Electronic structure and stability of semiconducting graphene nanoribbons

We present a systematic density functional theory study of the electronic properties, optical spectra, and relative thermodynamic stability of semiconducting graphene nanoribbons. We consider ribbons with different edge nature including bare and hydrogen-terminated ribbons, several crystallographic orientations, and widths up to 3 nm. Our results can be extrapolated to wider ribbons providing a qualitative way of determining the electronic properties of ribbons with widths of practical significance. We predict that in order to produce materials with band gaps similar to Ge or InN, the width of the ribbons must be between 2 and 3 nm. If larger bang gap ribbons are needed (like Si, InP, or GaAs), their width must be reduced to 1-2 nm. According to the extrapolated inverse power law obtained in this work, armchair carbon nanoribbons of widths larger than 8 nm will present a maximum band gap of 0.3 eV, while for ribbons with a width of 80 nm the maximum possible band gap is 0.05 eV. For chiral nanoribbons the band gap oscillations rapidly vanish as a function of the chiral angle indicating that a careful design of their crystallographic nature is an essential ingredient for controlling their electronic properties. Optical excitations show important differences between ribbons with and without hydrogen termination and are found to be sensitive to the carbon nanoribbon width. This should provide a practical way of revealing information on their size and the nature of their edges.     

Substrate Phonon‐Mediated Plasmon Hybridization in Coplanar Graphene Nanostructures for Broadband Plasmonic Circuits

The mode hybridization between adjacent graphene nanoribbons determines the integration density of graphene‐based plasmonic devices. Here, plasmon hybridization in graphene nanostructures is demonstrated through the characterization of the coupling strength of plasmons in graphene nanoribbons as a function of charge density and inter‐ribbon spacing using Fourier transform infrared microscopy. In combination with numerical simulations, it is shown that the plasmon coupling is strongly mediated by the substrate phonons. For polar substrates, the plasmon coupling strength is limited by the plasmon–phonon interactions. In contrast, a nonpolar substrate affects neither the energy distribution of the original plasmon modes in graphene nanostructures nor their plasmon interactions, which increases exponentially as the inter‐ribbon spacing decreases. To further explore the potential of graphene broadband plasmonics on nonpolar substrates, a scheme is proposed that uses a metal–dielectric heterostructure to prevent the overlap of plasmons between neighboring graphene nanoribbons. The device structures retain the plasmon resonance frequency of the graphene ribbons and maximally isolate the plasmonic components from the surrounding electromagnetic environment, allowing modular design in integrated plasmonic circuits.     

Effects of magnetic doping on weak antilocalization in narrow bi(2)se(3) nanoribbons

We report low-temperature, magnetotransport measurements of ferrocene-doped Bi(2)Se(3) 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 Bi(2)Se(3). The power law decay of the dephasing length on temperature also reflects one-dimensional localization regime in these narrow Bi(2)Se(3) nanoribbons. The emergence of weak localization in ferrocene-doped Bi(2)Se(3) nanoribbons presents ferrocene as an effective magnetic dopant source.     

On‐Surface Synthesis of 8‐ and 10‐Armchair Graphene Nanoribbons

Armchair graphene nanoribbons (AGNRs) with 8 and 10 carbon atoms in width (8‐ and 10‐AGNRs) are synthesized on Au (111) surfaces via lateral fusion of nanoribbons that belong to different subfamilies. Poly‐para‐phenylene (3‐AGNR) chains are pre‐synthesized as ladder ribbons on Au (111). Subsequently, synthesized 5‐ and 7‐AGNRs can laterally fuse with 3‐AGNRs upon annealing at higher temperature, producing 8‐ and 10‐AGNRs, respectively. The synthetic process, and their geometric and electronic structures are characterized by scanning tunneling microscopy/spectroscopy (STM/STS). STS investigations reveal the band gap of 10‐AGNR (2.0 ± 0.1 eV) and a large apparent band gap of 8‐AGNRs (2.3 ± 0.1 eV) on Au (111) surface.     

Ferromagnetism in graphene nanoribbons: split versus oxidative unzipped ribbons

Two types of graphene nanoribbons: (a) potassium-split graphene nanoribbons (GNRs), and (b) oxidative unzipped and chemically converted graphene nanoribbons (CCGNRs) were investigated for their magnetic properties using the combination of static magnetization and electron spin resonance measurements. The two types of ribbons possess remarkably different magnetic properties. While a low-temperature ferromagnet-like feature is observed in both types of ribbons, such room-temperature feature persists only in potassium-split ribbons. The GNRs show negative exchange bias, but the CCGNRs exhibit a "positive exchange bias". Electron spin resonance measurements suggest that the carbon-related defects may be responsible for the observed magnetic behavior in both types of ribbons. Furthermore, information on the proton hyperfine coupling strength has been obtained from hyperfine sublevel correlation experiments performed on the GNRs. Electron spin resonance finds no evidence for the presence of potassium (cluster) related signals, pointing to the intrinsic magnetic nature of the ribbons. Our combined experimental results may indicate the coexistence of ferromagnetic clusters with antiferromagnetic regions leading to disordered magnetic phase. We discuss the possible origin of the observed contrast in the magnetic behaviors of the two types of ribbons studied.     

Nanomaterial‐Enabled Stretchable Conductors: Strategies,Materials and Devices

Stretchable electronics are attracting intensive attention due to their promising applications in many areas where electronic devices undergo large deformation and/or form intimate contact with curvilinear surfaces. On the other hand, a plethora of nanomaterials with outstanding properties have emerged over the past decades. The understanding of nanoscale phenomena, materials, and devices has progressed to a point where substantial strides in nanomaterial‐enabled applications become realistic. This review summarizes recent advances in one such application, nanomaterial‐enabled stretchable conductors (one of the most important components for stretchable electronics) and related stretchable devices (e.g., capacitive sensors, supercapacitors and electroactive polymer actuators), over the past five years. Focusing on bottom‐up synthesized carbon nanomaterials (e.g., carbon nanotubes and graphene) and metal nanomaterials (e.g., metal nanowires and nanoparticles), this review provides fundamental insights into the strategies for developing nanomaterial‐enabled highly conductive and stretchable conductors. Finally, some of the challenges and important directions in the area of nanomaterial‐enabled stretchable conductors and devices are discussed.     

Highly Stable and Stretchable Conductive Films through Thermal‐Radiation‐Assisted Metal Encapsulation

Stretchable conductors are the basic units of advanced flexible electronic devices, such as skin‐like sensors, stretchable batteries and soft actuators. Current fabrication strategies are mainly focused on the stretchability of the conductor with less emphasis on the huge mismatch of the conductive material and polymeric substrate, which results in stability issues during long‐term use. Thermal‐radiation‐assisted metal encapsulation is reported to construct an interlocking layer between polydimethylsiloxane (PDMS) and gold by employing a semipolymerized PDMS substrate to encapsulate the gold clusters/atoms during thermal deposition. The stability of the stretchable conductor is significantly enhanced based on the interlocking effect of metal and polymer, with high interfacial adhesion (>2 MPa) and cyclic stability (>10 000 cycles). Also, the conductor exhibits superior properties such as high stretchability (>130%) and large active surface area (>5:1 effective surface area/geometrical area). It is noted that this method can be easily used to fabricate such a stretchable conductor in a wafer‐scale format through a one‐step process. As a proof of concept, both long‐term implantation in an animal model to monitor intramuscular electric signals and on human skin for detection of biosignals are demonstrated. This design approach brings about a new perspective on the exploration of stretchable conductors for biomedical applications.     

Metal Deposition on a Self‐Generated Microfibril Network to Fabricate Stretchable Tactile Sensors Providing Analog Position Information

Stretchable conductors and sensors have attracted great attention for use in electronic skin and healthcare monitoring. Despite the development of many stretchable conductors, there are still very few studies that utilize the conventional methods making electrodes and circuits used in current industry. A method is proposed to fabricate a stretchable electrode pattern and a stretchable tactile sensor by simply depositing linear metal lines through a mask on a stretchable substrate. A method is developed of a self‐generating microfibril network on the surface of stretchable block copolymer substrates. The formation mechanism of the microfibril network is studied with finite element method simulations. Metals (Au and Ag nanowires) are deposited directly on the substrate through a patterned mask. This study shows that strain‐insensitive circuit and strain‐sensitive sensor can be fabricated in a controlled way by adjusting the thickness of the deposited metal, which makes it easy to fabricate a tactile sensor by metal deposition. Also, by using the characteristic that the sensor has different sensitivity depending on the line pattern width, a novel sensor structure simultaneously providing analog‐type position information and pressure value is proposed.     

Nanowires and nanoribbons formed by methylphosphonic acid

The production and physical properties of nanowires and nanoribbons formed by methylphosphonic acid (MPA)--CH3PO(OH)2--were investigated. These structures are formed on an aluminum coated substrate when immersed in an ethanolic solution of MPA for several days. A careful investigation of the growth conditions resulted in a narrow window of solution concentrations and temperatures for the successful development of nanowires and nanoribbons. Several different techniques were employed to characterize these nanostructures: (1) Photoluminescence experiments showed a strong emission at 2.3 eV (green), which is visible to the naked eye; (2) X-ray diffraction experiments indicated a significant cristalinity, in agreement with atomic force microscopy (AFM) and transmission electron microscopy (TEM) morphology images, which show organized nano-scale wires and ribbons, (furthermore, AFM-Phase and TEM images also suggest that nanoribbons are formed by well-aligned nanowires); (3) Conductive-AFM experiments revealed an intermediary conductivity for these structures (10(-1)/Ohm x m), which is similar to some intrinsic semiconductors and; (4) finally, Infrared, Raman, and X-Ray Photoelectron Spectroscopies produced information about the contents, structure, and composition of both wires and ribbons.     

Mechanoresponsive Polymerized Liquid Metal Networks

Room‐temperature liquid metals, such as nontoxic gallium alloys, show enormous promise to revolutionize stretchable electronics for next‐generation soft robotic, e‐skin, and wearable technologies. Core–shell particles of liquid metal with surface‐bound acrylate ligands are synthesized and polymerized together to create cross‐linked particle networks comprising >99.9% liquid metal by weight. When stretched, particles within these polymerized liquid metal networks (Poly‐LMNs) rupture and release their liquid metal payload, resulting in a rapid 10⁸‐fold increase in the network's conductivity. These networks autonomously form hierarchical structures that mitigate the deleterious effects of strain on electronic performance and give rise to emergent properties. Notable characteristics include nearly constant resistances over large strains, electronic strain memory, and increasing volumetric conductivity with strain to over 20 000 S cm^?1 at >700% elongation. Furthermore, these Poly‐LMNs exhibit exceptional performance as stretchable heaters, retaining 96% of their areal power across relevant physiological strains. Remarkable electromechanical properties, responsive behaviors, and facile processing make Poly‐LMNs ideal for stretchable power delivery, sensing, and circuitry.     

First-principles study of heat transport properties of graphene nanoribbons

We use density-functional theory and the nonequilibrium Green's function method as well as phonon dispersion calculations to study the thermal conductance of graphene nanoribbons with armchair and zigzag edges, with and without hydrogen passivation. We find that low-frequency phonon bands of the zigzag ribbons are more dispersive than those of the armchair ribbons and that this difference accounts for the anisotropy in the thermal conductance of graphene nanoribbons. Comparing our results with data on large-area graphene, edge effects are shown to contribute to thermal conductance, enhance the anisotropy in thermal conductance of graphene nanoribbons, and increase thermal conductance per unit width. The edges with and without hydrogen passivation modify the atomic structure and ultimately influence the phonon thermal transport differently for the two ribbon types.     

Quasi‐Epitaxial Growth of Magnetic Nanostructures on 4H‐Au Nanoribbons

Phase engineering of nanomaterials is an effective strategy to tune the physicochemical properties of nanomaterials for various promising applications. Herein, by using the 4H‐Au nanoribbons as templates, four novel magnetic nanostructures, namely 4H‐Au @ 14H‐Co nanobranches, 4H‐Au @ 14H‐Co nanoribbons, 4H‐Au @ 2H‐Co nanoribbons, and 4H‐Au @ 2H‐Ni nanoribbons, are synthesized based on the quasi‐epitaxial growth. Different from the conventional epitaxial growth of metal nanomaterials, the obtained Co and Ni nanostructures possess different crystal phases from the Au template. Due to the large lattice mismatch between Au and the grown metals (i.e., Co and Ni), ordered misfit dislocations are generated at the Co/Au and Ni/Au interfaces. Notably, a new super‐structure of Co is formed, denoted as 14H. Both 4H‐Au @ 14H‐Co nanobranches and nanoribbons are ferromagnetic at room temperature, showing similar Curie temperature. However, their magnetic behaviors exhibit distinct temperature dependence, resulting from the competition between spin and volume fluctuations as well as the unique geometry. This work paves the way to the templated synthesis of nanomaterials with unconventional crystal phases for the exploration of phase‐dependent properties.     

DNA origami-based nanoribbons: assembly, length distribution, and twist

A variety of polymerization methods for the assembly of elongated nanoribbons from rectangular DNA origami structures are investigated. The most efficient method utilizes single-stranded DNA oligonucleotides to bridge an intermolecular scaffold seam between origami monomers. This approach allows the fabrication of origami ribbons with lengths of several micrometers, which can be used for long-range ordered arrangement of proteins. It is quantitatively shown that the length distribution of origami ribbons obtained with this technique follows the theoretical prediction for a simple linear polymerization reaction. The design of flat single layer origami structures with constant crossover spacing inevitably results in local underwinding of the DNA helix, which leads to a global twist of the origami structures that also translates to the nanoribbons.     

A High Aspect Ratio Serpentine Structure for Use As a Strain‐Insensitive,Stretchable Transparent Conductor

The development of strain‐insensitive stretchable transparent conductors (TCs) is essential for manufacturing stretchable electronics. Despite recent progress, achieving a high optoelectronic performance under applied strain of 50% continues to present a significant challenge in this research field. Herein, an ultratall and ultrathin high aspect ratio serpentine metal structure is described that exhibits a remarkable stretching ability (the resistance remains constant under applied strain of 100%) and simultaneously provides an excellent transparent conducting performance (with a sheet resistance of 7.6 Ω ^?1 and a transmittance of 90.5%). It is demonstrated that the highly stretchable transparent conducting properties can be attributed to the high aspect ratio feature. A high aspect ratio (aspect ratio of 17–367) structure permits facile deformation of the serpentine structure with in‐plane motion, leading to a high stretching ability. In addition, this structural feature avoids the classic tradeoff between optical transmittance and electrical conductance, providing a high electrical conductance without decreasing the optical transmittance. The practical utility of these devices is tested by using these TCs as stretchable interconnectors among LEDs or in wearable VOC gas sensors.     

A Highly Stretchable Liquid Metal Polymer as Reversible Transitional Insulator and Conductor

Materials with a temperature‐controlled reversible electrical transition between insulator and conductor are attracting huge attention due to their promising applications in many fields. However, most of them are intrinsically rigid and require complicated fabrication processes. Here, a highly stretchable (680% strain) liquid metal polymer composite as a reversible transitional insulator and conductor (TIC), which is accompanied with huge resistivity changes (more than 4 × 10⁹ times) reversibly through a tuning temperature in a few seconds is introduced. When frozen, the insulated TIC becomes conductive and recovers after warming. Both the phase change of the liquid metal droplets and the rigidity change of the polymer contribute directly to transition between insulator and conductor. A simplified model is established to predict the expansion and connection of liquid metal droplets. Along with high stretchability, straightforward fabrication methods, rapid triggering time, large switching ratio, good repeatability, the TIC offers tremendous possibilities for numerous applications, like stretchable switches, semiconductors, temperature sensors, and resistive random‐access memory. Accordingly, a system that can display numbers and letters via converting alternative TIC temperature to a binary signal on a computer is conceived and demonstrated. The present discovery suggests a general strategy for fabricating and stimulating a stretchable transitional insulator and conductor based on liquid metal and allied polymers.     

A Free‐Standing and Self‐Healable 2D Supramolecular Material Based on Hydrogen Bonding: A Nanowire Array with Sub‐2‐nm Resolution

In many 2D materials reported thus far, the forces confining atoms in a 2D plane are often strong interactions, such as covalent bonding. Herein, the first demonstration that hydrogen (H)‐bonding can be utilized to assemble polydiacetylene (a conductive polymer) toward a 2D material, which is stable enough to be free‐standing, is shown. The 2D material is well characterized by a large number of techniques (mainly different microscopy techniques). The H‐bonding allows splitting of the material into ribbons, which can reassemble, similar to a zipper, leading to the first example of a healable 2D material. Moreover, such technology can easily create 2D, organic, conductive nanowire arrays with sub‐2‐nm resolution. This material may have potential applications in stretchable electronics and nanowire cross‐bar arrays.     

The effects of encapsulation on deformation behavior and failure mechanisms of stretchable interconnects

In this paper, the effect of encapsulation on deformation behavior and failure mechanisms of stretchable interconnects is presented. Extensive numerical modeling is conducted for mechanical analysis of which the results are correlated with in-situ experimental observations. The numerical results reveal that by adding an encapsulation layer of various thickness (from 0.0 to 0.5 mm) on top of the stretchable interconnect, the out-of-plane deformation and in-plane geometrical opening are reduced. Consequently, not only the plastic strain in the metal increases but also the in-plane shear stress at the interconnect/substrate interface. In-situ electromechanical experiments combined with scanning electron micrographs and optical images confirm the numerical analysis. More specifically, it is found that two failure mechanisms are involved during the stretching process: interfacial delamination in a S-shape alongside the metal conductor and metal breakdown at the crests of the metal conductor. The encapsulated stretchable interconnect shows both failure mechanisms at a lower percentage elongation than the non-encapsulated stretchable interconnect. Even so, the onset point of interfacial delamination for the encapsulated stretchable interconnect occurs only at an impressive number of 63% elongation and metal rupture only at 120%. The in-plane shear strain contour, obtained by numerical simulation, agrees well with the delamination failure location observed in the experiment.     

Pulsed Laser Modulated Shock Transition from Liquid Metal Nanoparticles to Mechanically and Thermally Robust Solid–Liquid Patterns

In this work, a general mechanism is discovered to form liquid‐metal‐based, stable and stretchable conductive patterns on rigid and soft substrates. It is discovered that pulsed laser irradiation of liquid metal nanoparticles (LMNPs) with tunable conditions can induce transformation to stable and stretchable solid–liquid (S–L) dual phases on various surfaces. Formation of this unique solid–liquid composite phase is the key to change the wetting behavior of the conductive patterns on various substrates and enables mechanically stable patterns on various substrates. Pulsed‐laser‐driven thermo‐mechanical shock momentum is important for rupture and joining of the LMNPs, providing much better control than the traditional mechanical sintering. The solid nanophase forms a nanoporous matrix filled with and wetted by the LM, thereby providing a stabilization mechanism for the S–L composite patterned thin film. The mechanical and thermal reliability of the solid–liquid patterns is investigated. The S–L patterns can stretch up to 30% strain and cycle stably for 7000 cycles. It can be heated up to 177 °C with an input power of 0.58 W. The solid–liquid composite film provides great opportunity for various applications as a flexible conductor with unique mechanical and physics properties and further inspires design of LM devices for completely exposed applications.     

Magnetic behavior in zinc oxide zigzag nanoribbons

We use first principles calculations to investigate the magnetic properties of zinc oxide nanoribbons with zigzag-terminated edges. The polarized spin density of states is calculated as a function of the nanoribbons width and thickness. All nanoribbons formed by a single layer exhibit a magnetic behavior independently of the width. By analyzing the charge density and spin density, we determine that the oxygen-dominated edge exhibits unpaired spins. When the thickness of the ribbons is increased, a magnetic moment is observed only for specific thicknesses.     

One-dimensional single-crystalline bismuth oxide micro/nanoribbons: morphology-controlled synthesis and luminescent properties

Based on a facile vapor-phase transport method without any catalyst and template, one-dimensional single-crystalline bismuth oxide (Bi2O3) micro/nanoribbons were fabricated on silicon substrates in large quantities and morphology-controlled fabrication of Bi2O3 was achieved from a single precursor. The widths of Bi2O3 ribbons varied from 0.2 to 20 microm depending on the deposition temperatures. The thickness was in the range of 0.1-2 microm and the length reached several hundred micrometers and even millimeter range. The detailed composition and structural analysis confirmed the single-crystalline nature of alpha-Bi2O3 micro/nanoribbons with monoclinic structure. The photoluminescence spectrum of a single Bi2O3 ribbon showed a broadband emission from 450 to 750 nm in the visible region, consisting two peaks located at 589 and 697 nm which were primarily originated from the impurity ions and crystal defects. A self-catalyzed vapor-solid model was proposed to account for the growth mechanism of Bi2O3 ribbons with different morphologies.