Selective Synthesis of 2,2,4,4-Tetrasilylpentasilane.

A new structural isomer of nonasilane, 2,2,4,4-tetrasilylpentasilane or (H3Si)3SiSiH2Si(SiH3)3, is formed in disproportionational condensation of neopentasilane. This reaction can be catalyzed by a freshly cleaned borosilicate surface, and the catalyzed reaction can have over 85% selectivity for this branched nonasilane near 100 °C. A synthetic method has been developed from this catalytic reaction for making 98 wt % 2,2,4,4-tetrasilylpentasilane. The high-purity 2,2,4,4-tetrasilylpentasilane has a workable shelf life in 316 stainless steel containers.

Nanosoldering carbon nanotube junctions by local chemical vapor deposition for improved device performance.

The performance of carbon nanotube network (CNN) devices is usually limited by the high resistance of individual nanotube junctions (NJs). We present a novel method to reduce this resistance through a nanoscale chemical vapor deposition (CVD) process. By passing current through the devices in the presence of a gaseous CVD precursor, localized nanoscale Joule heating induced at the NJs stimulates the selective and self-limiting deposition of metallic nanosolder. The effectiveness of this nanosoldering process depends on the work function of the deposited metal (here Pd or HfB2), and it can improve the on/off current ratio of a CNN device by nearly an order of magnitude. This nanosoldering technique could also be applied to other device types where nanoscale resistance components limit overall device performance.

Silver cluster formation, dynamics, and chemistry in metal-organic frameworks.

Synthetic methods used to produce metal nanoparticles typically lead to a distribution of particle sizes. In addition, creation of the smallest clusters, with sizes of a few to tens of atoms, remains very challenging. Nanoporous metal-organic frameworks (MOFs) are a promising solution to these problems, since their long-range crystalline order creates completely uniform pore sizes with the potential for both steric and chemical stabilization. We report a systematic investigation of silver nanocluster formation within MOFs using three representative MOF templates. The as-synthesized clusters are spectroscopically consistent with dimensions < or =1 nm, with a significant fraction existing as Ag(3) clusters, as shown by electron paramagnetic resonance. Importantly, we show conclusively that very rapid TEM-induced MOF degradation leads to agglomeration and stable, easily imaged particles, explaining prior reports of particles larger than MOF pores. These results solve an important riddle concerning MOF-based templates and suggest that heterostructures composed of highly uniform arrays of nanoparticles within MOFs are feasible.

Solution-mediated selective nanosoldering of carbon nanotube junctions for improved device performance.

As-grown randomly aligned networks of carbon nanotubes (CNTs) invariably suffer from limited transport properties due to high resistance at the crossed junctions between CNTs. In this work, Joule heating of the highly resistive CNT junctions is carried out in the presence of a spin-coated layer of a suitable chemical precursor. The heating triggers thermal decomposition of the chemical precursor, tris(dibenzylideneacetone)dipalladium (Pd2(dba)3), and causes local deposition of Pd nanoparticles at the CNT junctions, thereby improving the on/off current ratio and mobility of CNT network devices by an average factor of ∼6. This process can be conducted either in air or under vacuum depending on the characteristics of the precursor species. The solution-mediated nanosoldering process is simple, fast, scalable with manufacturing techniques, and extendable to the nanodeposition of a wide variety of materials.