Title: Nano-chessboard superlattices formed by spontaneous phase separation in oxides

Authors: Beth S. Guiton and Peter K. Davies

Source: Nature Materials 6, 586 – 591 (2007)


The use of bottom-up fabrication of nanostructures for nanotechnology inherently requires two-dimensional control of the nanostructures at a particular surface. This could in theory be achieved crystallographically with a structure whose three-dimensional unit cell has two or more—tuneable—dimensions on the nanometre scale. Here, we present what is to our knowledge the first example of a truly periodic two-dimensional nanometre-scale phase separation in any inorganic material, and demonstrate our ability to tune the unit-cell dimensions. As such, it represents great potential for the use of standard ceramic processing methods for nanotechnology. The phase separation occurs spontaneously in the homologous series of the perovskite-based Li-ion conductor, (Nd_{2/3-x}Li_{3x})TiO_3, to give two phases whose dimensions both extend into the nanometre scale. This unique feature could lead to its application as a template for the assembly of nanostructures or molecular monolayers.

Notes: A commentary on this paper by Patrick M Woodward is also available in the same issue of Nature Materials.

Title: Elastic membranes of close-packed nanoparticle arrays

Author: Klara E. Mueggenburg, Xiao-Min Lin, Rodney H. Goldsmith and Heinrich M. Jaeger

Source: Nature Materials, Advanced Online Publication, July 22

Abstract: Nanoparticle superlattices are hybrid materials composed of close-packed inorganic particles separated by short organic spacers. Most work so far has concentrated on the unique electronic, optical and magnetic behaviour of these systems. Here, we demonstrate that they also possess remarkable mechanical properties. We focus on two-dimensional arrays of close-packed nanoparticles and show that they can be stretched across micrometre-size holes. The resulting free-standing monolayer membranes extend over hundreds of particle diameters without crosslinking of the ligands or further embedding in polymer. To characterize the membranes we measured elastic properties with force microscopy and determined the array structure using transmission electron microscopy. For dodecanethiol-ligated 6-nm-diameter gold nanocrystal monolayers, we find a Young’s modulus of the order of several GPa. This remarkable strength is coupled with high flexibility, enabling the membranes to bend easily while draping over edges. The arrays remain intact and able to withstand tensile stresses up to temperatures around 370 K. The purely elastic response of these ultrathin membranes, coupled with exceptional robustness and resilience at high temperatures should make them excellent candidates for a wide range of sensor applications.

Notes: Via Scienceblog

Title: Spontaneous Superlattice Formation in Nanorods Through Partial Cation Exchange

Authors: Richard D. Robinson, Bryce Sadtler, Denis O. Demchenko, Can K. Erdonmez, Lin-Wang Wang, and A. Paul Alivisatos

Source: Science 20 July 2007: Vol. 317. no. 5836, pp. 355 – 358


Lattice-mismatch strains are widely known to control nanoscale pattern formation in heteroepitaxy, but such effects have not been exploited in colloidal nanocrystal growth. We demonstrate a colloidal route to synthesizing CdS-Ag2S nanorod superlattices through partial cation exchange. Strain induces the spontaneous formation of periodic structures. Ab initio calculations of the interfacial energy and modeling of strain energies show that these forces drive the self-organization of the superlattices. The nanorod superlattices exhibit high stability against ripening and phase mixing. These materials are tunable near-infrared emitters with potential applications as nanometer-scale optoelectronic devices.

Most nanoparticle synthesis methods result in nanoparticles bounded by low-index, low-energy faces such as the {111} or {100} atomic planes. This makes intuitive sense, as any high-energy face should grow itself out of existence, leaving particles bound by more stable faces. Unfortunately, particles with mostly low-energy surfaces contain a low percentage of atomic edge and corner sites. The synthetic method of Tian et al. produces particles capped by {730} faces, a surface structure that contains a relatively high density of atomic step edges (see the right panel of the figure). The authors calculated that 43% of the total number of surface atoms reside along steps, which can be compared to 6%, 13%, and 35% for 5-nm-diameter platinum cubes, spheres, and tetrahedral particles, respectively.

From this perspective article of David L Feldheim; the synthetic method of Tian et al in question is an electrochemical method (electrodeposition). Some of the particle shapes shown in the paper of Tian et al reminded me of the particle shapes seen in the simulations of Saswata Bhattacharyya et al (See pp.18-19 of this pdf file for example) — I will try and get a preprint of their paper uploaded on the net, and link here. Here is the draft of the paper by Saswata Bhattacharyya et al on roughening transitions.

The perspective article by Volker Schmidt and Ulrich Goesle summarises the results rather neatly:

As expected, above the eutectic temperature, nanowire growth involves a liquid droplet on top of the germanium nanowires (…). However, when the authors reduced the temperature to below the eutectic temperature while keeping the supply of germanium constant, they observed two distinctly different phenomena (…). Some gold nanodroplets remained liquid even though the temperature was, in one case, more than 100°C below the T_E of 361°C. The authors observed this VLS-type growth mostly for nanowires with relatively large diameters.

In contrast, for nanowires with relatively small diameters, the gold droplet became solid as the temperature fell below T_E. The nanowires continued to grow, but did so much more slowly than in the case of VLS growth (…). Further cooling experiments showed that the transformation of the gold caps from liquid to solid at temperature below T_E could be delayed for tens of minutes. Kodambaka et al. show that this delay depends on various parameters, such as the vapor pressure, the temperature, and the diameter of the nanowires.

The bibliographic details of the paper referred to above are as follows:

Title: Germanium nanowire growth below the eutectic temperature

Authors: S Kodambaka, J Tersoff, M C Reuter, and F M Ross

Source: Science May 4 2007. Vol. 316, No. 5825, pp. 729-732.

Abstract: Nanowires are conventionally assumed to grow via the vapor-liquid-solid process, in which material from the vapor is incorporated into the growing nanowire via a liquid catalyst, commonly a low–melting point eutectic alloy. However, nanowires have been observed to grow below the eutectic temperature, and the state of the catalyst remains controversial. Using in situ microscopy, we showed that, for the classic Ge/Au system, nanowire growth can occur below the eutectic temperature with either liquid or solid catalysts at the same temperature. We found, unexpectedly, that the catalyst state depends on the growth pressure and thermal history. We suggest that these phenomena may be due to kinetic enrichment of the eutectic alloy composition and expect these results to be relevant for other nanowire systems.

Here is a review from the recent issue of Science by Simon J L Billinge and Igor Levin on the available experimental and theoretical methods for the determination of atomic structure at the nanoscale. Here is the abstract:

Emerging complex functional materials often have atomic order limited to the nanoscale. Examples include nanoparticles, species encapsulated in mesoporous hosts, and bulk crystals with intrinsic nanoscale order. The powerful methods that we have for solving the atomic structure of bulk crystals fail for such materials. Currently, no broadly applicable, quantitative, and robust methods exist to replace crystallography at the nanoscale. We provide an overview of various classes of nanostructured materials and review the methods that are currently used to study their structure. We suggest that successful solutions to these nanostructure problems will involve interactions among researchers from materials science, physics, chemistry, computer science, and applied mathematics, working within a “complex modeling” paradigm that combines theory and experiment in a self-consistent computational framework.

Take a look!