Phillip D. Hustad

Catalysts for the living insertion polymerization of alkenes: Access to new polyolefin architectures using Ziegler-Natta chemistry

Coordination-insertion polymerization systems have long been superior to their anionic, cationic, and radical polymerization counterparts with regard to stereochemical control. However, until five years ago, these metal-based insertion methods were inferior to ionic and radical mechanisms in the category of living polymerization, which is simply a polymerization that occurs with rapid initiation and negligible chain termination or transfer. In the last half decade, the living insertion polymerization of unactivated olefins has emerged as a powerful tool for the synthesis of new polymer architectures. Materials available today by this route range from simple homopolymers such as linear and branched polyethylene, to atactic or tactic poly(alpha-olefins), to end-functionalized polymers and block copolymers. This review article summarizes recent developments in this rapidly growing research area at the interface of synthetic and mechanistic organometallic chemistry, polymer chemistry, and materials science. While special emphasis is placed on polymer properties and novel polymeric architectures, most of which were inaccessible just a decade ago, important achievements with respect to ligand and catalyst design are also highlighted.

Semicrystalline thermoplastic elastomeric polyolefins: Advances through catalyst development and macromolecular design

We report the design, synthesis, morphology, phase behavior, and mechanical properties of semicrystalline, polyolefin-based block copolymers. By using living, stereoselective insertion polymerization catalysts, syndiotactic polypropylene-block-poly(ethylene-co-propylene)-block-syndiotactic polypropylene and isotactic polypropylene-block-regioirregular polypropylene-block-isotactic polypropylene triblock copolymers were synthesized. The volume fraction and composition of the blocks, as well as the overall size of the macromolecules, were controlled by sequential synthesis of each block of the polymers. These triblock copolymers, with semicrystalline end-blocks and mid-segments with low glass-transition temperatures, show significant potential as thermoplastic elastomers. They have low Youngs moduli, large strains at break, and better than 90% elastic recovery at strains of 100% or less. An isotactic polypropylene-block-regioirregular polypropylene-block-isotactic polypropylene-block-regioirregular polypropylene-block-isotactic polypropylene pentablock copolymer was synthesized that also shows exceptional elastomeric properties. Notably, microphase separation is not necessary in the semicrystalline isotactic polypropylenes to achieve good mechanical performance, unlike commercial styrenic thermoplastic elastomers.

Intra- and intermolecular NMR studies on the activation of arylcyclometallated hafnium pyridyl-amido olefin polymerization precatalysts.

Pyridyl-amido catalysts have emerged recently with great promise for olefin polymerization. Insights into the activation chemistry are presented in an initial attempt to understand the polymerization mechanisms of these important catalysts. The activation of C1-symmetric arylcyclometallated hafnium pyridyl-amido precatalysts, denoted Me2Hf{N(-),N,C(-)} (1, aryl = naphthyl; 2, aryl = phenyl), with both Lewis (B(C6F5)3 and [CPh3][B(C6F5)4]) and Brønsted ([HNR3][B(C6F5)4]) acids is investigated. Reactions of 1 with B(C6F5)3 lead to abstraction of a methyl group and formation of a single inner-sphere diastereoisomeric ion pair [MeHf{N(-),N,C(-)}][MeB(C6F5)3] (3). A 1:1 mixture of the two possible outer-sphere diastereoisomeric ion pairs [MeHf{N(-),N,C(-)}][B(C6F5)4] (4) is obtained when [CPh3][B(C6F5)4] is used. [HNR3][B(C6F5)4] selectively protonates the aryl arm of the tridentate ligand in both precatalysts 1 and 2. A remarkably stable [Me2Hf{N(-),N,C2}][B(C6F5)4] (5) outer-sphere ion pair is formed when the naphthyl substituent is present. The stability is attributed to a hafnium/eta(2)-naphthyl interaction and the release of an eclipsing H-H interaction between naphthyl and pyridine moieties, as evidenced through extensive NMR studies, X-ray single crystal investigation and DFT calculations. When the aryl substituent is phenyl, [Me2Hf{N(-),N,C2}][B(C6F5)4] (10) is originally obtained from protonation of 2, but this species rapidly undergoes remetalation, methane evolution, and amine coordination, giving a diastereomeric mixture of [MeHf{N(-),N,C(-)}NR3][B(C6F5)4] (11). This species transforms over time into the trianionic-ligated [Hf{N(-),C(-),N,C(-)}NR3][B(C6F5)4] (12) through activation of a C-H bond of an amido-isopropyl group. In contrast, ion pair 5 does not spontaneously undergo remetalation of the naphthyl moiety; it reacts with NMe2Ph leading to [MeHf{N(-),N}NMe2C6H4][B(C6F5)4] (7) through ortho-metalation of the aniline. Ion pair 7 successively undergoes a complex transformation ultimately leading to [Hf{N(-),C(-),N,C(-)}NMe2Ph][B(C6F5)4] (8), strictly analogous to 12. The reaction of 5 with aliphatic amines leads to the formation of a single diastereomeric ion pair [MeHf{N(-),N,C(-)}NR3][B(C6F5)4] (9). These differences in activation chemistry are manifested in the polymerization characteristics of these different precatalyst/cocatalyst combinations. Relatively long induction times are observed for propene polymerizations with the naphthyl precatalyst 1 activated with [HNMe3Ph][B(C6F5)4]. However, no induction time is present when 1 is activated with Lewis acids. Similarly, precatalyst 2 shows no induction period with either Lewis or Brønsted acids. Correlation of the solution behavior of these ion pairs and the polymerization characteristics of these various species provides a basis for an initial picture of the polymerization mechanism of these important catalyst systems.

Katalysatoren für die lebende Insertionspolymerisation von Alkenen: mit Ziegler‐Natta‐Chemie zu neuartigen Polyolefin‐Architekturen

Koordinations-Insertions-Polymerisationen sind, was die Stereokontrolle anbelangt, ihren anionischen, kationischen und radikalischen Gegenstucken schon lange uberlegen. Innerhalb des Bereichs lebender Polymerisationen (d. h. Polymerisationen mit rascher Initiierung und vernachlassigbarer Zahl von Kettenabbruchen oder -ubertragungen) waren diese Insertionsverfahren auf Metallbasis ionischen und radikalischen Reaktionen dagegen bis vor etwa funf Jahren unterlegen. Inzwischen wurden lebende Insertionspolymerisationen von nichtaktivierten Olefinen zu leistungsfahigen Syntheseverfahren fur neuartige Polymerarchitekturen entwickelt. Auf diesem Weg ist heute eine Bandbreite von Materialien zuganglich, die von einfachen Homopolymeren wie linearem und verzweigtem Polyethylen uber ataktische oder taktische Poly(α-olefine) und endgruppenfunktionalisierte Polymere bis hin zu Blockcopolymeren reicht. Dieser Aufsatz fasst neuere Entwicklungen in diesem schnell wachsenden Forschungsgebiet an der Schnittstelle von praparativer und mechanistischer metallorganischer Chemie, Polymerchemie und Materialwissenschaft zusammen. Wir gehen dabei besonders auf Eigenschaften und neuartige Architekturen von Polymeren ein, von denen die meisten vor zehn Jahren noch nicht existierten. Ferner berichten wir uber wichtige Fortschritte beim Design von Liganden und Katalysatoren.

New materials and processes for directed self-assembly

Directed self-assembly (DSA) of block copolymers (BCPs) is a promising technology for advanced patterning at future technology nodes, but significant hurdles remain for commercial implementation. The most widely studied material for DSA is poly(styrene-block-methyl methacrylate) (PS-PMMA), but the relatively weak segregation strength of PSPMMA results in some limitations. This paper reports on these limitations for PS-PMMA and highlights a path to success through use of more strongly segregated “high-χ” block copolymers. In general, stronger segregation is predicted to lower defectivity at equilibrium, but unfortunately, kinetics of self assembly also becomes much slower as segregation strength increases. Recognizing diffusion is much faster for cylinder morphologies than lamellar ones, we have investigated new cylinder-forming BCPs that enable defect elimination with thermal annealing processes. In addition, a formulation strategy is presented that further improves the kinetics of the assembly process, enabling tremendous improvements in defectivity over simple BCP systems. Excitingly, successful chemoepitaxy DSA with a high-χ lamellar BCP is also demonstrated using a thermal annealing process and no top coat. These technologies hold promise to enable DSA with thermal annealing processing across pitches from 40 - 16 nm.

A comparison of the pattern transfer of line-space patterns from graphoepitaxial and chemoepitaxial block co-polymer directed self-assembly

Block co-polymer directed self-assembly (BCP DSA) has become an area of fervent research activity as a potential alternative or adjunct to EUV lithography or self-aligned pitch multiplication strategies. This presentation will evaluate two DSA strategies for patterning line-space arrays at 30nm pitch: graphoepitaxial DSA with surface-parallel cylinder BCPs and chemoepitaxial DSA with surface-normal lamellar BCPs. A comparison of pattern transfer into hard-mask and substrate films will be made by consideration of line and space CDs, line profile of cross-sectional SEM images, and comparison of relative LWR/SWR. The processes will be benchmarked against Micron’s process used in manufacturing its 16nm half-pitch NAND part.

Direct access to functional (Meth)acrylate copolymers through transesterification with lithium alkoxides

A straightforward and efficient synthetic method that transforms poly(methyl methacrylate) (PMMA) into value-added materials is presented. Specifically, PMMA is modified by transesterification to produce a variety of functional copolymers from a single starting material. Key to the reaction is the use of lithium alkoxides, prepared by treatment of primary alcohols with LDA, to displace the methyl esters. Under optimized conditions, up to 65% functionalization was achieved and copolymers containing alkyl, alkene, alkyne, benzyl, and (poly)ether side groups could be prepared. The versatility of this protocol was further demonstrated through the functionalization of both PMMA homo and block copolymers obtained through either radical polymerization (traditional and controlled) or anionic procedures. The scope of this strategy was illustrated by extension to a range of architectures and polymer backbones.

New materials for directed self-assembly for advanced patterning

Directed Self-Assembly (DSA) of block copolymers is a candidate advanced patterning technology at future technology nodes. Although DSA promises resolution and cost benefits, a number of constraints and challenges remain for its implementation. Poly(styrene-block-methyl methacrylate) (PS-b-PMMA) has been widely studied in DSA and applied in various applications to demonstrate the potential of DSA to extend optical lithography, including line space and contact hole patterning and uniformity repair,. However, the relatively weak segregation strength of PS-b-PMMA limits its capability to pattern sub-10 nm features. This paper presents the use of strongly segregated high X block copolymers to enable sub-10 nm patterning. Chemoepitaxy DSA with high X lamellar block copolymers is demonstrated with two different strategies based on thermal annealing process and no top coat. These technologies hold promise to enable the implementation of DSA at future technology nodes.

Graphoepitaxial and chemoepitaxial methods for creating line-space patterns at 33nm pitch: comparison to a HVM process

Block copolymer directed self-assembly (BCP-DSA) may provide a less costly method of forming sub-38nm pitch line-space patterns relative to proven HVM methods, but DSA needs to provide equivalent or improved defect density and pattern quality to warrant consideration for displacing current HVM methods. This paper evaluates the process constraints of three DSA flows and compares the pattern quality after pattern transfer for each flow at its optimal process conditions to the same pattern created by a proven HVM process flow.

Impact of materials selection on graphoepitaxial directed self-assembly for line-space patterning

Directed self-assembly (DSA) of block copolymers (BCPs) is a promising technology for advanced patterning at future technology nodes, but significant hurdles remain for commercial implementation. While chemoepitaxy processes employing poly(styrene-block-methyl methacrylate) (PS-PMMA) are most widely studied for DSA line/space patterning, graphoepitaxy processes using more strongly segregated “high-X;” block copolymers have recently shown a lot of promise, with lower defectivity and line-width roughness (LWR) than comparative chemoepitaxy processes. This paper reports on some of the design considerations for optimizing line/space patterning with these materials. We have found that brush and block copolymer selection are critical to achieve high quality DSA. For example, brush thickness must be optimized to achieve matching space critical dimensions, and brush surface energy impacts kinetics of assembly. The X parameter of the block copolymer should be optimized to balance LWR, kinetics of assembly, and process window. Glass transition temperature (Tg) of the blocks showed little impact on performance. Overall, parameters of both BCP and brush must be simultaneously optimized to achieve high quality DSA.