Rodrigo A. Bernal

A Review of Mechanical and Electromechanical Properties of Piezoelectric Nanowires

Piezoelectric nanowires are promising building blocks in nanoelectronic, sensing, actuation and nanogenerator systems. In spite of great progress in synthesis methods, quantitative mechanical and electromechanical characterization of these nanostructures is still limited. In this article, the state-of-the art in experimental and computational studies of mechanical and electromechanical properties of piezoelectric nanowires is reviewed with an emphasis on size effects. The review covers existing characterization and analysis methods and summarizes data reported in the literature. It also provides an assessment of research needs and opportunities. Throughout the discussion, the importance of coupling experimental and computational studies is highlighted. This is crucial for obtaining unambiguous size effects of nanowire properties, which truly reflect the effect of scaling rather than a particular synthesis route. We show that such a combined approach is critical to establish synthesis-structure-property relations that will pave the way for optimal usage of piezoelectric nanowires.

Ultrahigh Strength and Stiffness in Cross-Linked Hierarchical Carbon Nanotube Bundles

IO N Utilizing the full mechanical capabilities of individual carbon nanotubes (CNT) – which can exhibit tensile strength and elastic modulus of up to 1TPa and 100 GPa, respectively [ 1–4 ] – has motivated a great deal of interest in CNT based nanocomposite materials. [ 5–10 ] Despite this signifi cant scientifi c effort, the strength, modulus, and toughness of CNT based fi bers and composites are typically dominated by weak shear interactions between adjacent shells, tubes, bundles, and matrix materials, [ 2 , 4 , 10 , 11 ] which has limited their application to hierarchical macroscopic composite materials. Here we demonstrate that the mechanical performance of double-walled nanotube (DWNT) bundles is greatly enhanced through high-energy electron-irradiation-induced shell–shell and tube–tube crosslinking. The effective tensile strength and elastic modulus are found to increase by an order of magnitude as compared to un-crosslinked bundles. This enhancement is attributed to covalent bonds formed between outer and inner DWNT shells as well as adjacent DWNT outer tubes within the bundle. Distinct failure mechanisms were also identifi ed through in situ transmission electron microscopy (TEM) tensile tests of individual DWNT bundles revealing a sword-in-sheath like failure mechanism for low cross-linked bundles and complete fracture of all shells for highly cross-linked bundles. The optimized irradiation-induced cross-linking enhancements of DWNT bundles demonstraed here are predicted to translate to up to order-of-magnitude improvements in the mechanical behavior of advanced composites. Engineering lateral interactions through cross-linking has become an essential tool in the development of advanced hierarchical composite materials, many of which are inspired by natural interfaces. [ 12–15 ] Successful hierarchical designs typically require both cross-linking to strong/stiff reinforcement elements (e.g. mineral crystals in the collagen fi brils in bone [ 14 ] ) coupled with soft-sacrifi cial cross-linking (e.g. hydrogen bonding between beta-sheet crystals in spider silk [ 16 ] ) between elements to enhance toughness. In the case of individual CNTs and CNT bundles, one successful approach has been covalent cross-linking via high energy

Individual GaN Nanowires Exhibit Strong Piezoelectricity in 3D

Semiconductor GaN NWs are promising components in next generation nano- and optoelectronic systems. In addition to their direct band gap, they exhibit piezoelectricity, which renders them particularly attractive in energy harvesting applications for self-powered devices. Nanowires are often considered as one-dimensional nanostructures; however, the electromechanical coupling leads to a third rank tensor that for wurtzite crystals (GaN NWs) possesses three independent coefficients, d(33), d(13), and d(15). Therefore, the full piezoelectric characterization of individual GaN NWs requires application of electric fields in different directions and measurements of associated displacements on the order of several picometers. In this Letter, we present an experimental approach based on scanning probe microscopy to directly quantify the three-dimensional piezoelectric response of individual GaN NWs. Experimental results reveal that GaN NWs exhibit strong piezoelectricity in three dimensions, with up to six times the effect in bulk. Based on finite element modeling, this finding has major implication on the design of energy harvesting systems exhibiting unprecedented levels of power density production. The presented method is applicable to other piezoelectric NW materials as well as wires manufactured along different crystallographic orientations.

Effect of Growth Orientation and Diameter on the Elasticity of GaN Nanowires. A Combined in Situ TEM and Atomistic Modeling Investigation

We characterized the elastic properties of GaN nanowires grown along different crystallographic orientations. In situ transmission electron microscopy tensile tests were conducted using a MEMS-based nanoscale testing system. Complementary atomistic simulations were performed using density functional theory and molecular dynamics. Our work establishes that elasticity size dependence is limited to nanowires with diameters smaller than 20 nm. For larger diameters, the elastic modulus converges to the bulk values of 300 GPa for c-axis and 267 GPa for a- and m-axis.

Nucleation-Controlled Distributed Plasticity in Penta-twinned Silver Nanowires

A unique size-dependent strain hardening mechanism, that achieves both high strength and ductility, is demonstrated for penta-twinned Ag nanowires (NWs) through a combined experimental-computational approach. Thin Ag NWs are found to deform via the surface nucleation of stacking fault decahedrons (SFDs) in multiple plastic zones distributed along the NW. Twin boundaries lead to the formation of SFD chains that locally harden the NW and promote subsequent nucleation of SFDs at other locations. Due to surface undulations, chain reactions of SFD arrays are activated at stress concentrations and terminated as local stress decreases, revealing insensitivity to defects imparted by the twin structures. Thick NWs exhibit lower flow stress and number of distributed plastic zones due to the onset of necking accompanied by more complex dislocation structures.

In situ TEM electromechanical testing of nanowires and nanotubes

The emergence of one-dimensional nanostructures as fundamental constituents of advanced materials and next-generation electronic and electromechanical devices has increased the need for their atomic-scale characterization. Given its spatial and temporal resolution, coupled with analytical capabilities, transmission electron microscopy (TEM) has been the technique of choice in performing atomic structure and defect characterization. A number of approaches have been recently developed to combine these capabilities with in-situ mechanical deformation and electrical characterization in the emerging field of in-situ TEM electromechanical testing. This has enabled researchers to establish unambiguous synthesis-structure-property relations for one-dimensional nanostructures. In this article, the development and latest advances of several in-situ TEM techniques to carry out mechanical and electromechanical testing of nanowires and nanotubes are reviewed. Through discussion of specific examples, it is shown how the merging of several microsystems and TEM has led to significant insights into the behavior of nanowires and nanotubes, underscoring the significant role in-situ techniques play in the development of novel nanoscale systems and materials.

Atom Probe Tomography of a-Axis GaN Nanowires: Analysis of Nonstoichiometric Evaporation Behavior

GaN nanowires oriented along the nonpolar a-axis were analyzed using pulsed laser atom probe tomography (APT). Stoichiometric mass spectra were achieved by optimizing the temperature, applied dc voltage, and laser pulse energy. Local variations in the measured stoichiometry were observed and correlated with facet polarity using scanning electron microscopy. Fewer N atoms were detected from nonpolar and Ga-polar surfaces due to uncorrelated evaporation of N(2) ions following N adatom diffusion. The observed differences in Ga and N ion evaporation behaviors are considered in detail to understand the influence of intrinsic materials characteristics on the reliability of atom probe tomography analysis. We find that while reliable analysis of III-N alloys is possible, the standard APT procedure of empirically adjusting analysis conditions to obtain stoichiometric detection of Ga and N is not necessarily the best approach for this materials system.

Pushing the envelope of in situ transmission electron microscopy.

Recent major improvements to the transmission electron microscope (TEM) including aberration-corrected electron optics, light-element-sensitive analytical instrumentation, sample environmental control, and high-speed and sensitive direct electron detectors are becoming more widely available. When these advances are combined with in situ TEM tools, such as multimodal testing based on microelectromechanical systems, key measurements and insights on nanoscale material phenomena become possible. In particular, these advances enable metrology that allows for unprecedented correlation to quantum mechanics and the predictions of atomistic models. In this Perspective, we provide a summary of recent in situ TEM research that has leveraged these new TEM capabilities as well as an outlook of the opportunities that exist in the different areas of in situ TEM experimentation. Although these advances have improved the spatial and temporal resolution of TEM, a critical analysis of the various in situ TEM fields reveals that further progress is needed to achieve the full potential of the technology.

Intrinsic Bauschinger Effect and Recoverable Plasticity in Pentatwinned Silver Nanowires Tested in Tension

Silver nanowires are promising components of flexible electronics such as interconnects and touch displays. Despite the expected cyclic loading in these applications, characterization of the cyclic mechanical behavior of chemically synthesized high-quality nanowires has not been reported. Here, we combine in situ TEM tensile tests and atomistic simulations to characterize the cyclic stress-strain behavior and plasticity mechanisms of pentatwinned silver nanowires with diameters thinner than 120 nm. The experimental measurements were enabled by a novel system allowing displacement-controlled tensile testing of nanowires, which also affords higher resolution for capturing stress-strain curves. We observe the Bauschinger effect, that is, asymmetric plastic flow, and partial recovery of the plastic deformation upon unloading. TEM observations and atomistic simulations reveal that these processes occur due to the pentatwinned structure and emerge from reversible dislocation activity. While the incipient plastic mechanism through the nucleation of stacking fault decahedrons (SFDs) is fully reversible, plasticity becomes only partially reversible as intersecting SFDs lead to dislocation reactions and entanglements. The observed plastic recovery is expected to have implications to the fatigue life and the application of silver nanowires to flexible electronics.

High Strain Rate Tensile Testing of Silver Nanowires: Rate-Dependent Brittle-to-Ductile Transition

The characterization of nanomaterials under high strain rates is critical to understand their suitability for dynamic applications such as nanoresonators and nanoswitches. It is also of great theoretical importance to explore nanomechanics with dynamic and rate effects. Here, we report in situ scanning electron microscope (SEM) tensile testing of bicrystalline silver nanowires at strain rates up to 2/s, which is 2 orders of magnitude higher than previously reported in the literature. The experiments are enabled by a microelectromechanical system (MEMS) with fast response time. It was identified that the nanowire plastic deformation has a small activation volume (<10b(3)), suggesting dislocation nucleation as the rate controlling mechanism. Also, a remarkable brittle-to-ductile failure mode transition was observed at a threshold strain rate of 0.2/s. Transmission electron microscopy (TEM) revealed that along the nanowire, dislocation density and spatial distribution of plastic regions increase with increasing strain rate. Furthermore, molecular dynamic (MD) simulations show that deformation mechanisms such as grain boundary migration and dislocation interactions are responsible for such ductility. Finally, the MD and experimental results were interpreted using dislocation nucleation theory. The predicted yield stress values are in agreement with the experimental results for strain rates above 0.2/s when ductility is pronounced. At low strain rates, random imperfections on the nanowire surface trigger localized plasticity, leading to a brittle-like failure.