Characterization of chemical bonding in low-k dielectric materialsfor interconnect isolation: a xas and eels study

The use of low dielectric constant materials in the on-chipinterconnect process reduces interconnect delay, power dissipation andcrosstalk noise. To achieve the requirements of the ITRS for 2007-2009minimal sidewall damage from etch, ash or cleans is required. In chemicalvapor deposited (CVD) organo-silicate glass (OSG) which are used asintermetal dielectric (IMD) materials the substitution of oxygen in SiO2by methyl groups (-CH3) reduces the permittivity significantly (from 4.0in SiO2 to 2.6-3.3 in the OSG), since the electronic polarizability islower for Si-C bonds than for Si-O bonds. However, plasma processing forresist stripping, trench etching and post-etch cleaning removes C and Hcontaining molecular groups from the near-surface layer of OSG.Therefore, compositional analysis and chemical bonding characterizationof structured IMD films with nanometer resolution is necessary forprocess optimization. OSG thin films as-deposited and after plasmatreatment are studied using X-ray absorption spectroscopy (XAS) andelectron energy loss spectroscopy (EELS). In both techniques, the finestructure near the C1s absorption or energy loss edge, respectively,allows to identify C-H, C-C, and C-O bonds. This gives the opportunity todifferentiate between individual low-k materials and their modifications.The O1s signal is less selective to individual bonds. XAS spectra havebeen recorded for non-patterned films and EELS spectra for patternedstructures. The chemical bonding is compared for as-deposited andplasma-treated low-k materials. The Fluorescence Yield (FY) and the TotalElectron Yield (TEY) recorded while XAS measurement are compared.Examination of the C 1s near-edge structures reveal a modified bonding ofthe remaining C atoms in the plasma-treated sample regions

Redox-Active Metaphosphate-Like Terminals Enable High-Capacity MXene Anodes for Ultrafast Na-Ion Storage

D transition metal carbides and/or nitrides, so-called MXenes, are noted as ideal fast-charging cation-intercalation electrode materials, which nevertheless suffer from limited specific capacities. Herein, it is reported that constructing redox-active phosphorus−oxygen terminals can be an attractive strategy for Nb$_4$C$_3$ MXenes to remarkably boost their specific capacities for ultrafast Na$^+$ storage. As revealed, redox-active terminals with a stoichiometric formula of PO$_2$- display a metaphosphate-like configuration with each P atom sustaining three P-O bonds and one P=O dangling bond. Compared with conventional O-terminals, metaphosphate-like terminals empower Nb$_4$C$_3$ (denoted PO$_2$-Nb$_4$C$_3$) with considerably enriched carrier density (fourfold), improved conductivity (12.3-fold at 300 K), additional redox-active sites, boosted Nb redox depth, nondeclined Na$^+$-diffusion capability, and buffered internal stress during Na$^+$ intercalation/de-intercalation. Consequently, compared with O-terminated Nb$_4$C$_3$, PO$_2$-Nb$_4$C$_3$ exhibits a doubled Na$^+$-storage capacity (221.0 mAh g$^{-1}$), well-retained fast-charging capability (4.9 min at 80% capacity retention), significantly promoted cycle life (nondegraded capacity over 2000 cycles), and justified feasibility for assembling energy−power-balanced Na-ion capacitors. This study unveils that the molecular-level design of MXene terminals provides opportunities for developing simultaneously high-capacity and fast-charging electrodes, alleviating the energy−power tradeoff typical for energy-storage devices

Interfacial Covalent Bonds Regulated Electron-Deficient 2D Black Phosphorus for Electrocatalytic Oxygen Reactions

Developing resource-abundant and sustainable metal-free bifunctional oxygen electrocatalysts is essential for the practical application of zinc–air batteries (ZABs). 2D black phosphorus (BP) with fully exposed atoms and active lone pair electrons can be promising for oxygen electrocatalysts, which, however, suffers from low catalytic activity and poor electrochemical stability. Herein, guided by density functional theory (DFT) calculations, an efficient metal-free electrocatalyst is demonstrated via covalently bonding BP nanosheets with graphitic carbon nitride (denoted BP-CN-c). The polarized P-N covalent bonds in BP-CN-c can efficiently regulate the electron transfer from BP to graphitic carbon nitride and significantly promote the OOH* adsorption on phosphorus atoms. Impressively, the oxygen evolution reaction performance of BP-CN-c (overpotential of 350 mV at 10 mA cm−2, 90% retention after 10 h operation) represents the state-of-the-art among the reported BP-based metal-free catalysts. Additionally, BP-CN-c exhibits a small half-wave overpotential of 390 mV for oxygen reduction reaction, representing the first bifunctional BP-based metal-free oxygen catalyst. Moreover, ZABs are assembled incorporating BP-CN-c cathodes, delivering a substantially higher peak power density (168.3 mW cm−2) than the Pt/C+RuO2-based ZABs (101.3 mW cm−2). The acquired insights into interfacial covalent bonds pave the way for the rational design of new and affordable metal-free catalysts. © 2021 The Authors. Advanced Materials published by Wiley-VCH Gmb

Fabrication of Highly Ordered Polymeric Nanodot and Nanowire Arrays Templated by Supramolecular Assembly Block Copolymer Nanoporous Thin Films

Realizing the vast technological potential of patternable block copolymers requires both the precise controlling of the orientation and long-range ordering, which is still a challenging topic so far. Recently, we have demonstrated that ordered nanoporous thin film can be fabricated from a simple supramolecular assembly approach. Here we will extend this approach and provide a general route to fabricate large areas of highly ordered polymeric nanodot and nanowire arrays. We revealed that under a mixture solvent annealing atmosphere, a near-defect-free nanoporous thin film over large areas can be achieved. Under the direction of interpolymer hydrogen bonding and capillary action of nanopores, this ordered porous nanotemplate can be properly filled with phenolic resin precursor, followed by curation and pyrolysis at middle temperature to remove the nanotemplate, a perfect ordered polymer nanodot arrays replication was obtained. The orientation of the supramolecular assembly thin films can be readily re-aligned parallel to the substrate upon exposure to chloroform vapor, so this facile nanotemplate replica method can be further extend to generate large areas of polymeric nanowire arrays. Thus, we achieved a successful sub-30 nm patterns nanotemplates transfer methodology for fabricating polymeric nanopattern arrays with highly ordered structure and tunable morphologies

Effect of Dopants on Zirconia Stabilization—An X-ray Absorption Study: I, Trivalent Dopants

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/65562/1/j.1151-2916.1994.tb06964.x.pd

Nanoindentation study of elastic anisotropy of Cu single crystals and grains in TSVs

This paper presents the results of nanoindentation experiments on Cu single crystals and Cu grains in through silicon via (TSV) structures used for 3D integrated circuit (IC) stacking, at sub-10nm and several-10nm penetration depths. The reduced moduli for Cu single crystals change from an average value to the uni-directional values, as the penetration depths decrease from several-10nm to sub-10nm. At sub-10nm deformation, about one third of the indentations on Cu(111) and Cu(110) show fully elastic behavior, while all indentations on Cu(100) shows elastic-plastic behavior. The reduced modulus values extracted from indents on Cu(111) and Cu(110) with fully elastic behavior are about 195GPa and 145GPa, respectively. For penetration depths of several-10nm up to 50nm, the reduced modulus for Cu(100) varies between 50GPa to 100GPa. The averaged reduced moduli determined at relatively large penetration depths are explained with lattice rotation beneath the indentations. Sinc e the activation of multiple slip systems is required for lattice rotation, the transition of the unidirectional reduced modulus to the averaged value with increasing penetration depths occurs differently for Cu(111) and Cu(100). Similar to the results from Cu single crystals, unidirectional reduced moduli are obtained for the Cu grains in TSV structures at sub-10nm penetration depths