The Young's modulus, strength, and toughness of nanostructures are important to proposed applications ranging from nanocomposites to probe microscopy, yet there is little direct knowledge of these key mechanical properties. Atomic force microscopy was used to determine the mechanical properties of individual, structurally isolated silicon carbide (SiC) nanorods (NRs) and multiwall carbon nanotubes (MWNTs) that were pinned at one end to molybdenum disulfide surfaces. The bending force was measured versus displacement along the unpinned lengths. The MWNTs were about two times as stiff as the SiC NRs. Continued bending of the SiC NRs ultimately led to fracture, whereas the MWNTs exhibited an interesting elastic buckling process. The strengths of the SiC NRs were substantially greater than those found previously for larger SiC structures, and they approach theoretical values. Because of buckling, the ultimate strengths of the stiffer MWNTs were less than those of the SiC NRs, although the MWNTs represent a uniquely tough, energy-absorbing material.

http://science.sciencemag.org/content/sci/277/5334/1971.full.pdf

Nanobeam mechanics: Elasticity, strength, and toughness of nanorods and nanotubes

A method combining laser ablation cluster formation and vapor-liquid-solid (VLS) growth was developed for the synthesis of semiconductor nanowires. In this process, laser ablation was used to prepare nanometer-diameter catalyst clusters that define the size of wires produced by VLS growth. This approach was used to prepare bulk quantities of uniform single-crystal silicon and germanium nanowires with diameters of 6 to 20 and 3 to 9 nanometers, respectively, and lengths ranging from 1 to 30 micrometers. Studies carried out with different conditions and catalyst materials confirmed the central details of the growth mechanism and suggest that well-established phase diagrams can be used to predict rationally catalyst materials and growth conditions for the preparation of nanowires.

/pdf/a-laser-ablation-method-for-the-synthesis-of-crystalline-102tprgisp.pdf

A laser ablation method for the synthesis of crystalline semiconductor nanowires

Dimensionality plays a critical role in determining the properties of materials due to, for example, the different ways that electrons interact in three-dimensional, twodimensional (2D), and one-dimensional (1D) structures.1-5 The study of dimensionality has a long history in chemistry and physics, although this has been primarily with the prefix “quasi” added to the description of materials; that is, quasi-1D solids, including square-planar platinum chain and metal trichalcogenide compounds,2,6 and quasi2D layered solids, such as metal dichalcogenides and copper oxide superconductors.3-5,7,8 The anisotropy inherent in quasi-1D and -2D systems is central to the unique properties and phases that these materials exhibit, although the small but finite interactions between 1D chains or 2D layers in bulk materials have made it difficult to address the interesting properties expected for the pure low-dimensional systems. Are pure low-dimensional systems interesting and worth pursuing? We believe that the answer to this question is an unqualified yes from the standpoints of both fundamental science and technology. One needs to look no further than past studies of the 2D electron gas in semiconductor heterostructures, which have produced remarkably rich and often unexpected results,9,10 and electron tunneling through 0D quantum dots, which have led to the concepts of the artificial atom and the creation of single electron transistors.11-15 In these cases, lowdimensional systems were realized by creating discrete 2D and 0D nanostructures. 1D nanostructures, such as nanowires and nanotubes, are expected to be at least as interesting and important as 2D and 0D systems.16,17 1D systems are the smallest dimension structures that can be used for efficient transport of electrons and optical excitations, and are thus expected to be critical to the function and integration of nanoscale devices. However, little is known about the nature of, for example, localization that could preclude transport through 1D systems. In addition, 1D systems should exhibit density of states singularities, can have energetically discrete molecularlike states extending over large linear distances, and may show more exotic phenomena, such as the spin-charge separation predicted for a Luttinger liquid.1,2 There are also many applications where 1D nanostructures could be exploited, including nanoelectronics, superstrong and tough composites, functional nanostructured materials, and novel probe microscopy tips.16-29 To address these fascinating fundamental scientific issues and potential applications requires answers to two questions at the heart of condensed matter chemistry and physics research: (1) How can atoms or other building blocks be rationally assembled into structures with nanometer-sized diameters but much longer lengths? (2) What are the intrinsic properties of these quantum wires and how do these properties depend, for example, on diameter and structure? Below we describe investigations from our laboratory directed toward these two general questions. The organization of this Account is as follows. In section II, we discuss the development of a general approach to the rational synthesis of crystalline nanowires of arbitrary composition. In section III, we outline key challenges to probing the intrinsic properties of 1D systems and illustrate solutions to these challenges with measurements of the atomic structure and electronic properties of carbon nanotubes. Last, we discuss future directions and challenges in section IV.

http://cmliris.harvard.edu/assets/AccChemRes_32_435.pdf

Chemistry and Physics in One Dimension: Synthesis and Properties of Nanowires and Nanotubes

Nanotubes from Carbon.

We fabricated field-effect transistors based on individual single- and multi-wall carbon nanotubes and analyzed their performance. Transport through the nanotubes is dominated by holes and, at room temperature, it appears to be diffusive rather than ballistic. By varying the gate voltage, we successfully modulated the conductance of a single-wall device by more than 5 orders of magnitude. Multi-wall nanotubes show typically no gate effect, but structural deformations—in our case a collapsed tube—can make them operate as field-effect transistors.

/pdf/single-and-multi-wall-carbon-nanotube-field-effect-371w7384lu.pdf

Single- and multi-wall carbon nanotube field-effect transistors

Laser vaporization experiments with graphite in a supersonic cluster beam apparatus indicate that the smallest fullerene to form in substantial abundance is C28. Although ab initio quantum chemical calculations predict that this cluster will favor a tetrahedral cage structure, it is electronically open shell. Further calculations reveal that C28 in this structure should behave as a sort of hollow superatom with an effective valence of 4. This tetravalence should be exhibited toward chemical bonding both on the outside and on the inside of the cage. Thus, stable closed-shell derivatives of C28 with large highest occupied molecular orbital—lowest unoccupied molecular orbital gaps should be attainable either by reacting at the four tetrahedral vertices on the outside of the C28 cage to make, for example, C28H4, or by trapping a tetravalent atom inside the cage to make endothedral fullerenes such as Ti@C28. An example of this second, inside route to C28 stabilization is reported here: the laser and carbon-arc production of U@C28.

https://science.sciencemag.org/content/sci/257/5077/1661.full.pdf

Uranium Stabilization of C28: A Tetravalent Fullerene

Carbon nanotubes produced in arcs have been found to have the form of multiwalled fullerenes, at least over short lengths. Sintering of the tubes to each other is the predominant source of defects that limit the utility of these otherwise perfect fullerene structures. The use of a water-cooled copper cathode minimized such defects, permitting nanotubes longer than 40 micrometers to be attached to macroscopic electrodes and extracted from the bulk deposit. A detailed mechanism that features the high electric field at (and field-emission from) open nanotube tips exposed to the arc plasma, and consequent positive feedback effects from the neutral gas and plasma, is proposed for tube growth in such arcs.

https://science.sciencemag.org/content/sci/266/5188/1218.full.pdf

Growth and sintering of fullerene nanotubes.

Elemental carbon can be synthesized in a variety of geometrical forms, from three-dimensional extended structures (diamond) to finite molecules (C(60) fullerite). Results are presented here on the magnetic susceptibility of the least well-understood members of this family, nanotubes and C(60) fullerite. (i) Nanotubes represent the cylindrical form of carbon, intermediate between graphite and fullerite. They are found to have significantly larger orientation-averaged susceptibility, on a per carbon basis, than any other form of elemental carbon. This susceptibility implies an average band structure among nanotubes similar to that of graphite. (ii) High-resolution magnetic susceptibility data on C(60) fullerite near the molecular orientational-ordering transition at 259 K show a sharp jump corresponding to 2.5 centimeter-gram-second parts per million per mole of C(60). This jump directly demonstrates the effect of an intermolecular cooperative transition on an intramolecular electronic property, where the susceptibility jump may be ascribed to a change in the shape of the molecule due to lattice forces.

S. M. McClure

Papers

Uranium Stabilization of C28: A Tetravalent Fullerene

Growth and sintering of fullerene nanotubes.

Magnetic Susceptibility of Molecular Carbon: Nanotubes and Fullerite

The electronic structure of Ca@C60

Growth and Sintering of Fullerene Nanotubes.