursors, we grow seven-atom-wide armchair GNRs on a Au(111) surface that display a specific hydrogen/deuterium (H/D) pattern with characteristic Raman modes.

Morphology-induced dielectric enhancement in polymer nanocomposites.

The mechanism of the recently discovered enhancement of dielectric properties in dilute polymer-nanoparticle composites is investigated by experiments and computer simulations. We show that the weakening of the hydrogen bonds between the nanoparticles and the polymer chains reduces the polymer-nanoparticle composite's dielectric enhancement. The subsequent multiscale simulations investigate the attachment of solvated highly dipolar polymers to oxide nanoparticles, which leads to deposition of nanoparticle-polymer blobs during solution casting and a reduced density compared to a neat polymer film.

Structural Insight in the Interfacial Effect in Ferroelectric Polymer Nanocomposites.

Both experimental results and theoretical models suggest the decisive role of the filler-matrix interfaces on the dielectric, piezoelectric, pyroelectric, and electrocaloric properties of ferroelectric polymer nanocomposites. However, there remains a lack of direct structural evidence to support the so-called interfacial effect in dielectric nanocomposites. Here, a chemical mapping of the interfacial coupling between the nanofiller and the polymer matrix in ferroelectric polymer nanocomposites by combining atomic force microscopy-infrared spectroscopy (AFM-IR) with first-principles calculations and phase-field simulations is provided.

Chirality-induced relaxor properties in ferroelectric polymers.

Relaxor ferroelectrics exhibit outstanding dielectric, electromechanical and electrocaloric properties, and are the materials of choice for acoustic sensors, solid-state coolers, transducers and actuators. Despite more than five decades of intensive study, relaxor ferroelectrics remain one of the least understood material families in ferroelectric materials and condensed matter physics. Here, by combining X-ray diffraction, atomic force microscope infrared spectroscopy and first-principles calculations, we reveal that the relaxor behaviour of ferroelectric polymers originates from conformational disorder, completely different from classic perovskite relaxors, which are typically characterized by chemical disorder.

Engineering Edge States of Graphene Nanoribbons for Narrow-Band Photoluminescence.

Solid-state narrow-band light emitters are on-demand for quantum optoelectronics. Current approaches based on defect engineering in low-dimensional materials usually introduce a broad range of emission centers. Here, we report narrow-band light emission from covalent heterostructures fused to the edges of graphene nanoribbons (GNRs) by controllable on-surface reactions from molecular precursors.

Large-Scale Phonon Calculations Using the Real-Space Multigrid Method.

Phonons are fundamental to understanding the dynamical and thermal properties of materials. However, first-principles phonon calculations are usually limited to moderate-size systems due to their high computational requirements. We implemented the finite displacement method (FDM) in the highly parallel real-space multigrid (RMG) suite of codes to study phonon properties.

Step edge-mediated assembly of periodic arrays of long graphene nanoribbons on Au(111).

The influence of substrate steps on the bottom-up synthesis of atomically precise graphene nanoribbons (GNRs) on an Au(111) surface is investigated. Straight surface steps are found to promote the assembly of long and compact arrays of polymers with enhanced interchain π-π stacking interactions, which create a steric hindrance effect on cyclodehydrogenation to suppress the H passivation of polymer ends. The modified two-stage growth process results in periodic arrays of GNRs with doubled average length near step edges.

Ferroelectric polymers exhibiting behaviour reminiscent of a morphotropic phase boundary.

Piezoelectricity-the direct interconversion between mechanical and electrical energies-is usually remarkably enhanced at the morphotropic phase boundary of ferroelectric materials, which marks a transition region in the phase diagram of piezoelectric materials and bridges two competing phases with distinct symmetries. Such enhancement has enabled the recent development of various lead and lead-free piezoelectric perovskites with outstanding piezoelectric properties for use in actuators, transducers, sensors and energy-harvesting applications. However, the morphotropic phase boundary has never been observed in organic materials, and the absence of effective approaches to improving the intrinsic piezoelectric responses of polymers considerably hampers their application to flexible, wearable and biocompatible devices.

Seamless Staircase Electrical Contact to Semiconducting Graphene Nanoribbons.

Electrical contact to low-dimensional (low-D) materials is a key to their electronic applications. Traditional metal contacts to low-D semiconductors typically create gap states that can pin the Fermi level (E). However, low-D metals possessing a limited density of states at E can enable gate-tunable work functions and contact barriers.

Controllable conversion of quasi-freestanding polymer chains to graphene nanoribbons.

In the bottom-up synthesis of graphene nanoribbons (GNRs) from self-assembled linear polymer intermediates, surface-assisted cyclodehydrogenations usually take place on catalytic metal surfaces. Here we demonstrate the formation of GNRs from quasi-freestanding polymers assisted by hole injections from a scanning tunnelling microscope (STM) tip. While catalytic cyclodehydrogenations typically occur in a domino-like conversion process during the thermal annealing, the hole-injection-assisted reactions happen at selective molecular sites controlled by the STM tip.

Selective sensing of ethylene and glucose using carbon-nanotube-based sensors: an ab initio investigation.

Functionalized carbon nanotubes have great potential for nanoscale sensing applications, yet many aspects of their sensing mechanisms are not understood. Here, two paradigmatic sensor configurations for detection of biologically important molecules are investigated through ab initio calculations: a non-covalently functionalized nanotube for glucose detection and a covalently functionalized nanotube for ethylene detection. Glucose and ethylene control key life processes of humans and plants, respectively, despite of their structural and chemical simplicity.

Active extracellular substances of ITRI-G1 induce microalgae self-disruption for microalgal biofuel.

Microalgal cultures are a clean and sustainable means to use solar energy for CO fixation and fuel production. Microalgae grow efficiently and are rich in oil, but recovering that oil is typically expensive and consumes much energy. Therefore, effective and low-cost techniques for microalgal disruption and oil or lipid extraction are required by the algal biofuel industry.

Continuous lipid extraction of microalgae using high-pressure carbon dioxide.

Sequestering carbon, purifying water, and creating biofuel materials using microalgae are of global interest in the R&D field. However, extracting algal oil consumes a high amount of energy, which is an obstacle for the biofuel market. Nontoxic and recyclable high-pressure CO2 extraction processes are being developed by numerous researchers; however, most of these processes use batch operations mixed with a large amount of co-solvent and require improvement.

Self-organized and cu-coordinated surface linear polymerization.

We demonstrate a controllable surface-coordinated linear polymerization of long-chain poly(phenylacetylenyl)s that are self-organized into a "circuit-board" pattern on a Cu(100) surface. Scanning tunneling microscopy/spectroscopy (STM/S) corroborated by ab initio calculations, reveals the atomistic details of the molecular structure, and provides a clear signature of electronic and vibrational properties of the poly(phenylacetylene)s chains. Notably, the polymerization reaction is confined epitaxially to the copper lattice, despite a large strain along the polymerized chain that subsequently renders it metallic.

Electronic control over attachment and self-assembly of alkyne groups on gold.

Self-assembled monolayers are the basis for molecular nanodevices, flexible surface functionalization, and dip-pen nanolithography. Yet self-assembled monolayers are typically created by a rather inefficient process involving thermally driven attachment reactions of precursor molecules to a metal surface, followed by a slow and defect-prone molecular reorganization. Here we demonstrate a nonthermal, electron-induced approach to the self-assembly of phenylacetylene molecules on gold that allows for a previously unachievable attachment of the molecules to the surface through the alkyne group.

Theory of nitrogen doping of carbon nanoribbons: edge effects.

Nitrogen doping of a carbon nanoribbon is profoundly affected by its one-dimensional character, symmetry, and interaction with edge states. Using state-of-the-art ab initio calculations, including hybrid exact-exchange density functional theory, we find that, for N-doped zigzag ribbons, the electronic properties are strongly dependent upon sublattice effects due to the non-equivalence of the two sublattices. For armchair ribbons, N-doping effects are different depending upon the ribbon family: for families 2 and 0, the N-induced levels are in the conduction band, while for family 1 the N levels are in the gap.

Supramolecular self-assembly of π-conjugated hydrocarbons via 2D cooperative CH/π interaction.

Supramolecular self-assembly on well-defined surfaces provides access to a multitude of nanoscale architectures, including clusters of distinct symmetry and size. The driving forces underlying supramolecular structures generally involve both graphoepitaxy and weak directional nonconvalent interactions. Here we show that functionalizing a benzene molecule with an ethyne group introduces attractive interactions in a 2D geometry, which would otherwise be dominated by intermolecular repulsion.

Quantum-interference-controlled three-terminal molecular transistors based on a single ring-shaped molecule connected to graphene nanoribbon electrodes.

We study molecular transistors where graphene nanoribbons act as three metallic electrodes connected to a ring-shaped 18-annulene molecule. Using the nonequilibrium Green function formalism combined with density functional theory, recently extended to multiterminal devices, we show that these nanostructures exhibit exponentially small transmission when the source and drain electrodes are attached in a configuration with destructive interference of electron paths around the ring. The third electrode, functioning either as an attached infinite-impedance voltage probe or as an "air-bridge" top gate covering half of molecular ring, introduces dephasing that brings the transistor into the "on" state with its transmission in the latter case approaching the maximum limit for a single conducting channel device.

Negative differential resistance in C60-based electronic devices.

Unlike single-C(60)-based devices, molecular assemblies based on two or more appropriately connected C(60) molecules have the potential to exhibit negative differential resistance (NDR). In this work, we evaluate electron transport properties of molecular devices built from two C(60) molecules connected by an alkane chain, using a nonequilibrium Green function technique implemented within the framework of density functional theory. We find that electronic conduction in these systems is mediated by the lowest unoccupied molecular orbitals (LUMOs) of C(60), as in the case of a single-C(60)-based device.

First-principles methodology for quantum transport in multiterminal junctions.

We present a generalized approach for computing electron conductance and I-V characteristics in multiterminal junctions from first-principles. Within the framework of Keldysh theory, electron transmission is evaluated employing an O(N) method for electronic-structure calculations. The nonequilibrium Green function for the nonequilibrium electron density of the multiterminal junction is computed self-consistently by solving Poisson equation after applying a realistic bias.

Functional implications of multistage copper binding to the prion protein.

The prion protein (PrP) is responsible for a group of neurodegenerative diseases called the transmissible spongiform encephalopathies. The normal function of PrP has not yet been discovered, but indirect evidence suggests a linkage to its ability to bind copper. In this article, low-copper-concentration bindings of Cu(2+) to PrP are investigated by using a recently developed hybrid density functional theory (DFT)/DFT method.