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To extend directed self-assembly (DSA) of poly(styrene-b-methyl methacrylate) (PS- b -PMMA) for higher resolution, placement accuracy and potentially improved pattern line edge roughness (LER), we have developed a next-generation material platform of organic high-χ block copolymers (“HC series”, AZEMBLY TM EXP PME-3000 series). The new material platform has a built-in orientation control mechanism which enables block copolymer domains to vertically selforient without topcoat/additive or delicate solvent vapor annealing. Furthermore, sub-10 nm lines and spaces (L/S) patterning by two major chemoepitaxy DSA, LiNe and SMART TM processes, was successfully implemented on 12” wafer substrates by using the PME-3000 lamellar series. The results revealed that the new material platform is compatible with the existing PS- b -PMMA-based chemical prepatterns and standard protocols. We also introduced the built-in orientation control strategy to the conventional PS- b -PMMA system, producing a new generation of PS-b-PMMA materials with facile orientation control. The modified PS- b -PMMA (m-PS- b -PMMA) performed LiNe flow DSA yielding a comparable CD process window with improved LER/LWR/SWR after the L/S patterns were transferred into a Si substrate.

A macrocyclic tetranuclear platinum(II) complex [Pt(en)(4,4'-bpy)](4)(NO(3))(8) (1(NO(3))(8); en = ethylenediamine, 4,4'-bpy = 4,4'-bipyridine) and a mononuclear platinum(IV) complex [Pt(en)(2)Br(2)]Br(2) (2Br(2)) formed two kinds of Pt(II)/Pt(IV) mixed valence assemblies when reacted: a discrete host-guest complex 12Br(10) (3) and an extended 1-D zigzag sheet 1(2)(3)Br(8)(NO(3))(6) (4). Single crystal X-ray analysis showed that the dimensions of the assemblies could be stoichiometrically controlled. Resonance Raman spectra suggested the presence of an intervalence interaction, which is typically observed for quasi-1-D halogen-bridged M(II)/M(IV) complexes. The intervalence interaction indicates the presence of an isolated {Pt(II)X-Pt(IV)-XPt(II)} moiety in the structure of 4. On the basis of electronic spectra and polarized reflectance measurements, we conclude that 4 exhibits intervalence charge transfer (IVCT) bands. A Kramers-Kronig transformation was carried out to obtain an optical conductivity spectrum, and two sub-bands corresponding to slightly different Pt(II)-Pt(IV) distances were observed.

To extend scaling beyond poly(styrene-b-methyl methacrylate) (PS-b-PMMA) for directed self-assembly (DSA), high quality organic high-x block copolymers (HC series) were developed and applied to implementation of sub-10 nm L/S DSA. Lamellae-forming block copolymers (BCPs) of the HC series showed the ability to form vertically oriented polymer domains conveniently with the in-house PS-r-PMMA underlayers (AZEMBLY EXP NLD series) without the use of an additional topcoat. The orientation control was achieved with low bake temperatures (≤200 °C) and short bake times (≤5 min). Also, these process-friendly materials are compatible with existing 193i-based graphoepitaxy and chemoepitaxy DSA schemes. In addition, it is notable that 8.5 nm organic lamellae domains were amenable to pattern development by simple dry etch techniques. These successful demonstrations of high-x L/S DSA on 193i-defined guiding patterns and pattern development can offer a feasible route to access sub-10 nm node patterning technology.