Topological Constraint Theory Analysis of Rigidity Transition in Highly Coordinate Amorphous Hydrogenated Boron Carbide

Topological constraint theory (TCT) has revealed itself to be a powerful tool in interpreting the behaviors of amorphous solids. The theory predicts a transition between a “rigid” overconstrained network and a “floppy” underconstrained network as a function of connectivity or average coordination number, 〈r〉. The predicted results have been shown experimentally for various glassy materials, the majority of these being based on 4-fold-coordinate networks such as chalcogenide and oxide glasses. Here, we demonstrate the broader applicability of topological constraint theory to uniquely coordinated amorphous hydrogenated boron carbide (a-BC:H), based on 6-fold-coordinate boron atoms arranged into partially hydrogenated interconnected 12-vertex icosahedra. We have produced a substantial set of plasma-enhanced chemical vapor deposited a-BC:H films with a large range of densities and network coordination, and demonstrate a clear threshold in Young\u27s modulus as a function of 〈r〉, ascribed to a rigidity transition. We investigate constraint counting strategies in this material and show that by treating icosahedra as “superatoms,” a rigidity transition is observed within the range of the theoretically predicted 〈r〉c value of 2.4 for covalent solids with bond-stretching and bond-bending forces. This experimental data set for a-BC:H is unique in that it represents a uniform change in connectivity with 〈r〉 and demonstrates a distinct rigidity transition with data points both above and below the transition threshold. Finally, we discuss how TCT can be applied to explain and optimize mechanical and dielectric properties in a-BC:H and related materials in the context of microelectronics applications

Carbon‐Enriched Amorphous Hydrogenated Boron Carbide Films for Very‐Low‐k Interlayer Dielectrics

A longstanding challenge in ultralarge‐scale integration has been the continued improvement in low‐dielectric‐constant (low‐k) interlayer dielectric materials and other specialized layers in back‐end‐of‐the‐line interconnect fabrication. Modeled after the success of carbon‐containing organosilicate materials, carbon‐enriched amorphous hydrogenated boron carbide (a‐BxC:Hy) films are grown by plasma‐enhanced chemical vapor deposition from ortho‐carborane and methane. These films contain more extraicosahedral sp3 hydrocarbon groups than nonenriched a‐BxC:Hy films, as revealed by FTIR and NMR spectroscopy, and also exhibit lower dielectric constants than their nonenriched counterparts, notably due to low densities combined with a low distortion and orientation contribution to the total polarizability. Films with dielectric constant as low as 2.5 are reported with excellent electrical stability (leakage current of 10−9 A cm−2 at 2 MV cm−1 and breakdown voltage of >6 MV cm−1), good thermal conductivity of 0.31 ± 0.03 W m−1 K−1, and high projected Young’s modulus of 12 ± 3 GPa. These properties rival those of leading SiOC:H materials, and position a‐BxC:Hy as an important complement to traditional Si‐based materials to meet the complex needs of next‐generation interconnect fabrication.Carbon‐enriched amorphous hydrogenated boron carbide films are demonstrated with dielectric constant (k) as low as 2.5—attributed to low densities combined with network‐rigidifying CH2 bridging groups—as well as excellent electrical, thermal, and mechanical properties, rivaling those of state‐of‐the‐art silicon‐based low‐k dielectric materials.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/141869/1/aelm201700116_am.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/141869/2/aelm201700116.pd

Six RNA Viruses and Forty-One Hosts: Viral Small RNAs and Modulation of Small RNA Repertoires in Vertebrate and Invertebrate Systems

We have used multiplexed high-throughput sequencing to characterize changes in small RNA populations that occur during viral infection in animal cells. Small RNA-based mechanisms such as RNA interference (RNAi) have been shown in plant and invertebrate systems to play a key role in host responses to viral infection. Although homologs of the key RNAi effector pathways are present in mammalian cells, and can launch an RNAi-mediated degradation of experimentally targeted mRNAs, any role for such responses in mammalian host-virus interactions remains to be characterized. Six different viruses were examined in 41 experimentally susceptible and resistant host systems. We identified virus-derived small RNAs (vsRNAs) from all six viruses, with total abundance varying from “vanishingly rare” (less than 0.1% of cellular small RNA) to highly abundant (comparable to abundant micro-RNAs “miRNAs”). In addition to the appearance of vsRNAs during infection, we saw a number of specific changes in host miRNA profiles. For several infection models investigated in more detail, the RNAi and Interferon pathways modulated the abundance of vsRNAs. We also found evidence for populations of vsRNAs that exist as duplexed siRNAs with zero to three nucleotide 3′ overhangs. Using populations of cells carrying a Hepatitis C replicon, we observed strand-selective loading of siRNAs onto Argonaute complexes. These experiments define vsRNAs as one possible component of the interplay between animal viruses and their hosts

Hydrogen uptake by high purity niobium studied by nuclear analytical methods

Niobium RF superconducting cavities form the basic component of particle accelerators. The presence of trace amounts of hydrogen in niobium is believed to have a detrimental effect on the mechanical and superconducting properties. We have used prompt gamma-ray activation analysis (PGAA) and neutron incoherent scattering to measure bulk hydrogen content in niobium, and the nuclear reaction method to study hydrogen as a function of depth. The methods were used to study native hydrogen concentrations in the niobium, and to study the effects of vacuum heating and acid treatment on the hydrogen concentration

Thermal conductivity-structure-processing relationships for amorphous nano-porous organo-silicate thin films

© 2019, Springer Science+Business Media, LLC, part of Springer Nature. While numerous thermal conductivity investigations of amorphous dielectrics have been reported, relatively few have attempted to correlate to the influence of processing conditions and the resulting atomic structure. In this regard, we have investigated the influence of growth conditions, post deposition curing, elemental composition, atomic structure, and nano-porosity on the thermal conductivity for a series of organo-silicate (SiOCH) thin films. Time-domain thermoreflectance (TDTR) was specifically utilized to measure thermal conductivity while the influence of growth conditions and post deposition curing on composition, mass density, atomic structure, and porosity were examined using nuclear reaction analysis (NRA), Rutherford backscattering spectroscopy (RBS), Fourier-transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR), ellipsometric porosimetry (EP), and positronium annihilation lifetime spectroscopy (PALS). Analytical models describing the thermal conductivity dependence on mass density and vol% porosity were found to generally over-predict the measured thermal conductivity, but improved agreement was obtained when considering only the heat carrying network density determined by FTIR. Ashby’s semi-empirical relation, which assumes only 1/3 of the heat carrying bonds are aligned to the heat transport direction, was also found to reasonably describe the observed trends. However, the thermal conductivity results were best described via a model proposed by Sumirat (J Porous Mater 9:439 (2006)) which considers the effect of both vol% porosity and phonon scattering by nanometer sized pores. Post-deposition curing was additionally observed to increase thermal conductivity despite an increase in nano-porosity. This effect was attributed to an increase in the Si–O–Si network bonding produced by the cure