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Directed Self-Assembly of block copolymers is a lithographic technique being developed to reach sub-10 nm technological nodes. Recently, high chi block copolymers have been developed to achieve higher resolution. In this paper, the high chi system investigated is a modified polystyrene-b-poly(methyl methacrylate)(PS-b-PMMA) presenting a pitch of 18 nm. One critical step for its integration is the PMMA removal selectively to the PS. Two approaches to remove the PMMA phase are presented, highlighting the challenges encountered due to its smaller dimensions. The first one is a full dry approach based on a CH4/N2 chemistry, which presents some bridge formation due to intensive sidewalls passivation and to a species confinement effect accentuated by the small 9-nm critical dimension of the lines. Therefore, the main high chi PS-b-PMMA dry etching difficulties come from the trade-off between obtaining high selectivity and avoiding bridge formation. The second approach is a mixed wet and dry PMMA removal process based on UV exposure followed by solvent rinse. An Ar/O2 dry brush layer opening was developed and the pattern transfer into the SiO2 and Si underlayers is demonstrated for the high chi PS-b-PMMA.

Directed Self-Assembly (DSA) of Block Copolymers (BCP) by chemo-epitaxial alignment is a promising high resolution lithography technique compatible with CMOS high-volume manufacturing. It allows overcoming limitations in resolution and local stochasticity by conventional, imaging based, lithography. However, for BCP with pitches below 20 nm and guide patterning by immersion lithography (193i), multiplication factors ≥ 4 become necessary, imposing stringent requirements on the guides and defectivity becomes hard to control. The Arkema-CEA (ACE) process flow overcomes this limit by creating the guides by a self-aligned double patterning (SADP) process flow, followed by the deposition of a cross-linkable neutral mat and selective grafting of the guides. This paper reports on the transfer of the process flow to immersion lithography, details challenges encountered in process optimization, notably the dependence of the wetting of the neutral layer on the surface energy and the morphology of the spacers. Last, the paper presents a metrology and defectivity roadmap combined with preliminary, promising results.

Directed Self-Assembly (DSA) of Block Copolymer (BCP) is a promising lithography approach to achieve high resolution pattern dimensions. The current chemo-epitaxy process used to induce block copolymer self-alignment is showing today its limitations. This is due to the resolution limitation of conventional lithography technics needed for the guide formation, used to achieve BCP alignment. This paper introduces a new chemo-epitaxy process, named ACE (Arkema-CEA), which is based on sidewall image transfer (SIT) patterning. This process has the great advantage to offer guides of small critical dimension (CD) and pitch that allows the integration of high χ BCP. In this paper, different parameters of the ACE process are investigated (commensurability, spacer CD …) in order to precisely determine the DSA process window defining the best conditions for BCP alignment. Process window with multiplication factor ranging from 2 to 4 are obtained on BCP under investigation.

A mild procedure for the conjugate addition of the trifluoromethyl anion to activated Michael acceptors such as arylidenemalononitriles (15 examples) and arylidene Meldrum’s acids (9 examples) using phenyl trifluoromethyl sulfone through a reductive magnesium metal mediated procedure is described. The new methodology is used to prepare befloxatone, a reversible and selective monoamine oxidase A inhibitor.

High chi organic lamellar-forming block copolymers were prepared with 18 nm intrinsic period Lo value. The BCPs were coated on a neutral layer on silicon substrates and were either thermally annealed or exposed to solvent vapors both in a 300mm track. The effect of lowering the glass transition temperature (Tg) on the high chi BCP was investigated. Process temperatures and times were varied. It was found that the BCP having lower Tg exhibits faster kinetics and is able to reach alignment in a shorter time than a similar BCP having higher Tg. Fingerprint defect analysis also shows that the BCP with lower Tg has lower defects. The results show that fingerprint formation can be achieved with either ether or ester type solvents depending on the BCP used. The results show that a track process for solvent annealing of high-χ BCPs is feasible and could provide the path forward for incorporation of BCP in future nodes. Finally, directed self-assembly was demonstrated by implemented high chi polymers on a graphoepitaxy test vehicles. CD and line width roughness was evaluated on patterns with a multiplication factor up to 7.

Conference, San Jose CA, Feb 22-25, 2016. Sponsor(s) : SPIE; Tokyo Ohka Kogyo Co; International audience; Properties of new block copolymers systems, specifically designed to reach large periods for the features, are compared to the ones exhibited by classical PS-b-PMMA materials of same dimensions. Conducted studies, like free-surface defects analysis, mild-plasma tomography experiments, graphoepitaxy-guided structures, etch-transfer. indicate much better performances, in terms of achievable film-thicknesses with perpendicular features, defects levels, and dimensional uniformities, for the new system than for the classical PS-b-PMMA. These results clearly highlight unique and original solutions toward an early introduction of DSA technology into large lithographic nodes.

The title reaction can be also applied to the synthesis of compound (IX), a useful precursor for the preparation of befloxatone, which is a reversible and selective monoamine oxidase A inhibitor.

A novel chiral difluoroallylboronate (I) is applied to the reaction with various aromatic and aliphatic aldehydes affording α-gem-difluorohomoallyl alcohols.

Contrary to previous reports, the homologation of benzyloxydifluorovinyllithium with bulky chiral iodomethylboronates readily provides a series of chiral γ,γ-difluoroallylboronates. Asymmetric fluoroallylboration of aldehydes with a 2-phenylbornane-2,3-diol-derived reagent provides gem-difluorinated homoallyl alcohols in good yields and 77-95% ee. Preparation of a chiral α-pyrone in >99% ee has also been described.

Still—Gennari olefination of substrates (II) affords exclusively the (Z)-isomers (IV) which are transformed to the required pyrones (VI) (important building blocks of natural products) via (Z)-alcohols (V).

Background: GABA derivatives are important for the development of drugs for disorders of the CNS and PNS. Results: We describe a simple synthesis of N-benzyl γ-phenyl-γ-aminobutyric acids, via the reductive amination of the corresponding γ-keto acids with benzylamines using ammonia borane. Conclusion: This procedure provides an efficient and economical method for the synthesis of GABA derivatives.

Horner-Wadsworth-Emmons (HWE) or Still-Gennari olefination of TBS-protected 3,3-difluoro-4-hydroxy-2-ones, derived from the difluoroallylboration of aldehydes, provides the Z-isomer of 4,4,-difluoropent-2-enoates. These, upon hydrolysis, followed by Yamaguchi cyclization, afford 5,5-difluoro-4-methyl-5,6-dihydro-α-pyrones in high yields.

The reaction of aldehydes and ketones with primary and secondary amines under conditions A) and B) affords secondary and tertiary amine products in excellent yields.