The fascinating story of olefin (or alkene) metathesis (eq
1) began almost five decades ago, when Anderson and
Merckling reported the first carbon-carbon double-bond
rearrangement reaction in the titanium-catalyzed polymerization of norbornene. Nine years later, Banks and Bailey reported “a new disproportionation reaction . . . in which olefins are converted to homologues of shorter and longer carbon chains...”. In 1967, Calderon and co-workers named this metal-catalyzed redistribution of carbon-carbon double bonds olefin metathesis, from the Greek word “μeτάθeση”, which means change of position. These contributions have since served as the foundation for an amazing research field, and olefin metathesis currently represents a powerful transformation in chemical synthesis, attracting a vast amount of interest both in industry and academia.

https://core.ac.uk/download/pdf/4884240.pdf

Ruthenium-based heterocyclic carbene-coordinated olefin metathesis catalysts.

: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Large-scale applications of transition metal-catalyzed couplings for the synthesis of pharmaceuticals.

In recent years, olefin cross metathesis (CM) has emerged as a powerful and convenient synthetic technique in organic chemistry; however, as a general synthetic method, CM has been limited by the lack of predictability in product selectivity and stereoselectivity. Investigations into olefin cross metathesis with several classes of olefins, including substituted and functionalized styrenes, secondary allylic alcohols, tertiary allylic alcohols, and olefins with α-quaternary centers, have led to a general model useful for the prediction of product selectivity and stereoselectivity in cross metathesis. As a general ranking of olefin reactivity in CM, olefins can be categorized by their relative abilities to undergo homodimerization via cross metathesis and the susceptibility of their homodimers toward secondary metathesis reactions. When an olefin of high reactivity is reacted with an olefin of lower reactivity (sterically bulky, electron-deficient, etc.), selective cross metathesis can be achieved using fee...

A General Model for Selectivity in Olefin Cross Metathesis

A mean-field phase diagram for conformationally symmetric diblock melts using the standard Gaussian polymer model is presented. Our calculation, which traverses the weak- to strong-segregation regimes, is free of traditional approximations. Regions of stability are determined for disordered (DIS) melts and for ordered structures including lamellae (L), hexagonally packed cylinders (H), body-centered cubic spheres (QIm3m), close-packed spheres (CPS), and the bicontinuous cubic network with Ia3d symmetry (QIa3d). The CPS phase exists in narrow regions along the order−disorder transition for χN ≥ 17.67. Results suggest that the QIa3d phase is not stable above χN ∼ 60. Along the L/QIa3d phase boundaries, a hexagonally perforated lamellar (HPL) phase is found to be nearly stable. Our results for the bicontinuous Pn3m cubic (QPn3m) phase, known as the OBDD, indicate that it is an unstable structure in diblock melts. Earlier approximation schemes used to examine mean-field behavior are reviewed, and compa...

Unifying Weak- and Strong-Segregation Block Copolymer Theories

A method of preparing a cyclic monomer, comprising: forming a first mixture comprising a precursor compound, bis(pentafluorophenyl)carbonate, and a catalyst; wherein the precursor compound has a structure comprising a) two or more carbons, and b) two functional groups selected from the group consisting of primary amine, secondary amine, thiol group, hydroxyl group, and combinations thereof; and agitating the first mixture at a temperature effective to form a second mixture comprising the cyclic monomer, the cyclic monomer selected from the group consisting of a cyclic carbonate, a cyclic carbamate, a cyclic urea, a cyclic thiocarbonate, a cyclic thiocarbamate, and a cyclic dithiocarbonate.

Method of Preparing Cyclic Carbonates, Cyclic Carbamates, Cyclic Ureas, Cyclic Thiocarbonates, Cyclic Thiocarbamates, and Cyclic Dithiocarbonates

A study on the optimization of etch transfer processes using 200-mm-scale production type plasma etch tools for circuit relevant patterning in the sub-30-nm pitch regime using directed self-assembly (DSA) line–space patterning is presented. This work focuses on etch stack selection and process tuning, such as plasma power, chuck temperature, and end point strategy, to improve critical dimension control, pattern fidelity, and process window. Results from DSA patterning of gate structures featuring a high-k dielectric, a metal nitride and poly Si gate electrode, and a SiN capping layer are also presented. These results further establish the viability of DSA pattern generation as a potential method for Complementary metal–oxide–semiconductor (CMOS) integrated circuit patterning beyond the 10-nm node.

Pattern transfer of directed self-assembly patterns for CMOS device applications

An interconnect structure and method for fabricating the interconnect structure having enhanced performance and reliability, by minimizing oxygen intrusion into a seed layer and an electroplated copper layer of the interconnect structure, are disclosed. At least one opening in a dielectric layer is formed. A sacrificial oxidation layer disposed on the dielectric layer is formed. The sacrificial oxidation layer minimizes oxygen intrusion into the seed layer and the electroplated copper layer of the interconnect structure. A barrier metal layer disposed on the sacrificial oxidation layer is formed. A seed layer disposed on the barrier metal layer is formed. An electroplated copper layer disposed on the seed layer is formed. A planarized surface is formed, wherein a portion of the sacrificial oxidation layer, the barrier metal layer, the seed layer, and the electroplated copper layer are removed. In addition, a capping layer disposed on the planarized surface is formed.

Semiconductor interconnect structure having enhanced performance and reliability

Directed self-assembly (DSA) of block copolymers (BCPs) has become a promising patterning technique for 7nm node hole shrink process due to its material-controlled CD uniformity and process simplicity.[1] For such application, cylinder-forming BCP system has been extensively investigated compared to its counterpart, lamella-forming system, mainly because cylindrical BCPs will form multiple vias in non-circular guiding patterns (GPs), which is considered to be closer to technological needs.[2-5] This technological need to generate multiple DSA domains in a bar-shape GP originated from the resolution limit of lithography, i.e. those vias placed too close to each other will merge and short the circuit. In practice, multiple patterning and self-aligned via (SAV) processes have been implemented in semiconductor manufacturing to address this resolution issue.[6] The former approach separates one pattern layer with unresolvable dense features into several layers with resolvable features, while the latter approach simply utilizes the superposition of via bars and the pre-defined metal trench patterns in a thin hard mask layer to resolve individual vias, as illustrated in Fig 1 (upper). With proper design, using DSA to generate via bars with the SAV process could provide another approach to address the resolution issue.

DSA via hole shrink for advanced node applications

Directed polymer self-assembly which combines lithographically defined substrates and self-assembled polymers has
been considered as a potential candidate to extend conventional patterning techniques. In the past few years, successful
demonstration of directed self-assembly of block copolymer shows that this method can afford sub-lithographic
resolution or enhances dimensional control. However, integration of polymer self-assembly into standard lithographic
processes remains a challenge and requires new materials. In this paper, we demonstrate robust and thermally crosslinked
underlayer materials which control the orientation of block copolymer assemblies and are compatible with
standard lithographic processes. These new materials allow simple integration of perpendicularly oriented polystyrene-b-
polymethylmethacrylate (PS-b-PMMA) domains into standard manufacturing processes.

Daniel P. Sanders

Papers

Method of Preparing Cyclic Carbonates, Cyclic Carbamates, Cyclic Ureas, Cyclic Thiocarbonates, Cyclic Thiocarbamates, and Cyclic Dithiocarbonates

Pattern transfer of directed self-assembly patterns for CMOS device applications

Semiconductor interconnect structure having enhanced performance and reliability

DSA via hole shrink for advanced node applications

Integration of Polymer Self-Assembly for Lithographic Application