Polymers with silicone containing functional end-groups for substrate modification for directed self-assembly applications field

Abstract

Described is a polymer of structure (I), prepared by anionic polymerization which has a polydispersity of 1.00 to 1.05, wherein A is styrenic polymeric segment selected from structure (A-1) or structure (A-2), where m is the number of styrene repeat units and n is the number of styrene repeat unit functionalized by the moiety X, where m is an integer ranging from 5 to 200, and n is an integer ranging from 2 to 4 and were the moiety X either has structure (X-1) or (X-2).

Description

ATTORNEY DOCKET NO.: P24-254NEW POLYMER BRUSHES WITH MULTIPLE SILICONE CONTAINING FUNCTIONAL END-GROUPS FOR SUBSTRATE MODIFICATION FOR DIRECTED SELF-ASSEMBLY APPLICATIONSFIELD

[0001] The disclosed subject matter pertains to ultrathin polymer brushes with multiple silicon containing functional groups with improved resistance to dewetting for use in directed self-assembly.BACKGROUND

[0002] Self-assembly of block copolymers is a method useful for generating smaller and smaller patterned features for the manufacture of microelectronic devices in which the critical dimensions (CD) of features on the order of nanoscale can be achieved. Self-assembly methods are desirable for extending the resolution capabilities of microlithographic technology for repeating features such as an array of contact holes or posts. In a conventional lithography approach, ultraviolet (UV) radiation may be used to expose through a mask onto a photoresist layer coated on a substrate or layered substrate. Positive or negative photoresists are useful, and these can also contain a refractory element such as silicon to enable dry development with conventional integrated circuit (IC) plasma processing. In a positive photoresist, UV radiation transmitted through a mask causes a photochemical reaction in the photoresist such that the exposed regions are removed with a developer solution or by conventional IC plasma processing. Conversely, in negative photoresists, UV radiation transmitted through a mask causes the regions exposed to radiation to become less removable with a developer solution or by conventional IC plasma processing. An integrated circuit feature, such as a gate, via or interconnect, is then etched into the substrate or layered substrate, and the remaining photoresist is removed. When using conventional lithographic exposure processes, the dimensions of features of the integrated circuit feature are limited. Further reduction in pattern dimensions is difficult to achieve with radiation exposure due to limitations related to aberrations, focus, proximity effects, minimum achievable exposure wavelengths and maximum achievable numerical apertures. The need for large-scale integration has led to a continued shrinking of the circuit dimensions and features in the devices. In the past, the final resolution of the features has been dependent upon the wavelength of light used to expose the photoresist, which has its own limitations. Directed (a.k.a. guided) self-assembly techniques, suchATTORNEY DOCKET NO.: P24-254 as graphoepitaxy and chemoepitaxy using block copolymer imaging, which employ a patterned area on a substrate, are highly desirable techniques used to enhance resolution while reducing CD variation. These techniques can be employed to either enhance conventional UV lithographic techniques or to enable even higher resolution and CD control in approaches employing EUV, e-beam, deep UV or immersion lithography. The directed self-assembly block copolymer comprises a block of etch resistant copolymeric unit and a block of highly etchable copolymeric unit, which when coated, aligned, and etched on a substrate give regions of very high-density patterns.

[0003] For directed (guided), or unguided self-assembly, of a block copolymer film, respectively, on a patterned or non-pattemed substrate area, typically the self-assembly process of this block polymer layer occurs during annealing of this film overlying a neutral layer. This neutral layer over a semiconductor substrate may be an unpattemed neutral layer, or in chemoepitaxy or graphoepitaxy, this neutral layer may contain, respectively, graphoepitaxy or chemoepitaxy guiding features (formed through the above-described UV lithographic technique). Neutral layers may be in the form of a grafted brush type neutral layer, or alternatively in the form of a crosslinked neutral layer (neutral layer MAT). During annealing of the block copolymer film, the underlying, neutral layer, directs the nano-phase separation of the block copolymer domains. One example is the formation phase separated domains which are lamellas or cylinders perpendicular to the underlying neutral layer surface. These nano-phase separated block copolymer domains, form a pre-pattern (e.g., line and space L / S) which may be transferred into the substrate through an etching process (e.g., plasma etching). In graphoepitaxy, or in chemoepitaxy, these guiding features may dictate both pattern rectification and pattern multiplication. In the case of an unpattemed neutral layer this produces a repeating array of for instance L / S or CH. For example, in a conventional block copolymer such as poly(styrene-b-methyl methacrylate (P(S-b-MMA)), in which both blocks have similar surface energies at the BCP-air interface, this can be achieved by coating and thermally annealing the block copolymer on a layer of non-preferential or neutral material that is grafted or cross-linked at the polymer-substrate interface.

[0004] In the graphoepitaxy directed self-assembly method, the block copolymers self organizes around a substrate that is pre-patterned with conventional lithography (Ultraviolet, Deep UV, e-beam, Extreme UV (EUV) exposure source) to form repeating topographical features such as a line / space (L / S) or contact hole (CH) pattern. In anATTORNEY DOCKET NO.: P24-254 example of a L / S directed self-assembly array, the block copolymer can form selfaligned lamellar regions which can form parallel line-space patterns of different pitches in the trenches between pre-pattemed lines, thus enhancing pattern resolution by subdividing the space in the trench between the topographical lines into finer patterns. For example, a diblock copolymer or a triblock copolymer which is capable of microphase separation and comprises a block rich in carbon (such as styrene or containing some other element like Si, Ge, Ti) which is resistant to plasma etch, and a block which is highly plasma etchable or removable, can provide a high-resolution pattern definition. Examples of highly etchable blocks can comprise monomers which are rich in oxygen, and which do not contain refractory elements and can form blocks which are highly etchable, such as methyl methacrylate. The plasma etching gases used in the etching process of defining the self-assembly pattern typically are those used in processes employed to make integrated circuits (IC). In this manner, very fine patterns can be created in typical IC substrates than were definable by conventional lithographic techniques, thus achieving pattern multiplication. Similarly, features such as contact holes can be made denser by using graphoepitaxy in which a suitable block copolymer arranges itself by directed self-assembly around an array of contact holes or posts defined by conventional lithography, thus forming a denser array of regions of etchable and etch resistant domains which when etched give rise to a denser array of contact holes. Consequently, graphoepitaxy has the potential to offer both pattern rectification and pattern multiplication.

[0005] In chemical epitaxy, or pinning chemical epitaxy, the self-assembly of the block copolymer is formed on a surface whose guiding features are regions of differing chemical affinity, having no, or insignificant topography (a.k.a. non-guiding topography) which predicates the directed self-assembly process. For example, the surface of a substrate could be patterned with conventional lithography (UV, Deep UV, e-beam EUV) to create surfaces of different chemical affinity in a line and space (L / S) pattern in which exposed areas whose surface chemistry had been modified by irradiation alternate with areas which are unexposed and show no chemical change. These areas present no topographical difference but do present a surface chemical difference or pinning to direct self-assembly of block copolymer segments. Specifically, the directed self-assembly of a block copolymer whose block segments contain etch resistant (such as styrene repeat unit) and rapidly etching repeat units (suchATTORNEY DOCKET NO.: P24-254 as methyl methacrylate repeat units) would allow precise placement of etch resistant block segments and highly etchable block segments over the pattern. This technique allows for the precise placement of these block copolymers and the subsequent pattern transfer of the pattern into a substrate after plasma or wet etch processing. Chemical epitaxy has the advantage that it can be fine-tuned by changes in the chemical differences to help improve line-edge roughness and CD control, thus allowing for pattern rectification. Other types of patterns such as repeating contact holes (CH) arrays could also be pattern rectified using chemoepitaxy.

[0006] Neutral layers are layers on a substrate or the surface of a treated substrate which have no affinity for either of the block segment of a block copolymer employed in directed self-assembly. In the graphoepitaxy method of directed self-assembly of block copolymer, neutral layers are useful as they allow the proper placement or orientation of block polymer segments for directed self-assembly which leads to proper placement of etch resistant block polymer segments and highly etchable block polymer segments relative to the substrate. For instance, in surfaces containing line and space features which have been defined by conventional radiation lithography, a neutral layer allows block segments to be oriented so that the block segments are oriented perpendicular to the surface of the substrates, an orientation which is ideal for both pattern rectification and pattern multiplication depending on the length of the block segments in the block copolymer as related to the length between the lines defined by conventional lithography. If a substrate interacts too strongly with one of the block segments it would cause it to he flat on that surface to maximize the surface of contact between the segment and the substrate; such a surface would perturb the desirable perpendicular alignment which can be used to either achieve pattern rectification or pattern multiplication based on features created through conventional lithography. Modification of selected small areas or pinning of substrate to make them strongly interactive with one block of the block copolymer and leaving the remainder of the surface coated with the neutral layer can be useful for forcing the alignment of the domains of the block copolymer in a desired direction, and this is the basis for the pinned chemoepitaxy or graphoepitaxy employed for pattern multiplication. Neutral layer materials may be of two types, one type is a polymer brush material which forms a grafted layer on a substrate, another type is a crosslinking (MAT type) material which forms a crosslinked polymer layer on a substrate.ATTORNEY DOCKET NO.: P24-254

[0007] Pinning layer are layers on a substrate which have a preference for either the highly etchable block copolymer segment or the etch resistant block copolymer segments. These materials may, similarly to neutral layer, be either brush type materials which graft on a substrate or a crosslinkable polymer (MAT), which can form a crosslinked pinning layer on a substrate.

[0008] Directed self-assembly is a process well-known in photolithography industries for enabling arrays of line & space and contact holes printing on silicon wafer using organic diblock copolymers (ref. 1 to 5). [1. Rahman, Md. S. et al., Multi-pitch tolerance block copolymers with enhanced kinetics for directed self-assembly applications", WO 2022 / 223670 Al; 2. Liu, C. et al., "Chemical patterns for directed self-assembly of lamellae-forming block copolymers with density multiplication of features", Macromolecules, 2013, 46, 1415-1424; 3. Tsai, H. et al., "Two-dimensional pattern forming using graphoepitaxy of PS-6-PMMA block copolymers for advanced FinFET device and circuit fabrication. ACS Nano, 8, 5227- 5232; 4. Mansky, P. et al., "Controlling polymer-surface interactions with random copolymer brushes", Science, 275, 1458-1460 (2005); 5. Hinsberg et al.," Selfassembling materials for lithographic patterning: Overview, status and moving forward, " Proceedings of SPIE, vol. 7637, 76370G-1 (2010)].

[0009] Polymer brushes have unique chain-end functionality that can undergo chemical reaction with substrate to form covalent bonding. The process will modify the substrate chemically for enabling chemoepitaxy pre-pattern formation for directed self-assembly. Ultrathin polymer brushes on substrates are required for certain advanced applications for directed self-assembly. These ultrathin brushes require polymers which have very short chains and consequently have very low molecular weight (Mn<5,000 g / mol) and are generally prone to dewetting while baking during lithographic processing resultin to non-uniform grafting on substrates of low molecular weight polystyrene or PMMA brushes with terminal -CH2OH end groups. Moreover, the chemical linkage that established, the -C-O-Si bond with silicon wafer or oxidized silicon wafer is hydrolytically weak and can break away at moist condition, or over time. Another issue with coating low molecular weight PS brushes (M> <5,000 g / mol) on silicon wafer is that they can dewet significantly while annealing. Hydroxyl functional group is generally used as end group for polymer grafting-to chemistry.ATTORNEY DOCKET NO.: P24-254BRIEF DESCRIPTION OF DRAWINGS

[0010] FIG. 1 Schematic of PS-SiMe2H end functionalized with H

[0011] FIG. 2 Schematic of PS-6-(SSiMe2H)3end functionalized with H

[0012] FIG. 3 GPC profile of PS-6-(SSiMe2H)3-H

[0013] FIG. 4 Schematic of PS-6-(SSiMe2H)3 end functionalized with SiMe2H

[0014] FIG. 5 GPC profile of PS-Si(Me)2-H

[0015] FIG. 6 GPC profile of PS-6-(SSiMe2H)3- SiMe2H (Example 3)

[0016] FIG. 7 Schematic of PS-b-(SSiMe2H)3 end functionalized with CH2-CH2-CH2- OH

[0017] FIG. 8. GPC profile of PS-(SSiMe2H)3- CH2-CH2-CH2-OH

[0018] FIG. 9 Coating (~30 nm FT) of PS-SiMe2H (Example 2) on dielectric substrates at different annealing condition and observation of dewetting by optical image after annealing

[0019] FIG. 10 Coating (~30 nm FT) of PS-CH2-CH2-CH2-OH (Comp Ex 2) on dielectric substrates at different annealing condition and observation of dewetting by optical image after annealing.

[0020] FIG. 11 Partial grafting condition of PS-CH2CH2CH2OH brush (comparative example 1) compared to dimethylsilane terminal PS (example 1) brushes at 200°C / 2 min / air. Presence of free surface Si-OH activates slow hydrolysis of PS grafts in the case of PS-CH2-O-Si linkage.

[0021] FIG. 12. Fully grafted PS-CH2CH2CH2OH brush (comparative example 1) and dimethylsilane terminal PS (example 1) brushes at 250°C / 30 min / N2 with absence of free Si-OH group on the substrates.SUMMARY

[0022] To overcome the challenges described in the background section, the disclosed and claimed subject matter pertains to new approach to for ultrathin brushes where the grafting is done using multiple silicon containing functional groups such as silyl hydride or silyldimethylamine functionalities at the chain-end of the vinyl polymer brushes. The mentioned silyl functional end groups will interact with substrate dangling hydroxyl groups and form -Si-O-Si linkage which is hydrolytically stable and also suppresses dewetting of low molecular weight brushes. FIG. 1 shows schematically a comparison of grafting using an alcohol 1) which is a reversible equilibrium of a partial graft and 2) an irreversible partial graft using as an exampleATTORNEY DOCKET NO.: P24-254 silyl hydride. As shown in FIG. 1 a free hydroxyl or acid protons in the substrate catalyze the hydrolysis of grafted chains in the case of PSCH2 CH2 CH2OH (1) and formation of strong hydrolytically stable, chemical bond of Si-O-Si linkage in the case of PS-6-(SiMe2H)3-H (2). This unique behavior was demonstrated using different types of brush polymer comprising styrenic moi eties.

[0023] More specifically the disclosed and claimed subject matter pertains to a polymer of structure (I), prepared by anionic polymerization which has a poly dispersity of 1.00 to 1.05, wherein A is styrenic polymeric segment selected from structure (A- 1 ) or structure (A-2), where m is the number of styrene repeat units and n is the number of styrene repeat unit functionalized by the moiety X, where m is an integer ranging from 5 to 200, and n is an integer ranging from 2 to 4, where X is H, or a moiety X-2 or X-3, where Rxia, Rxib, Rx2a, Rx2b, Rx2c and RX2d are individually selected from a Ci-4 alkyl, Ei is a Ci-18 alkyl, E2 is H, a moiety of structure (X-l), structure (X-2) or structure (X-3), where Rz2, Rzs and Rz4, are independently selected from H, a C1-8 alkyl, and an aryl, and further where Rz, Rzi, are either independently selected from H, a C1-8 alkyl, an aryl, or form together a C3 to C4 alkylene moiety which forms 5 to 6 cyclic alkane, and nz is either 0 or 1, provided that when structure (A-l) is present at least one of E2 or X is structure (X-2) or structure (X-3), and then when structure (A-2) is present at least one of E2 or X is structure (X-2) or structure (X-3).

[0024] Also disclosed and claimed is subject matter pertains to a composition comprised of said copolymer of structure (I) and an organic spin casting solvent and using said composition in lithographic processes which employ self-assembly orATTORNEY DOCKET NO.: P24-254 directed self-assembly (DS A) in the manufacture of IC devices.DETAILED DESCRIPTION

[0025] It is to be understood that both the foregoing general description and the following detailed description are illustrative and explanatory, and are not restrictive of the subject matter, as claimed. In this application, the use of the singular includes the plural, the word "a" or "an" means "at least one", and the use of "or" means "and / or," unless specifically stated otherwise. Furthermore, the use of the term "including," as well as other forms such as "includes" and "included," is not limiting. Also, terms such as "element" or "component" encompass both elements and components comprising one unit and elements or components that comprise more than one unit, unless specifically stated otherwise. As used herein, the conjunction "and" is intended to be inclusive and the conjunction "or" is not intended to be exclusive unless otherwise indicated. For example, the phrase "or, alternatively" is intended to be exclusive. As used herein, the term "and / or" refers to any combination of the foregoing elements including using a single element.

[0026] The term Cxwhere x is a positive integer designates the number of carbons in a moiety. Similarly, the term Ci to C3 alkyl or Ci-4 alkyl embodies methyl and C2 to C4 linear alkyls and C3 to C4 branched alkyl moi eties, for example as follows: methyl(- CH3), ethyl (-CH2-CH3), n-propyl (-CH2-CH2-CH3), isopropyl (-CH(CH3)2, n-butyl (- CH2-CH2-CH2-CH3), tert-butyl (-C(CH3)3), isobutyl (CH2-CH(CH3)2, 2-butyl (- CH(CH3)CH2-CH3). Similarly, the term Ci to Cs alkyl or C1-8 embodies, Ci to Cs linear alkyls (methyl is considered a linear alkyl), C3 to Cs branched alkyls, C4 to Cs cycloalkyls (e.g., cyclopentyl, cyclohexyl etc.) or C5-8 alkylenecycloalkyls (e.g., -CH2- cyclohexyl, CFh-CFh-cyclopentyl etc. Other designation such as Ci-18, C1-6, C1-15 are defined in the same way unless otherwise indicated.

[0027] The term C2 to Cs alkylene or C2-8 embodies C2 to Cs linear alkylene moieties (e.g., ethylene, propylene etc.) and C3 to Cs branched alkylene moieties (e.g., -CH(CH3)-, -CH(CH3)-CH2-, etc.) unless otherwise indicated.

[0028] The term “g / mol,” is an abbreviation of grams per mole. The term “Kg / mol,” is an abbreviation of kilograms per mole.

[0029] The term “CH,” is an abbreviation for contact hole lithographic features, the term “L / S,” is an abbreviation for line and space lithographic features.

[0030] The term “b,” in a copolymer structure indicates that this is a block copolymer.ATTORNEY DOCKET NO.: P24-254Similarly, the term “co,” in a copolymer structure indicates that this is a random copolymer.Polymers of Structure (I)

[0031] The disclosed and claimed subject matter pertains to a polymer of structure (I), prepared by anionic polymerization which has a poly dispersity of 1.00 to 1.05, wherein A is styrenic polymeric segment selected from structure (A- 1) or structure (A-2), where m is the number of styrene repeat units and n is the number of styrene repeat unit functionalized by the moiety X, where m is an integer ranging from 5 to 200, and n is an integer ranging from 2 to 4.

[0032] In this embodiment X is H, or a moiety of structure (X-2) or a moiety of structure (X-3), where Rxia, Rxib, Rx2a, Rx2b, Rx2c and RX2d are individually selected from a Ci-4 alkyl, Ei is a Ci-i8 alkyl. Further in this embodiment E2 is H, a moiety of structure (X-l), a moiety of structure (X-2) or a moiety of structure (X-3).

[0033] Further, in this embodiment in moiety of structure (X-l), Rz2, Rzs and Rz4, are independently selected from H, a C1-8 alkyl, and an aryl, and further where Rz, Rzi, are either independently selected from H, a C1-8 alkyl, an aryl, or form together a C3 to C4 alkylene moiety which forms 5 to 6 cyclic alkane, and nz is either 0 or 1.

[0034] Further, in this embodiment, when A, said styrenic polymeric segment moiety, has structure (A-l), and E2 is a moiety of structure (X-l) then X is either a moiety of structure (X-2) or a moiety of structure (X-3), and when A, said styrenic polymeric segment has structure (A-2) then X is either a moiety of structure (X-2) or a moiety of structure (X-3).ATTORNEY DOCKET NO.: P24-254

[0035] In another aspect of said disclosed and claimed subject matter, said polymer of structure (I), has a poly dispersity from 1.00 to 1.02.

[0036] In another aspect of said disclosed and claimed subject matter, in said polymer of structure (I), Rxia, Rxib, Rx2a, Rx2b, Rx2c and Rx2d are individually selected from a Ci- 3 alkyl. In another aspect of this embodiment, Rxia, R ib, Rx2a, Rx2b, Rx2c and RX2d are individually selected from a C1-2 alkyl. In another aspect of this embodiment, Rxia, Rxib, Rx2a, Rx2b, RX2C and Rx2d are methyl.

[0037] In another aspect of said disclosed and claimed subject matter, in said polymer of structure (I), A has structure (A- 1 ). In one aspect of this embodiment X has structure (X-2), and E2 is H. In another aspect of this embodiment X has structure (X-2), an E2 has structure (X-l). In another aspect of this embodiment X has structure (X-3), and E2 is H. In another aspect of this embodiment X has structure (X-3), and E2 has structure (X-l). In another aspect of this embodiment X has structure (X-2), and E2 is has structure (X-2). In another aspect of this embodiment X has structure (X-2), and E2 has structure (X-3). In another aspect of this embodiment X has structure (X-3), and E2 has structure (X-2). In another aspect of this embodiment X has structure (X-3), and E2 has structure (X-3).

[0038] In the embodiments of structure (A-l) where E2 has structure (X-l), in some embodiment E2 more specifically has structure (X-l a). In one aspect of this embodiment, Rz, Rzi, Rz2, Rzs, and Rz4 are all H. In another aspect, of this embodiment, Rz, Rzi, Rz2, and Rzs, are all H and Rz4 is a C1-8 alkyl, or more specifically RZ4 is a C1-4 alkyl, or even more specifically Rz4 is methyl. In another aspect of this embodiment, Rz, Rzi, Rz2, and Rzs, are all H and Rz4 is an aryl, or more specifically RZ4 is phenyl. In another aspect of this embodiment Rz, Rzi, Rzs, and Rz4, are all H and RZ2 is a C1-8 alkyl or more specifically Rz2 is a Ci-4 alkyl, or even more specifically RZ2 is methyl. In another aspect of this embodiment, Rz, Rzi, Rzs, and Rz4, are all H and RZ2 is an aryl, or more specifically Rz2 is phenyl.

[0039] In the embodiments of structure (A-l) where E2 has structure (X-l), in some embodiment E2 more specifically has structure (X-lb). In another aspect, of this embodiment, Rz, Rzi, and Rz2. are all H. In another aspect, of this embodiment, Rz, Rzi, are all H and Rz2 is a C1-8 alkyl, or more specifically Rz2 is a Ci-4 alkyl, or even more specifically Rz2 is methyl. In another aspect, of this embodiment, Rz, Rzi, are all H and Rz2 is an aryl, or more specifically Rz2 is phenyl.ATTORNEY DOCKET NO.: P24-254

[0040] In the embodiments of structure (A-2) where E2 has structure (X-l), in some embodiment E2 more specifically has structure (X-l a). In one aspect of this embodiment, Rz, Rzi, Rz2, Rzs, and Rz4 are all H. In another aspect, of this embodiment, Rz, Rzi, Rz2, and Rzs, are all H and Rz4 is a C1-8 alkyl, or more specifically RZ4 is a C1-4 alkyl, or even more specifically Rz4 is methyl. In another aspect of this embodiment, Rz, Rzi, Rz2, and Rzs, are all H and Rz4 is an aryl, or more specifically RZ4 is phenyl. In another aspect of this embodiment Rz, Rzi, Rzs, and Rz4, are all H and RZ2 is a C1-8 alkyl or more specifically Rz2 is a C1-4 alkyl, or even more specifically RZ2 is methyl. In another aspect of this embodiment, Rz, Rzi, Rzs, and Rz4, are all H and RZ2 is an aryl, or more specifically Rz2 is phenyl.

[0041] In the embodiments of structure (A-2) where E2 has structure (X-l), in some embodiment E2 more specifically has structure (X-lb). In another aspect, of this embodiment, Rz, Rzi, and Rz2. are all H. In another aspect, of this embodiment, Rz, Rzi, are all H and Rz2 is a C1-8 alkyl, or more specifically Rz2 is a Ci-4 alkyl, or even more specifically Rz2 is methyl. In another aspect, of this embodiment, Rz, Rzi, are all H and Rz2 is an aryl, or more specifically Rz2 is phenyl.Rz Rzi RZ3RZ RZ<— ! 1— C IH - C I - C I>-) - OH — ! 1— C \H> - C I— \ )— OHRZ2RZ4 (X-l a)RZ2 (X-lb)

[0042] In another aspect of said disclosed and claimed subject matter, in said polymer of structure (I), A has structure (A-2). In one aspect of this embodiment X has structure (X-2), and E2 is H. In another aspect of this embodiment X has structure (X-2), an E2 has structure (X-l). In another aspect of this embodiment X has structure (X-3), and E2 is H. In another aspect of this embodiment X has structure (X-3), and E2 has structure (X-l). In another aspect of this embodiment X has structure (X-2), and E2 is has structure (X-2). In another aspect of this embodiment X has structure (X-2), and E2 has structure (X-3). In another aspect of this embodiment X has structure (X-3), and E2 has structure (X-2). In another aspect of this embodiment X has structure (X-3), and E2 has structure (X-3).

[0043] In another aspect of said disclosed and claimed subject matter, in said polymer has structure (II).ATTORNEY DOCKET NO.: P24-254

[0044] In another aspect of said disclosed and claimed subject matter, in said polymer has structure (II-l). In another aspect of this embodiment, it has structure (Il-la). In another aspect of this embodiment, it has structure (Il-lb).

[0045] In another aspect of said disclosed and claimed subject matter, in said polymer has structure (II- 1c). In another aspect of this embodiment, it has structure (II- Id). In another aspect of this embodiment, it has structure (II- le). In another of this embodiment it has structure. (Il-lf). In another aspect of this embodiment, it has structure (Il-lg).

[0046] In one aspect of structures (II- le), and (II- 1g), Rz, Rzi, Rz2, Rzs, and Rz4 are all H. In one aspect of structures (II- le), and (II- 1g), Rz, Rzi, Rz2, and Rzs, are all H and RZ4 is a Ci-8 alkyl, in another aspect of this embodiment Rz4 is a Ci-4 alkyl, in another aspect of this embodiment Rz4 is methyl. In one aspect of structures (II- le), and (Illg), Rz, Rzi, RZ2, and Rzs, are all H and Rz4 is an aryl, in another aspect of this embodiment Rz4 is phenyl. In one aspect of structures (Il-le), and (II- 1 g), Rz, Rzi, Rzs, and RZ4, are all H and Rz2 is a Ci-8 alkyl, in another aspect of this embodiment Rz2 is a Ci-4 alkyl, in another aspect of this embodiment Rz2 is methyl. In one aspect ofATTORNEY DOCKET NO.: P24-254 structures (Il-le), and (Il-lg), Rz, Rzi, Rzs, and Rz4, are all H and Rz2 is an aryl, in another aspect of this embodiment Rz2 is phenyl. In one aspect of structures (II- Id), and (II- 1 f), Rz, Rzi, and Rz2. are all H. In one aspect of structures (Il-ld), and (Il-lf),Rz, Rzi, are all H and Rz2 is a Ci-8 alkyl, in one aspect of this embodiment Rz2 is a Ci-4 alkyl, in another aspect of this embodiment Rz2 is methyl. In one aspect of structures(II- Id), and (II- If), Rz, Rzi, are all H and Rz2 is an aryl in another aspect of this embodiment Rz2 is phenyl.

[0047] In another aspect of said disclosed and claimed subject matter, in said polymer has structure (II-2). In another aspect of this embodiment, it has structure (II-2a). InATTORNEY DOCKET NO.: P24-254

[0048] In another aspect of said disclosed and claimed subject matter, in said polymer has structure (II-3). In another aspect of this embodiment, it has structure (II-3a). In another aspect of this embodiment it has structure (II-3b).

[0049] In another aspect of said disclosed and claimed subject matter, in said polymer has structure (II-4).ATTORNEY DOCKET NO.: P24-254

[0050] In another aspect of said disclosed and claimed subject matter, said polymer has structure (II-5). In another aspect of this embodiment, it has structure (II-5a). In another aspect of this embodiment, it has structure (II-5b).

[0051] In another aspect of said disclosed and claimed subject matter, said polymer has structure (II-5c), In another aspect of this embodiment, it has structure (II-5d). In another aspect of this embodiment, it has structure (II-5e). In another aspect of this embodiment, it has structure (II-5f). In another aspect of this embodiment, it has structure (II-5g).

[0052] In one aspect of structures (II-5e), and (II-5g), Rz, Rzi, Rz2, Rzs, and Rz4 are all H. In one aspect of structures (II-5e), and (II-5g), Rz, Rzi, Rz2, and Rzs, are all H and RZ4 is a Ci-8 alkyl, in another aspect of this embodiment Rz4 is a Ci-4 alkyl, in another aspect of this embodiment Rz4 is methyl. In one aspect of structures (II-5e), and (II-5g), Rz, Rzi, Rz2, and Rzs, are all H and Rz4 is an aryl, in another aspect of this embodiment Rz4 is phenyl. In one aspect of structures (II-5 e), and (II-5g), Rz, Rzi, Rzs,ATTORNEY DOCKET NO.: P24-254 and RZ4, are all H and Rz2 is a Ci-8 alkyl, in another aspect of this embodiment Rz2 is a Ci-4 alkyl, in another aspect of this embodiment Rz2 is methyl. In one aspect of structures (II-5e), and (II-5g), Rz, Rzi, Rzs, and Rz4, are all H and Rz2 is an aryl, in another aspect of this embodiment Rz2 is phenyl. In one aspect of structures (II-5d), and (II-5f), Rz, Rzi, and Rz2. are all H. In one aspect of structures (II-5d), and (II-5f), Rz, Rzi, are all H and Rz2 is a Ci-8 alkyl, in one aspect of this embodiment Rz2 is a Ci- 4 alkyl, in another aspect of this embodiment Rz2 is methyl. In one aspect of structures(II-5d), and (II-5f), Rz, Rzi, are all H and Rz2 is an aryl in another aspect of this embodiment Rz2 is phenyl.

[0053] In another aspect of said disclosed and claimed subject matter, said polymer has structure (II-6). In another aspect of this embodiment, it has structure (II-6a). In another aspect of this embodiment, it has structure (II-6b).ATTORNEY DOCKET NO.: P24-254

[0054] In another aspect of said disclosed and claimed subject matter, said polymer has structure (II-7). In another aspect of this embodiment, it has structure (II-7a). In another aspect of this embodiment, it has structure (II-7b).

[0055] In another aspect of said disclosed and claimed subject matter, said polymer has structure (II-8) . In another aspect of this embodiment, it has structure (II-8a). In another aspect of this embodiment, it has structure (II-8b).ATTORNEY DOCKET NO.: P24-254

[0056] In another aspect of said disclosed and claimed subject matter, said polymer has structure (III),

[0057] In another aspect of said disclosed and claimed subject matter, said polymer has structure (III-l). In another aspect of this embodiment, it has structure (Ill-la). In another aspect of this embodiment, it has structure (III- lb).

[0058] In another aspect of said disclosed and claimed subject matter, said polymer has structure has structure (III- 1 c). In another aspect of this embodiment, it has structureATTORNEY DOCKET NO.: P24-254(III-lc). In another aspect of this embodiment, it has structure (Ill-Id). In another aspect of this embodiment, it has structure (Ill-le). In another aspect of this embodiment, it has structure (III- If). In another aspect of this embodiment, it has structure (Ill-lg).

[0059] In one aspect of structures (III- 1 e), and (Ill-lg), Rz, Rzi, Rz2, Rzs, and Rz4 are all H. In one aspect of structures (Ill-le), and (Ill-lg), Rz, Rzi, Rz2, and Rzs, are all H and RZ4 is a Ci-8 alkyl, in another aspect of this embodiment Rz4 is a Ci-4 alkyl, in another aspect of this embodiment Rz4 is methyl. In one aspect of structures (Ill-le), and (III- 1g), Rz, Rzi, Rz2, and Rzs, are all H and Rz4 is an aryl, in another aspect of this embodiment Rz4 is phenyl. In one aspect of structures (Ill-le), and (Ill-lg), Rz, Rzi, Rzs, and Rz4, are all H and Rz2 is a Ci-8 alkyl, in another aspect of this embodiment Rz2 is a Ci-4 alkyl, in another aspect of this embodiment Rz2 is methyl. In one aspect of structures (Ill-le), and (Ill-lg), Rz, Rzi, Rzs, and Rz4, are all H and Rz2 is an aryl, in another aspect of this embodiment Rz2 is phenyl. In one aspect of structures (III- Id), and (Ill-lf), Rz, Rzi, and Rz2. are all H. In one aspect of structures (Ill-Id), and (III- If), Rz, Rzi, are all H and Rz2is a Ci-8 alkyl, in one aspect of this embodiment Rz2 is a Ci-4 alkyl, in another aspect of this embodiment Rz2 is methyl. In one aspect of structures (Ill-Id), and (Ill-lf), Rz, Rzi, are all H and Rz2 is an aryl in another aspect of this embodiment Rz2 is phenyl.(Ill-le)ATTORNEY DOCKET NO.: P24-254g)

[0060] In another aspect of said disclosed and claimed subject matter, said polymer has structure has structure (III-2). In another aspect of this embodiment, it has structure (III-2a). In another aspect of this embodiment, it has structure (III-2b).

[0061] In another aspect of said disclosed and claimed subject matter, said polymer has structure has structure (III-3). In another aspect of this embodiment, it has structure (III-3a). In another aspect of this embodiment, it has structure (III-3b).ATTORNEY DOCKET NO.: P24-254

[0062] In another aspect of said disclosed and claimed subject matter, said polymer has structure has structure (III-4).

[0063] In another aspect of said disclosed and claimed subject matter, said polymer has structure has structure (III-5). In another aspect of this embodiment, it has structure (III-5a). In another aspect of this embodiment, it has structure (III-5b).

[0064] In another aspect of said disclosed and claimed subject matter, said polymer has structure has structure (III-6). In another aspect of this embodiment, it has structure (III-6a). In another aspect of this embodiment, it has structure (III-6b). In another aspect of this embodiment, it has structure (III-6c). In another aspect of this embodiment, it has structure (III-6d.

[0065] In one aspect of structures (III-6b), and (III-6d), Rz, Rzi, Rz2, Rzs, and Rz4 are all H. In one aspect of structures ((III-6b), and (III-6d), Rz, Rzi, Rz2, and Rzs, are all HATTORNEY DOCKET NO.: P24-254 and RZ4 is a Ci-8 alkyl, in another aspect of this embodiment Rz4 is a Ci-4 alkyl, in another aspect of this embodiment Rz4 is methyl. In one aspect of structures (III-6b), and (III-6d), Rz, Rzi, Rz2, and Rzs, are all H and Rz4 is an aryl, in another aspect of this embodiment Rz4 is phenyl. In one aspect of structures (III-6b), and (III-6d), Rz, Rzi, Rzs, and Rz4, are all H and Rz2 is a Ci-8 alkyl, in another aspect of this embodiment Rz2 is a Ci-4 alkyl, in another aspect of this embodiment Rz2 is methyl. In one aspect of structures (III-6b), and (III-6d), Rz, Rzi, Rzs, and Rz4, are all H and Rz2 is an aryl, in another aspect of this embodiment Rz2 is phenyl. In one aspect of structures (III-6a), and (III-6c), Rz, Rzi, and Rz2. are all H. In one aspect of structures (III-6a), and (III- 6c), Rz, Rzi, are all H and Rz2is a Ci-8 alkyl, in one aspect of this embodiment Rz2 is a Ci-4 alkyl, in another aspect of this embodiment Rz2 is methyl. In one aspect of structures (III-6a), and (III-6c), Rz, Rzi, are all H and Rz2 is an aryl in another aspect of this embodiment Rz2 is phenyl.

[0066] In another aspect of said disclosed and claimed subject matter, said polymer has structure has structure (III-7). In another aspect of this embodiment, it has structure (III-7a). In another aspect of this embodiment, it has structure (III-7b).ATTORNEY DOCKET NO.: P24-254

[0067] In another aspect of said disclosed and claimed subject matter, said polymer has structure has structure (III-8). In another aspect of this embodiment, it has structure (III-8a). In another aspect of this embodiment, it has structure (III-8b).

[0068] In another aspect of said disclosed and claimed subject matter, said polymer has structure has structure (III-9). In another aspect of this embodiment, it has structure (III-9a). In another aspect of this embodiment, it has structure (III-9b).ATTORNEY DOCKET NO.: P24-254

[0069] In another aspect of said disclosed and claimed subject matter, said above described polymers are ones where Ei is C1-15 alkyl; in another aspect of this embodiment Ei is a Cl-10 alkyl; in another aspect of this embodiment Ei is a Ci-8 alkyl; in yet another embodiment Ei is a Ci-6 alkyl; in still another aspect of this embodiment El is selected from the group consisting of methyl(-CH3), ethyl (-CH2- CH3), n-propyl (-CH2-CH2-CH3), isopropyl (-CH(CH3)2, n-butyl (-CH2-CH2-CH2-CH3), tert-butyl (-C(CH3)3), isobutyl (CH2-CH(CH3)2, 2-butyl (-CH(CH3)CH2-CH3) (secbutyl); in still another aspect of this embodiment Ei is sec-butyl.Compositions with Disclosed and Claimed Polymers

[0070] Another aspect of said disclosed and claimed subject matter is a composition comprising any one of the above disclosed and claimed polymers and an organic spin casting solvent. In one aspect of this embodiment said composition has a concentration of from about 0.3 wt. % to about 3 wt. % in said organic spin casting solvent.Organic Spin Coating Solvent

[0071] The organic spin coating solvent for said composition which comprises the disclosed and claimed block copolymer, is any suitable organic solvents for dissolving the aforementioned disclosed and claimed block copolymer. These include a glycol ether derivative such as ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, propylene glycol n-propyl ether, or diethylene glycol dimethyl ether; a glycol ether ester derivative such as ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate (PGMEA); carboxylates such as ethyl acetate, n-butyl acetate and amyl acetate;ATTORNEY DOCKET NO.: P24-254 carboxylates of di-basic acids such as diethyloxylate and diethylmalonate; dicarboxylates of glycols such as ethylene glycol diacetate and propylene glycol diacetate; and hydroxy carboxylates such as methyl lactate, ethyl lactate (EL), ethyl glycolate, and ethyl-3-hydroxy propionate; a ketone ester such as methyl pyruvate or ethyl pyruvate; an alkoxycarboxylic acid ester such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate, or methylethoxypropionate; a ketone derivative such as methyl ethyl ketone, acetyl acetone, cyclopentanone, cyclohexanone or 2-heptanone; a ketone ether derivative such as diacetone alcohol methyl ether; a ketone alcohol derivative such as acetol or diacetone alcohol; a ketal or acetal like 1,3 di oxalane and di ethoxypropane; lactones such as butyrolactone; an amide derivative such as dimethylacetamide or dimethylformamide, anisole, and mixtures thereof.

[0072] In one aspect of this composition said organic spin casting solvent is a glycol ether ester derivative. In one aspect of this embodiment said organic spin casting solvent is PGMEA.Process of using Compositions

[0073] Another aspect of the disclosed and claimed subject matter is a process for directing a multiplied pattern in a block copolymer film, said process comprising: a. providing a block copolymer having two or more spontaneously separating blocks; b. providing a substrate; c. coating, on the substrate, a first coating using the above described composition, and thermally curing the first coating, forming a pinning coating, d. disposing the block copolymer on at least a portion of the pinning coating.

[0074] Another aspect is the above described process further comprisings steps c. to f, wherein, e. before disposing the block copolymer in step d., forming a pattern in the pinning coating by a lithographic process; and f providing a second coating in the pattern from with a second formulation which is a neutral layer coating formulation; and thereafter rinsing with a rinse solution forming a pattern comprising pinning regions and neutral layer regions on the substrate on which the block copolymer is coated; g. annealing the coated layer of block copolymer, produced in step f. to form aATTORNEY DOCKET NO.: P24-254 directed self-assembled block copolymer layer layer; h. using the directed self-assembled block copolymer layer as a mask, etch a pattern into the substrate using a plasma.ATTORNEY DOCKET NO.: P24-254EXAMPLES

[0075] The foregoing description is intended primarily for purposes of illustration. Although the disclosed and claimed subject matter has been shown and described with respect to an exemplary embodiment thereof, it should be understood by those skilled in the art that the foregoing and various other changes, omissions, and additions in the form and detail thereof may be made therein without departing from the spirit and scope of the disclosed and claimed subject matter.

[0076] Experiments are given below as examples. All the polymers synthesized in this disclosure were characterized by Gel permeation chromatography (PSS Inc. Germany) equipped with 100A, 500 A, 103 A, 105 A and 106 A p-ultrastyragel columns using THF solvent as an eluent (1 mL / min) for molecular weight measurements (M>. GPC, and Mw, GPC) and poly dispersity indices using polystyrene standards for calibration as a reference. Composition of polymers and end-functionality were determined using 300 MHz 1H- NMR using CDCh as a deuterated solvent.

[0077] Coating studies were performed using blanket dielectric SiO2 / Si. The films were baked at desired temperature ranging from 200°C to 250°C and for times ranging from 2mint to 30min and rinsed with PGMEA.

[0078] Chemicals were obtained from Sigma- Aldrich. Oxetane was purified by titrating against scc-BuLi. until cloudy and distilled under reduced pressure PS-CH2- CH2-CH2-OH materials (comparative examples 1 and 2) were prepared by anionic polymerization of styrene in cyclohexane and terminated with trimethylene oxide.

[0079] Contact Angles were measures using Dataphysics OCA20 Spin coating of test samples was done on a TEL Act8 track.

[0080] Thickness were measured using J. A Woollam M2000DI

[0081] FIG. 2 shows a Schematic depiction the synthesis of PS- / »-(SSiMe2H)3-X copolymer copolymer which is a copolymer of styrene and styrene functionalized with a -Si(CH3)2H at the para position ( where the anionic polymerization is terminated with an OH bearing materials (e.g. alcohol (e.g. isopropanol), H2O and the like) to produce a polymer where the end group E2 is H.Comparative Example 1: Synthesis of PS-CH2-CH2-CH2-OH (3 K brush)

[0082] A single neck RBF with three-way septum adaptor was assembled. This was pumped under high vacuum and refilled with nitrogen. Then styrene (20g. 0.0067ATTORNEY DOCKET NO.: P24-254 moles) was added using a glass syringe and cannula transferred cyclohexane (200 mL) was added. Then 1.4 molar Sec-BuLi was added 4.8 mL using a glass syringe and left under stirring for 60-90 min. The reaction was then terminated with 5 times excess trimethylene oxide followed by degassed isopropanol (5 mL) was added. Then this mixture was precipitate in excess IP A. Filter, dry in vacuum oven at 70°C to give 19.2 grams of polymer. Theory Mn= 3 kg / mol GPC Mn= 3 k,JH NMR Mn= 2.9k.Comparative Example 2: Synthesis of PS-CH2-CH2-CH2-OH (5 K brush).

[0083] This sample was synthesized using the comparative example 1 procedure by adjusting the styrene monomer to obtain 5K brush. Theory Mn = 5 kg / mol GPC Mn= 5 k, 'H NMR Mn= 4.9k.Example 1: Synthesis of PS- / i-(SSiVIe2lI)3-H

[0084] A single neck RBF with three-way septum adaptor was assembled. This was pumped under high vacuum and refilled with nitrogen. Then styrene (20 g, 0.008moles) was added using a glass syringe and cannula transfered cyclohexane (200 mL) was added. Then 1.4 molar Sec-BuLi was added (g. 5.7 mL) using glass syringe and left under stirring for 60-90 min. Then Toluene (15 mLg.) was taken in an ampoule and added dimethyl(4-vinylphenyl)silane (SSiMe2H) (4.54g .028 molesjand carried out azeotropic distillation under vacuum and refilled the ampoule with nitrogen. This solution containing 0.028 moles of (SSi Me2H) was then added to the RBF via cannula transfer. After a few minutes degassed isopropanol (5 mL was added. Then this mixture was precipitate in excess IP A. Filter, dry in vacuum oven at 70 °C to give 23 grams of polymer. Theoiy Mn =2500 +486.93 = 3 kg / mol GPC Mn = 3.3k 1.06 'H NMR Mn = 2400 + 486.93 = 2.9k. FIG. 3 shows the GPC profile of PS- / »-(SSi Me2H)3-H

[0085] FIG. 4 shows a Schematic depiction the synthesis of PS-(SSi Me2H)3-X copolymer copolymer which is a copolymer of styrene and styrene functionalized with a -Si(CH3)2H at the para position where the anionic polymerization is terminated with a halodialkylsilane (e.g. chlorodimethylsilane).

[0086] Example 2: Synthesis of PS-SiMe2H (5K):Synthesis of dimethylsilane terminated polystyrene macroinitiator (A / „ = 5,000 g / mol) prepared by anionic polymerization

[0086] Into a dry 250 mL round bottom reactor equipped with nitrogen / vacuum three- way septum adapter and magnetic stir bar was added 100 mL dry cyclohexane. Then, 22 mL (20 g) purified and degassed styrene was added into the reactor. Subsequently,ATTORNEY DOCKET NO.: P24-2543 mL of sec- butyllithium (scc-BuLi) (1.4 M) was added into the reactor under fast stirring. The reaction solution turned into orange initially and the reaction was stirred over 1 hour at 35 °C. After this, 1 mL of dimethylchlorosilane (distilled), was added into the reactor via syringe. The orange color of the reaction mixture disappeared slowly, and white precipitate came out. The reaction mixture was open to air and the solution was filtered. The polymer was recovered by precipitation in excess isopropanol (4 times of the polymer solution), filtered, and dried at 65° C for 12 h under vacuum giving 19.2 g of PS-Si(Me)2H with Mn (GPC) = 4,990 g / mol and / M, = 1.031 (96 % yield).

[0087] FIG. 5 shows GPC of PS-Si(Me)2H example 2.Example 2a: Synthesis of PS-SiMeiH (3K):

[0088] Into a dry 250 mL round bottom reactor equipped with nitrogen / vacuum three- way septum adapter and magnetic stir bar was added 100 mL dry cyclohexane. Then, 22 mL (20 g) purified and degassed styrene was added into the reactor. Subsequently, 4.8 mL of scc-butyllithium (scc-BuLi) (1.4 M) was added into the reactor under fast stirring. The reaction solution turned into orange initially and the reaction was stirred over 1 hour at 35 °C. After this, 1 mL of dimethylchlorosilane (distilled), was added into the reactor via syringe. The orange color of the reaction mixture disappeared slowly, and white precipitate came out. The reaction mixture was open to air and the solution was filtered. The polymer was recovered by precipitation in excess isopropanol (4 times of the polymer solution), filtered, and dried at 65° C for 12 h under vacuum giving(GPC) = 3,800 g / mol and ALM = 1.033 (96 % yield).Example 3: Synthesis of PS- / »-(SSi Me2H)3-SiMe2H

[0089] A single neck RBF with three-way septum adaptor was assembled. This was pumped under high vacuum and refilled with nitrogen. Then styrene (20g. 0.008 moles) was added using a glass syringe and cannula transfered cyclohexane (200 mL) was added. Then 1.4 molar Sec-BuLi was added (5.7 mL) using glass syringe and left under stirring for 60-90 min. Then Toluene (15 mL) was taken in an ampoule and added dimethyl(4-vinylphenyl)silane (SSi Me2H) (4.5g, 0.028 moles)and carried out azeotropic distillation under vacuum and refilled the ampoule with nitrogen. This solution containing 0.028moles of (SSi Me2H) was then added to the RBF via cannula transfer. After a few minutes degassed chlorodimethyl silane (3.8 g. 0.04 moles) wasATTORNEY DOCKET NO.: P24-254 added followed by degassed isopropanol (5 mL) was added. Then this mixure was precipitate in excess IP A. Filter, dry in vacuum oven at 70 °C to give 23.4 grams of polymer. Theory Mn=2500 +486.93 = 3 kg / mol GPC Mn= 3.4k 1.12 1H NMR Mn= 2300 + 586.93 = 2.9k. FIG. 6 shows the GPC profile of PS- / »-(SSi Me2H)3-SiMe2H

[0090] FIG. 7 shows a Schematic depiction the synthesis of PS-(SSi Me2H)3-X copolymer copolymer which is a copolymer of styrene and styrene functionalized with a -Si(CH3)2H at the para position where the anionic polymerization is terminated with an oxirane or oxetane comprising moiety (e.g. oxetane TMO).Example 4: Synthesis of PS- / »-(SSi Me2H)3- CH2-CH2-CH2-OH

[0091] A single neck RBF with three-way septum adaptor was assembled. This was pumped under high vacuum and refilled with nitrogen. Then styrene (20 g. 0.008 moles) was added using a glass syringe and cannula transferred cyclohexane (200 mL) was added. Then 1.4 molar Sec-BuLi was added (5.7 mL) using glass syringe and left under stirring for 60-90 min. Then Toluene (15 mL) was taken in an ampoule and added dimethyl(4-vinylphenyl)silane (SSi Me2H) (4.5g 0.028moles)and carried out azeotropic distillation under vacuum and refilled the ampoule with nitrogen. This solution containing 0.028 moles of (SSi Me2H) was then added to the RBF via cannula transfer. After a few minutes purified TMO was added followed by degassed isopropanol and then precipitate in excess IP A. Filter, dry in vacuum oven at 70 °C. Theory Mn=2500 +486.93 = 3 kg / mol GPC Mn= 3.3k 1.06 'H NMR Mn= 2500 + 486.93 = 3k. FIG. 8 shows the GPC profile of PS-6-(SSi Me2H)3- CH2-CH2-CH2-OH.Preparation of Comparative Testing Solutions PS-CH2-CH2-CH2-OH (Comparative Examples 1 and 2)

[0092] PS-CH2-CH2-CH2-OH comparative Examples 1 and 2 were individually dissolved in PGMEA to prepare a 1-2 wt. % solution and filtered through a 0.2 micron syringe PTFE filter.Brush formation on substrates with Comparative Testing Solution PS-CH2-CH2- CH2-OH

[0093] The comparative testing solution with PS-CH2-CH2-CH2-OH comparative Example 1 and 2 were applied by spin coating followed by annealing at 200 / 250°C and then rinsed with PGMEA.ATTORNEY DOCKET NO.: P24-254Preparation of Testing Solution for Synthesis Example 1 to 4

[0094] The polymer of Examples 1, 2 and 3 were individually dissolved in PGMEA to prepare a 1-2 wt% solution and filtered through a 0.2 micron syringe PTFE filter.Brush formation on substrates with Examples 1, 2, 3 or 4.

[0095] Individually the testing solution for Synthesis Example 1, 2, 3 or 4 were applied by spin coating followed by annealing at 200 / 250°C and then rinsed with PGMEA.

[0096] FIG. 9 shows a coating of (~30 nm FT) of PS-6-(SSi Me2H)3-H on 1.2 nm of native silicon oxide on a silicon water at different annealing condition and observation of dewetting by optical image after annealing.

[0097] FIG. 10 shows Coating (~30 nm FT) of PS-CH2-CH2-CH2-OH on dielectric substrates at different annealing condition and observation of dewetting by optical image after annealing. The brushes at the Mnof 3,000 g / mol was synthesized for PS- CH2-CH2-CH2-OH (comparative example 1) and PS-6-(SSi Me2H)3-H and tested for coating on silicon wafer to examine film uniformity under annealing condition.

[0098] As seen from FIG. 9 and FIG. 10, the there is an absence of dewetting is noticed at two different annealing conditions on SiO and SiARC substrates for PS-6-(SSi Me2H)s-H (FIG. 9), whereas FIG. 10 shows substantial dewetting for PS-CH2OH under the same condition on these substrates.

[0099] Table 1 shows the film thickness and contact angle (CA) data for two different repeat test (Wafer 1 and 2) using 3K samples (Example 1) where within essentially the same contact angle was achieved despite different thicknesses.

[0100] Table 1*Processing conditions :8 ” Si wafer \ PS- b-(SSi WQiHp-H) (3K): Spin-coat @1500 rpm FAB-6 \ Soft-bake 110° C / lmin / air Anneal 250°C / 30 min / N2 RTA \ 2m EBR dynamic rinse \ Soft-bake 110° C / 1 min / air \ FT measurement 18 pts \ Contact angle measurement 5 pts

[0101] Grafting studies were conducted (Table 2). As shown in FIG. 11 and 12, andATTORNEY DOCKET NO.: P24-254Table 2, below, a clear cleavage of PS-CH2CH2CH2OH brush (comparative example 1) is evident over the weeks as decrease in CA, and C / Si observed over silicon oxide coupon at partial grafting condition of 200°C / 2min / air. On the other hand, at this condition, the grated chains of PS-Z>-(SSi Me2H)3-H did not show any cleavage over time indicating strong chemical bonding with silicon oxide substrate (FIG. 11. Similarly, when grafted at higher temperatures both the systems show stable over again. This suggests that the presence of free Si-OH group on the substrate in partial grafting situations, there is a significant catalytic influence for cleavage and the linkage C-O-Si bond is in equilibrium with remaining(free) substrate Si-OH (FIG. 12).Table 2 Comparison of coating dewetting and grafting data for PSCH2CH2CH2OH (3K), PS-Z>-(SSiMe2H)3-H (A / n3K)

Claims

ATTORNEY DOCKET NO.: P24-254What is claimed is:

1. A polymer of structure (I), prepared by anionic polymerization which has a polydispersity of 1.00 to 1.05, wherein A is styrenic polymeric segment selected from structure (A-l) or structure (A-2), where m is the number of styrene repeat units and n is the number of styrene repeat unit functionalized by the moiety X, where m is an integer ranging from 5 to 200, and n is an integer ranging from 2 to 4, where X is H, a moiety of structures (X-2) or a moiety of structure (X-3), where Rxia, Rxib, Rx2a, Rx2b, RX2C and Rx2d are individually selected from a Ci-4 alkyl, Ei is a Ci-i8 alkyl,E2 is H, a moiety of structure (X-l), a moiety of structure (X-2) or a moiety of structure (X-3), where Rz2, Rzs and Rz4, are independently selected from H, a Ci-8 alkyl, and an aryl, and further where Rz, Rzi, are either independently selected from H, a Ci-8 alkyl, an aryl, or form together a C3 to C4 alkylene moiety which forms 5 to 6 cyclic alkane, and nz is either 0 or 1, provided that when A, said styrenic polymeric segment moiety, has structure (A-l), and E2 is a moiety of structure (X-l) then X is either a moiety of structure (X-2) or a moiety of structure (X-3), and when A, said styrenic polymeric segment has structure (A-2) then X is either a moiety of structure (X-2) or a moiety of structure (X-3),2. The polymer of claim 1, which has a poly dispersity from 1.00 to 1.02.

3. The polymer of claim 1, or 2, wherein Rxia, Rxib, Rx2a, Rx2b, Rx2c and Rx2d are individually selected from a C1-3 alkyl.ATTORNEY DOCKET NO.: P24-2544. The polymer of any one of claims 1 to 3, wherein Rxia, Rxib, Rx2a, Rx2b, Rx2c and Rx2d are individually selected from a C1-2 alkyl.

5. The polymer of any one of claims 1 to 4, wherein Rxia, Rxib, Rx2a, Rx2b, Rx2c and Rx2d are methyl.

6. The polymer of any one of claims 1 to 5, where A has structure (A-l).

7. The polymer of claim 6, where X is has structure (X-2), and E2 is H.

8. The polymer of claim 6, where X has structure (X-2), an E2 has structure (X-l)9. The copolymer of claim 6, where X is has structure (X-3), and E2 is H.

10. The copolymer of claim 6, where X is has structure (X-3), and E2 has structure(X-l).

11. The copolymer of claim 6, where X is has structure (X-2), and E2 is (X-2).

12. The polymer of claim 6, where X is has structure (X-2), and E2 is (X-3).

13. The copolymer of claim 6, where X has structure (X-3), and E2 is (X-2).

14. The polymer of claim 6, where X has structure (X-3), and E2 is (X-3).

15. The polymer of any one of claims 1 to 5, where A is (A-2).

16. The polymer of claim 15, where X has structure (X-2), and E2 is H.

17. The polymer of claim 13, where X has structure (X-2), and E2 has structure (X- 1).

18. The polymer of claim 15, where X has structure (X-3), and E2 is H.

19. The polymer of claim 15, where X has structure (X-3), and E2 has structure (X- 1).

20. The polymer of claim 15, where X has structure (X-2), and E2 is (X-2).

21. The copolymer of claim 15, where X has structure (X-2), and E2 is (X-3).

22. The copolymer of claim 15, where X has structure (X-3), and E2 is (X-2).

23. The copolymer of claim 15, where X has structure (X-3), and E2 is (X-3).

24. The copolymer of any one of claims 1 to 6, which has structure (II),25. The copolymer of any one of claims 1 to 6, which has structure (II- 1),ATTORNEY DOCKET NO.: P24-25426. The copolymer of any one of claims 1 to 6, and 25, which has structure (II-l a),la).

27. The copolymer of any one of claims 1 to 6, and 25, which has structure (II- 1 b),28. The copolymer of any one of claims 1 to 6, which has structure (II-lc),lc).

29. The copolymer of any one of claims 1 to 6, and 28, which has structure (II- Id),ATTORNEY DOCKET NO.: P24-254ld).

30. The copolymer of any one of claims 1 to 6, and 28, which has structure (II-le),le).

31. The copolymer of any one of claims 1 to 6, and 28, which has structure (II-l f),32. The copolymer of any one of claims 1 to 6, and 28, which has structure (II- 1g),33. The polymer of any one of claims 1 to 6, which has structure (II-2),ATTORNEY DOCKET NO.: P24-25434. The polymer of any one of claims 1 to 6, and 33, which has structure (II-2a),35. The polymer of any one of claims 1 to 6, and 33, which has structure (II-2b),36. The polymer of any one of claims 1 to 6, which has structure (II-3),37. The polymer of any one of claims 1 to 6, and 36, which has structure (II-3a),ATTORNEY DOCKET NO.: P24-25438. The polymer of any one of claims 1 to 6, and 36, which has structure (II-3b),39. The copolymer of any one of claims 1 to 6, which has structure (II-4),40. The copolymer of any one of claims 1 to 6, which has structure (II-5),41. The copolymer of any one of claims 1 to 6, and 40, which has structure (II-5a),ATTORNEY DOCKET NO.: P24-25442. The copolymer of any one of claims 1 to 6, and 40, which has structure (II-5b),43. The copolymer of any one of claims 1 to 6, which has structure (II-5c),44. The copolymer of any one of claims 1 to 6, and 43, which has structure (II-5d),45. The copolymer of any one of claims 1 to 6, and 43, which has structure (II-5e),ATTORNEY DOCKET NO.: P24-25446. The copolymer of any one of claims 1 to 6, and 43, which has structure (II-5f),47. The copolymer of any one of claims 1 to 6, and 43, which has structure (II-5g),48. The polymer of any one of claims 1 to 6, which has structure (II-6),49. The polymer of any one of claims 1 to 6, and 48, which has structure (II-6a),ATTORNEY DOCKET NO.: P24-25450. The polymer of any one of claims 1 to 6, and 48, which has structure (II-6b),51. The polymer of any one of claims 1 to 6, which has structure (II-7),52. The polymer of any one of claims 1 to 6, and 51, which has structure (II-7a),53. The polymer of any one of claims 1 to 6, and 51, which has structure (II-7b),ATTORNEY DOCKET NO.: P24-25454. The polymer of any one of claims 1 to 6, which has structure (II-8),55. The polymer of any one of claims 1 to 6, and 54, which has structure (II-8a),56. The polymer of any one of claims 1 to 6, and 54, which has structure (II-8b),57. The copolymer of any one of claims 1 to 5, and 13, which has structure (III),58. The copolymer of any one of claims 1 to 5, and 13, which has structure (III- 1),ATTORNEY DOCKET NO.: P24-25459. The copolymer of any one of claims 1 to 5, 13 and 58, which has structure (III- la),la).

60. The copolymer of any one of claims 1 to 5, 13 and 58, which has structure (III- lb),lb).

61. The copolymer of any one of claims 1 to 5, and 13, which has structure (III- 1 c),62. The copolymer of any one of claims 1 to 5, 13 and 61, which has structure (III- ld),63. The copolymer of any one of claims 1 to 5, 13 and 61, which has structure (III-ATTORNEY DOCKET NO.: P24-254 le),le).

64. The copolymer of any one of claims 1 to 5, 13 and 61, which has structure (III- lf),-lf).

65. The copolymer of any one of claims 1 to 5, 13 and 61, which has structure (III- lg),-lg).

66. The polymer of any one of claims 1 to 5, and 13 which has structure (III-2),67. The polymer of any one of claims 1 to 5, 13 and 66, which has structure (III- 2a),44ATTORNEY DOCKET NO.: P24-25468. The polymer of any one of claims 1 to 5, 13 and 66, which has structure (III-2b),69. The polymer of any one of claims 1 to 5 and 13, which has structure (III-3),70. The polymer of any one of claims 1 to 5, 13 and 69, which has structure (III-3a),71. The polymer of any one of claims 1 to 5, 13 and 47, 69, which has structure (III-3b),ATTORNEY DOCKET NO.: P24-25472. The copolymer of any one of claims 1 to 5 and 13, which has structure (III-4),73. The copolymer of any one of claims 1 to 5 and 13, which has structure (III-5),74. The copolymer of any one of claims 1 to 5, 13 and 73, which has structure (III-5a),75. The copolymer of any one of claims 1 to 5, 13 and 73, which has structure (III-5b),76. The copolymer of any one of claims 1 to 5 and 13, which has structure (III-6),77. The copolymer of any one of claims 1 to 5, 13 and 76, which has structure (III-ATTORNEY DOCKET NO.: P24-2546a),78. The copolymer of any one of claims 1 to 5, 13 and 76, which has structure (III-6b),79. The copolymer of any one of claims 1 to 5, 13 and 76, which has structure (III- 6c),80. The copolymer of any one of claims 1 to 5, 13 and 76, which has structure (III- 6d),81. The polymer of any one of claims 1 to 5 and 13, which has structure (III-7),ATTORNEY DOCKET NO.: P24-25482. The polymer of any one of claims 1 to 5, 13 and 81, which has structure (III- 7a),83. The polymer of any one of claims 1 to 5, 13 and 81, which has structure (III-7b),84. The polymer of any one of claims 1 to 5, and 13, which has structure (III-8),85. The polymer of any one of claims 1 to 5, 13 and 84, which has structure (III- 8a),ATTORNEY DOCKET NO.: P24-25486. The polymer of any one of claims 1 to 5, 13 and 84, which has structure (III-8b),87. The polymer of any one of claims 1 to 5 and 13, which has structure (III-9),(III-9).

88. The polymer of any one of claims 1 to 5, 13 and 87, which has structure (HI-9a),89. The polymer of any one of claims 1 to 5, 13 and 87, which has structure (III-9b),90. A composition comprising a polymer of any one of claim 1 to 89 and an organic spin casting solvent.

91. The composition of claim 90, where said polymer has a concentration of from about 0.3 wt. % to about 3 wt. % in said organic spin casting solvent.ATTORNEY DOCKET NO.: P24-25492. A process for directing a multiplied patern in a block copolymer film, said process comprising: a. providing a block copolymer having two or more spontaneously separating blocks; b. providing a substrate; c. coating, on the substrate, a first coating using the composition of claim 90 or 91 , and thermally curing the first coating, forming a pinning coating, d. disposing the block copolymer on at least a portion of the pinning coating.

93. The process of claim 91, further comprising, e. before disposing the block copolymer in step d., forming a patern in the pinning coating by a lithographic process; and f providing a second coating in the patern from with a second formulation which is a neutral layer coating formulation; and thereafter rinsing with a rinse solution forming a patern comprising pinning regions and neutral layer regions on the substrate on which the block copolymer is coated; g. annealing the coated layer of block copolymer, produced in step f. to form a directed self-assembled block copolymer layer layer; h. using the directed self-assembled block copolymer layer as a mask, etch a patern into the substrate using a plasma.

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