S. O. Kucheyev

Ultralight, ultrastiff mechanical metamaterials

Microlattices make marvelous materials Framework or lattice structures can be remarkably strong despite their very low density. Using a very precise technique known as projection microstereolithography, Zheng et al. fabricated octet microlattices from polymers, metals, and ceramics. The design of the lattices meant that the individual struts making up the materials did not bend under pressure. The materials were therefore exceptionally stiff, strong, and lightweight. Science, this issue p. 1373 Ultralow-density materials that deform through tension or compression rather than bending show much higher stiffness. The mechanical properties of ordinary materials degrade substantially with reduced density because their structural elements bend under applied load. We report a class of microarchitected materials that maintain a nearly constant stiffness per unit mass density, even at ultralow density. This performance derives from a network of nearly isotropic microscale unit cells with high structural connectivity and nanoscale features, whose structural members are designed to carry loads in tension or compression. Production of these microlattices, with polymers, metals, or ceramics as constituent materials, is made possible by projection microstereolithography (an additive micromanufacturing technique) combined with nanoscale coating and postprocessing. We found that these materials exhibit ultrastiff properties across more than three orders of magnitude in density, regardless of the constituent material.

Mechanically robust and electrically conductive carbon nanotube foams

We describe the fabrication of ultralow-density carbon nanotube (CNT) foams that simultaneously exhibit high electrical conductivities and robust mechanical properties. Our approach utilizes carbon nanoparticles as a binder to crosslink randomly oriented bundles of single-walled CNTs. The resulting CNT foams are the stiffest low-density nanoporous solids reported and exhibit elastic behavior up to strains as large as ∼80%. The use of the carbon binder also allows bulk electrical conductivity to be maintained at low densities.

Surface-enhanced Raman scattering on nanoporous Au

Colloidal solutions of metal nanoparticles are currently among the most studied substrates for sensors based on surface-enhanced Raman scattering (SERS). However, such substrates often suffer from not being cost-effective, reusable, or stable. Here, we develop nanoporous Au as a highly active, tunable, stable, biocompatible, and reusable SERS substrate. Nanoporous Au is prepared by a facile process of free corrosion of AgAu alloys followed by annealing. Results show that nanofoams with average pore widths of ∼250nm exhibit the largest SERS signal for 632.8nm excitation. This is attributed to the electromagnetic SERS enhancement mechanism with additional field localization within pores.

Macroscopic 3D nanographene with dynamically tunable bulk properties.

Polymer-derived, monolithic three-dimensional nanographene (3D-NG) bulk material with tunable properties is produced by a simple and inexpensive approach. The material is mass-producible, and combines chemical inertness and mechanical strength with a hierarchical porous architecture and a graphene-like surface area. This provides an opportunity to control its electron transport and mechanical properties dynamically by means of electrochemical-induced interfacial electric fields.

Optical defects produced in fused silica during laser-induced breakdown

Fused silica irradiated with ∼3-ns 1064-, 355-, and 266-nm laser pulses as well as with ∼120-fs 825-nm pulses is studied by a combination of photoluminescence (PL) and Raman scattering spectroscopies. Results show that, for laser fluences above the laser-induced breakdown threshold, in all the cases studied, irradiation results in the formation of four defect-related PL bands centered on ∼1.9 (655), 2.2 (565), 2.7 (460), and 4.3 eV (290 nm). Bands centered on 1.9, 2.7, and 4.3 eV are attributed to nonbridging oxygen hole centers (1.9 eV) and oxygen-deficiency defects (2.7 and 4.3 eV). However, defects giving rise to a broad band at ∼2.2 eV are unknown. For all the laser-modified samples studied, Raman spectroscopy reveals a dramatic increase in the intensity of D1 and D2 lines, associated with in-phase breathing motions of oxygen atoms in puckered four- and planar three-membered ring structures, respectively. This indicates laser-induced material densification. Based on these results, we discuss physical ...

Super-Compressibility of Ultralow-Density Nanoporous Silica

Porosity generally embrittles ceramics, and low-density nanoporous oxides typically exhibit very brittle behavior. In contrast to such expectations, we find that an effective fracture strain of nanoporous silica increases with increasing porosity. At ultralow relative densities of <0.5%,[1] nanoporous monoliths start exhibiting super-compressible deformation with large effective fracture strains of >50%. We attribute such a super-compressible behavior to consequences of an increase in the average aspect ratio of ligaments with decreasing monolith density. These results have important implications for designing novel supercompressive materials and for understanding observations of super-compressibility for other low-density nanoporous systems such as carbon-nanotube-based nanofoams. Understanding effects of porosity on mechanical properties of solids has been a subject of numerous previous investigations, driven by their important technological implications. Indeed, most brittle structural materials, such as masonry materials, ceramics, and bones, are to some extent porous, with the size of pores and/or ligaments often being at the nanoscale. Porosity of different materials covers a very wide range, from zero (i.e., full density solids) to >99% for aerogels (AGs). The AGs are representative materials for the limiting case of low-density/high-porosity systems with submicron uniformity. They are sol-gel-derived solids made from nanoscale ligaments randomly interconnected into a macroscopic three-dimensional structure with open-cell porosity tunable up to ∼99.95%.[2] Numerous previous studies[2] have focused on conventional silica AGs with densities above ∼50 mg cm−3, first made by Kistler a number of decades ago.[3] Ligaments in these AGs are made of amorphous SiO2 with variable surface hydroxylation. Successful synthesis of ultralow-density[4] silica AGs has also been reported.[5–7] Ultralow-density nanofoams are currently of interest for thermonuclear fusion energy applications as scaffolds for condensed hydrogen fuel layers in fusion targets.[8] They are also attractive materials for solid-state targets for ultrabright x-ray lasers,[9] energy absorbing structures,[10] compliant electrical contacts,[11] and electromechanical devices.[12] Poor mechanical properties of nanofoams limit their use in these applications.

Atomic layer deposition of ZnO on ultralow-density nanoporous silica aerogel monoliths

We report on atomic layer deposition of an ∼2-nm-thick ZnO layer on the inner surface of ultralow-density (∼0.5% of the full density) nanoporous silica aerogel monoliths with an extremely large effective aspect ratio of ∼105 (defined as the ratio of the monolith thickness to the average pore size). The resultant monoliths are formed by amorphous-SiO2 core/wurtzite-ZnO shell nanoparticles which are randomly oriented and interconnected into an open-cell network with an apparent density of ∼3% and a surface area of ∼100m2g−1. Secondary ion mass spectrometry and high-resolution transmission electron microscopy imaging reveal excellent uniformity and crystallinity of ZnO coating. Oxygen K-edge and Zn L3-edge soft x-ray absorption near-edge structure spectroscopy shows broadened O p- as well as Zn s- and d-projected densities of states in the conduction band.

Lattice damage produced in GaN by swift heavy ions

Wurtzite GaN epilayers bombarded at 300 K with 200 MeV Au-197(16+) ions are studied by a combination of transmission electron microscopy (TEM) and Rutherford backscattering/channeling spectrometry (RBS/C). Results reveal the formation of near-continuous tracks propagating throughout the entire similar to1.5-mum-thick GaN film. These tracks, similar to100 Angstrom in diameter, exhibit a large degree of structural disordering but do not appear to be amorphous. Throughout the bombarded epilayer, high-resolution TEM reveals planar defects which are parallel to the basal plane of the GaN film. The gross level of lattice disorder, as measured by RBS/C, gradually increases with increasing ion fluence up to similar to10(13) cm(-2). For larger fluences, delamination of the nitride film from the sapphire substrate occurs. Based on these results, physical mechanisms of the formation of lattice disorder in GaN in such a high electronic stopping power regime are discussed

Implant isolation of ZnO

We study ion-irradiation-induced electrical isolation in n-type single-crystal ZnO epilayers. Emphasis is given to improving the thermal stability of isolation and obtaining a better understanding of the isolation mechanism. Results show that an increase in the dose of 2 MeV 16O ions (up to ∼2 orders of magnitude above the threshold isolation dose) and irradiation temperature (up to 350 °C) has a relatively minor effect on the thermal stability of electrical isolation, which is limited to temperatures of ∼300–400 °C. An analysis of the temperature dependence of sheet resistance suggests that effective levels associated with irradiation-produced defects are rather shallow (<50 meV). For the case of implantation with keV Cr, Fe, or Ni ions, the evolution of sheet resistance with annealing temperature is consistent with defect-induced isolation, with a relatively minor effect of Cr, Fe, or Ni impurities on the thermal stability of isolation. Results also reveal a negligible ion-beam flux effect in the case o...

Ruthenium/aerogel nanocomposites via atomic layer deposition

We present a general approach to prepare metal/aerogel nanocomposites via template directed atomic layer deposition (ALD). In particular, we used a Ru ALD process consisting of alternating exposures to bis(cyclopentadienyl)ruthenium (RuCp2) and air at 350 °C to deposit metallic Ru nanoparticles on the internal surfaces of carbon and silica aerogels. The technique does not affect the morphology of the aerogel template and offers excellent control over metal loading by simply adjusting the number of ALD cycles. We also discuss the limitations of our ALD approach and suggest ways to overcome these.