Neutral Brushes with Tunable Polarity for the Self-Assembly of Block Copolymers with Poly(styrene) and Poly(methyl methacrylate)-Containing Segments

Abstract

The present invention relates to a repeating unit of structure (I), a repeating unit of structure (II), and two terminal groups R 3 and R 4 With respect to the random copolymer of structure (A) comprising the terminal group R 3 is a moiety of structure (IIIa) and is a C1-C8 alkyl, or is a moiety of structure (III) and is an end group R 4 is a moiety derived from anionic polymerization termination and is selected from the group consisting of H, C1-C8 alkyl, C1-C8 alkylcarbonyl, C1-C8 trialkylsilyl, C1-C8 dialkylsilyl, C1-C8 monoalkylsilyl, silane, and benzyl-based moieties, or is a moiety of structure (IV), and R 3 and R 4 cannot both be simultaneously selected from the moieties of structure (III) and structure (IV), respectively, and R 3 is a part of structure (III) or R 4 is part of structure (IV). The present invention also relates to a composition comprising this copolymer and an organic spin-coating solvent, and to the use of this composition to form a grafted neutral layer for use in DSA processing.

Description

[Technical field]

[0001] The present invention relates to neutral brush compositions for use in directed self-assembly processing. [Background technology]

[0002] Self-assembly of block copolymers is a useful method for generating ever smaller patterned features for the manufacture of microelectronic devices, which can achieve critical dimensions (CD) of features on the nanoscale order. Self-assembly methods are desirable for extending the resolution capabilities of microlithography techniques for repeating features such as arrays of contact holes or posts. In conventional lithography approaches, ultraviolet (UV) radiation can 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 they can also contain refractory elements such as silicon to allow dry development using conventional integrated circuit (IC) plasma processing techniques. In positive photoresists, UV radiation passing through the mask causes a photochemical reaction in the photoresist that renders the exposed areas removable with a developer solution or by conventional IC plasma processing. Conversely, in negative photoresists, UV radiation passing through the mask renders the exposed areas less removable with a developer solution or by conventional IC plasma processing. Integrated circuit features such as gates, vias, or interconnects are then etched into the substrate or layered substrate, and the remaining photoresist is removed. With conventional lithographic exposure processes, there is a limit to the feature size of integrated circuit features. Further reduction in pattern size is difficult to achieve with radiation exposure due to limitations related to aberrations, focus, proximity effects, minimum achievable exposure wavelength, and maximum achievable numerical aperture. Due to the need for large scale integration, device circuit dimensions and features have been continually scaled down. In the past, the final resolution of features has depended on the wavelength of light used to expose the photoresist, which is itself limited. Guided (also known as guided) self-assembly techniques such as graphoepitaxy and chemoepitaxy using block copolymer imaging with patterned regions on the substrate are highly desirable techniques used to improve resolution while reducing CD variation.These techniques can be used to augment conventional UV lithography techniques or to enable higher resolution and CD control in approaches using EUV, e-beam, deep UV or immersion lithography. Directed self-assembling block copolymers contain blocks of etch-resistant and easily etched copolymer units that, when coated, aligned and etched on a substrate, provide areas of very dense patterns.

[0003] For guided or unguided self-assembly of block copolymer films on patterned or unpatterned substrate regions, respectively, the self-assembly process of the block copolymer layer typically occurs during annealing of the film over a neutral layer. The neutral layer on the semiconductor substrate may be an unpatterned neutral layer, or in chemoepitaxy or graphoepitaxy, the neutral layer may contain graphoepitaxy or chemoepitaxy-derived features (formed via UV lithography techniques as described above), respectively. While the block copolymer film is annealed, the underlying neutral layer induces nanophase separation of the block copolymer domains. An example is the formation of phase-separated domains that are lamellae or cylinders perpendicular to the underlying neutral layer surface. These nanophase-separated block copolymer domains form pre-patterns (e.g., lines and spaces L / S) that can be transferred into the substrate via an etching process (e.g., plasma etching). In graphoepitaxy or chemoepitaxy, these guiding figures can induce both pattern modification and pattern multiplication. In the case of unpatterned neutral layers, this produces, for example, repeating arrays of L / S or CH. For example, in conventional block copolymers such as poly(styrene-b-methyl methacrylate) (P(Sb-MMA)), where both blocks have similar surface energies at the BCP-air interface, this can be achieved by coating and thermal annealing the block copolymer onto a layer of non-preferential or neutral material that has been grafted or crosslinked at the polymer-substrate interface.

[0004] In graphoepitaxy-induced self-assembly, block copolymers self-assemble on substrates pre-patterned with conventional lithography (ultraviolet, deep UV, e-beam, extreme UV (EUV) exposure sources) to form repeating topographical features such as line / space (L / S) or contact hole (CH) patterns. In one example of L / S-induced self-assembly arrays, block copolymers can form self-aligned lamellar regions that can form parallel line-space patterns of different pitches in trenches between pre-patterned lines to enhance pattern resolution by dividing the spaces in the trenches between topographical lines into finer patterns. For example, diblock or triblock copolymers capable of microphase separation, including carbon-rich blocks (e.g., styrene or containing some other elements such as Si, Ge, Ti) that are resistant to plasma etching, and blocks that are highly etchable or removable by plasma, can provide high-resolution pattern definition. An example of a highly etchable block may include a monomer, such as methyl methacrylate, that is oxygen-rich and free of refractory elements and yet capable of forming a highly etchable block. The plasma etching gases used in the etching process that defines the self-assembled pattern are typically those used in processes used in the manufacture of integrated circuits (ICs). In this manner, very fine patterns can be produced in typical IC substrates compared to those that can be defined by conventional lithography techniques, thus achieving pattern multiplication. Similarly, graphoepitaxy can be used to produce more dense features such as contact holes. In graphoepitaxy, a suitable block copolymer aligns itself by directed self-assembly around an array of contact holes or posts defined by conventional lithography to form a denser array of regions of etchable and etch-resistant domains, which when etched, gives a denser array of contact holes. As a result, graphoepitaxy has the potential to provide both pattern modification and pattern multiplication.

[0005] In chemical epitaxy or pinned chemical epitaxy, the self-assembly of block copolymers is formed on a surface with a guiding feature that is a region of different chemical affinity that has no or no significant topography on which to base the guiding self-assembly process (in other words, non-guiding topography). For example, the surface of a substrate can be patterned with conventional lithography (UV, deep UV, e-beam, EUV) to form a line-and-space (L / S) pattern of surfaces with different chemical affinities, where exposed regions, where the surface chemistry has been modified by irradiation, alternate with unexposed regions that show no chemical change. These regions do not provide topographical differences, but rather surface chemical differences or pinning that guide the self-assembly of the block copolymer segments. Specifically, the directed self-assembly of block copolymers with block segments containing etch-resistant repeat units (e.g., styrene repeat units) and fast-etching repeat units (e.g., methyl methacrylate repeat units) allows for precise placement of the etch-resistant and fast-etching block segments on a pattern. This technique allows for precise placement of these block copolymers and subsequent pattern transfer to a substrate after plasma or wet etching processing. Chemical epitaxy has the advantage that it can be fine-tuned by changing chemical differences, which helps improve line edge roughness and CD control, thus allowing pattern modification. Other types of patterns, such as repeating contact hole (CH) arrays, can also be pattern modified using chemoepitaxy.

[0006] These neutral layers are layers on the substrate or surfaces of the treated substrate that have no affinity for any of the block segments of the block copolymers used for directed self-assembly. Neutral layers are useful in graphoepitaxy methods of directed self-assembly of block copolymers because they allow for the proper placement or orientation of the block polymer segments for directed self-assembly, which results in the proper placement of the etch-resistant and highly etchable block polymer segments relative to the substrate. For example, in a surface containing line-and-space features defined by conventional radiation lithography, the neutral layer allows for the orientation of the block segments such that they are oriented perpendicular to the surface of the substrate, which is an ideal orientation for both pattern modification and pattern multiplication depending on the length of the block segments in the block copolymer relative to the length between the lines defined by conventional lithography. If the substrate interacts too strongly with one of the block segments, the segment will lie flat on its surface, maximizing the contact area between the segment and the substrate; such a surface will disrupt the desired vertical alignment that can be used to achieve either pattern modification or pattern multiplication based on features generated by conventional lithography. Modifying or pinning selected small regions of the substrate to make them interact strongly with one block of the block copolymer, while leaving the remainder of the substrate coated with a neutral layer, can be useful to align the domains of the block copolymer in a desired direction, and this is the basis of pinned chemoepitaxy or graphoepitaxy used for pattern multiplication. The pinned regions can be hydrophilic, with a relatively large affinity for polar block copolymer segments, such as, for example, polymethylmethacrylate block segments in a block copolymer of styrene and methylmethacrylate, or alternatively, hydrophobic, with a relatively large affinity for, for example, polystyrene block segments in a block copolymer of styrene and methylmethacrylate.

[0007] For DSA LiNe flow processes using block copolymers such as 50:50 block copolymers of styrene and methyl methacrylate (PS-b-PMMA), typically 50 / 50 random copolymers of styrene and methyl methacrylate (PS-r-PMMA) with reactive chain end functional groups produced by radical polymerization are used. These types of copolymers are produced using radical polymerization methods, which give copolymers with high polydispersity (PDI=1.6-1.8) and therefore form less uniform grafted neutral layers. Neutral brushes based on PS-b-PMMA produced by anionic polymerization are also known, but these materials have hydrophobicity that is not easy to adjust. In addition, polymers and copolymers based on alkyl or aryl methacrylates, for example, polymers and copolymers based on benzyl methacrylate without graftable end groups, produced by radical polymerization and with high polydispersity, are known, but polymers with reactive end groups and narrow polydispersity are desired in DSA applications. Such materials are needed not only because they can potentially form uniform neutral layers, but also because their hydrophobicity can be easily fine-tuned by varying the ratio of alkyl methacrylate repeat units to aryl methacrylate repeat units. Such tunable materials would not only eliminate the problem of lack of neutral layer uniformity in the DSA LiNe flow process, but also prevent the problem of defective DSA guide pattern collapse much more efficiently than conventional neutral brushes such as PS-r-MMA-OH or PS-b-MMA-OH. [Brief description of the drawings]

[0008] [Figure 1] FIG. 1 shows a representative copolymer that may be obtained using hydroxyl-protected diphenylethylene as the initiator adduct with sec-BuLi. [Diagram 2]FIG. 2 shows the copolymer that might be obtained by initiating with a sec-BuLi-1,1-diphenylethene adduct that is capped and terminated with a protected 2-hydroxyethyl 2-phenylacrylate. [Diagram 3] FIG. 3 shows 1 FOV SEM images of each fingerprint pattern on silicon wafer using A) PS-b-PMMA on P(BnMA-r-BPMA25%)-OH (Mn: 13K, brush FT: 4.2nm ± 0.3, WCA: 81.0 ± 2.3), B) PS-b-PMMA on P(BnMA-r-CHMA25%)-OH (Mn: 23K, brush FT: 3.8nm ± 0.3, WCA: 79.4 ± 0.5), and C) PS-b-PMMA on P(BnMA-r-AMMA20%-OH) (Mn: approx. 7.0K, brush FT: 7.9nm ± 0.3, WCA: 80.8 ± 0.5). Process conditions: Si wafer, coated NLD, 200°C / 30min / N2 (polymer A, B&C, 230°C), toluene immersion for 15min, N2 blow drying, PME-7167Ctg65: L0=48 nm, FT=50 nm, 270°C / 1h (N2). [Prior art documents] [Non-patent literature]

[0009] [Non-Patent Document 1] Macromolecules 2019,52,2987-2994 [Non-Patent Document 2] Macromol.Rapid Commun.2018,39,1800479 [Non-Patent Document 3] A.Deiter Shluter et al Synthesis of Polymers,2014,Volume 1,p315 [Non-Patent Document 4] Encyclopedia of Polymer Science and Technology,2014,Vol 7,p.625 Summary of the Invention

[0010] One aspect of the present invention is novel graftable copolymers that can be tuned for their neutrality towards either hydrophilicity or hydrophobicity enhancement in terms of how they interact with polar or non-polar block copolymer segments in block copolymers such as PS-b-PMMA block copolymers, depending on the composition of alkyl or aryl substituted methacrylate monomers with repeat units such as benzyl methacrylate and its derivatives. One approach to these polymers is to initiate (alkyl or aryl) methacrylates by using novel hydroxyl-protected diphenylethylenes as initiator adducts with sec-BuLi, thereby forming brushes with well-defined, pre-determined molecular weights and low polydispersity for the vertical assembly of block copolymers such as PS-b-PMMA type di- or multi-block copolymers. Another approach in the present invention is to use standard alkyl lithium initiators, but terminate the living polymer chains with protected hydroxyalkyl 2-aryl acrylates, e.g. protected 2-hydroxyethyl 2-phenyl acrylate, again forming brushes with well-defined, pre-determined molecular weights and low polydispersity.

[0011] By using any of these anionic copolymerizations, various compositions of these methacrylates can be prepared to adjust the hydrophilicity or hydrophobicity to induce slight changes in neutrality for the appropriate application requirements in DSA. Figures 1 and 2 show representative examples of such materials, where Figure 1 shows a representative copolymer that would be obtained using hydroxyl-protected diphenylethylene as the initiator adduct with sec-BuLi. Figure 2 shows a copolymer that would be obtained starting with sec-BuLi 1,1-diphenylethene adduct capped and terminated with protected 2-hydroxyethyl 2-phenylacrylate.

[0012] The present invention, in one of its aspects, describes a random copolymer of structure (A), which comprises: The repeating unit of structure (I), in which R m1 is a C1-C8 alkyl and R1 is a benzyl-containing moiety of structure (V), where R benz is a substituent independently selected from H, C1-C4 alkyl, and C1-C4 alkoxy, L3 is C1-C4 alkylene, and "*" represents the point of attachment of the substituent to the repeat unit, and n1 indicates the number of the repeat unit in the copolymer, and further, the mole % of the repeat unit is from about 40 mole % to about 100 mole %; The repeating unit of structure (II), wherein R m2 is a C1-C8 alkyl; R2 is a moiety selected from C1-C20 linear alkyl, C3-C20 branched alkyl, and C5-C20 cyclic alkyl, a cyclohexyl alkylene moiety of structure (VI), an anthracenyl alkylene moiety of structure (VII), a naphthalenyl alkylene moiety of structure (VIII), and a biphenyl moiety of structure (VIV); wherein L4 and L5 are each independently selected from a C1-C4 alkylene; L6 and L7 are each independently selected from a direct valence bond or a C1-C4 alkylene moiety; R cycl , R anth , R naph , R biph are each independently selected from H, C1-C4 alkyl, and C1-C4 alkoxy, n2 represents the number of such repeat units in the copolymer, and further, the mole % of such repeat units is from about 0 mole % to about 60 mole %, and further, the total mole % of repeat units in said copolymer of structures (I) and (II) repeat units is 100 mole %; • two end groups R3 and R4; Including, however, The terminal group R3 is derived from an anionic initiator and is a moiety of structure (IIIa) or is a moiety of structure (III), where L1 is a C1-C8 alkylene and R5 is H, an acetal protecting group, or a trialkylsilyl protecting group, R6 is a C1-C8 alkyl, and R e1 and R e2 are independently selected from H, C1-C8 alkyl, and C1-C8 alkoxy, and "*" represents the point of attachment of this end group to said copolymer of Structure (A); and the end group R4 is a moiety derived from an anionic polymerization termination, where R4 is selected from the group consisting of H, C1-C8 alkyl, C1-C8 alkylcarbonyl (alkyl-C(=O)-), C1-C8 trialkylsilyl ((alkyl)3Si), C1-C8 dialkylsilyl ((alkyl)2HSi), C1-C8 monoalkylsilyl- ((alkyl)H2Si-), silane (-H3Si-), and benzyl-based moieties, or a moiety of formula (IV), where L R2 is a C2-C8 alkylene and R7 is H, an acetal protecting group, or a trialkylsilyl protecting group, R8 is selected from the group consisting of H, C1-C8 alkyl, C1-C8 alkylcarbonyl (alkyl-C(=O)-), C1-C8 trialkylsilyl ((alkyl)3Si), C1-C8 dialkylsilyl ((alkyl)2HSi), C1-C8 monoalkylsilyl- ((alkyl)H2Si-), silane (-H3Si-), and a benzyl-based moiety, and R e3 is selected from H, C1-C8 alkyl, and C1-C8 alkoxy, and "*" represents the point of attachment of the end group to the copolymer of structure (A), and further Both R3 and R4 cannot be simultaneously selected from the moieties of structure (III) and (IV), respectively; and R3 is a moiety of structure (III) or R4 is a moiety of structure (IV).

[0013] [ka] Another aspect of the present invention is a composition comprising a polymer of the present invention having structure (A) and an organic spin-casting solvent, wherein the copolymer has end group (III) present and R5 is H, or end group (IV) present and R7 is H.

[0014] Yet another aspect of the present invention is a method of grafting the composition of the present invention comprising a copolymer of structure (A) onto a substrate and using the grafted layer as a neutral layer in directed self-assembly (DSA) processing. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] It is to be understood that both the general description above and the detailed description below are exemplary and explanatory, and are not intended to be limiting with respect to the invention as claimed. In this application, unless specifically stated otherwise, the use of the singular includes the plural, the singular means "at least one," and the use of "or" means "and / or." Furthermore, the use of "comprises," "includes," and other verb forms such as "included," "included," and the like are not limiting. Also, the use of "element" or "component" includes both elements and components that contain one unit, and elements or components that contain more than one unit, unless specifically stated otherwise. Unless otherwise indicated, the conjunction "and" as used herein is intended to be inclusive, and the conjunction "or" is not intended to be exclusive. For example, the phrase "or instead of" is intended to be exclusive. As used herein, the conjunction "and / or" refers to any combination of the elements described above, including the use of a single element.

[0016] The term "C1-C4 alkyl" includes methyl and C2-C4 linear alkyl and C3-C4 branched alkyl moieties, such as 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), and the like. Similarly, the term C1-C8 alkyl includes methyl, C2-C8 linear alkyl, C3-C8 branched alkyl, C4-C8 cycloalkyl (e.g., cyclopentyl, cyclohexyl, etc.), or C5-C8 alkylenecycloalkyl (e.g., -CH2-cyclohexyl, CH2-CH2-cyclopentyl, etc.).

[0017] The term "C2-C5 alkylene" includes C2-C5 linear alkylene moieties (such as ethylene, propylene, etc.) and C3-C5 branched alkylene moieties (such as -CH(CH3)-, -CH(CH3)-CH2-, etc.).

[0018] Diblock and triblock copolymers of styrenic and alkyl 2-methylene alkanoate derived repeat unit moieties useful as components in the compositions of the invention described herein can be prepared by a variety of methods, including anionic polymerization, atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT) polymerization, and living radical polymerization (Macromolecules 2019, 52, 2987-2994 (Non-Patent Document 1); Macromol. Rapid Commun. 2018, 39, 1800479 (Non-Patent Document 2); A. Deiter Shluter et al Synthesis of Polymers, 2014, Volume 1, p315 (Non-Patent Document 3); Encyclopedia of Polymer Science and Technology, 2014, Vol 7, p. 625 (Non-Patent Document 4)).

[0019] The random copolymer poly(styrene-co-methyl methacrylate) is abbreviated as "P(S-co-MMA)" and the oligomeric form of this material is abbreviated as oligo(S-co-MMA). Similarly, the block copolymer poly(styrene-block-methyl methacrylate) is abbreviated as P(Sb-MMA) while the oligomer of this material is abbreviated as oligo(Sb-MMA). The oligomer oligo(styrene-co-p-octylstyrene)-block-(methyl methacrylate-co-di(ethylene glycol) methyl ether methacrylate) uses the same abbreviations to refer to the random block copolymer elements, specifically oligo(S-co-p-OS)-bP(MMA-co-DEGMEMA) (S=styrene, p-OS=para-octylstyrene, MMA=methacrylate, DEGMEMA=di(ethylene glycol) methyl ether methacrylate) to refer to the repeat units in this block copolymer where two blocks are random copolymers.

[0020] FOV is an abbreviation for "field of view" in a top-down scanning electron microscope (SEM) in SEM images in this application. "L / S" is an abbreviation for "line and space" lithography features.

[0021] PGMEA and PGME are abbreviations for 1-methoxypropan-2-yl acetate and 1-methoxypropan-2-ol, respectively.

[0022] The section headings used herein are for organizational purposes only and should not be construed as limiting the subject matter described. All references or portions of references cited herein, including but not limited to patents, patent applications, papers, books, and treatises, are incorporated herein in their entirety for all purposes. In the event that the definition of a term in one or more of the references and similar materials incorporated herein conflicts with that herein, the definition in the present application shall control.

[0023] Unless otherwise indicated, "alkyl" refers to a hydrocarbon group that can be linear or branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, and the like), or cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, and the like), or polycyclic (e.g., norbornyl, adamantyl, and the like). These alkyl moieties can be substituted or unsubstituted as described below. The term "alkyl" refers to such moieties having C1-C8 carbons. For structural reasons, it is understood that linear alkyls start at C1, while branched alkyls and cyclic alkyls start at C3, and polycyclic alkyls start at C5. Furthermore, moieties derived from alkyls described below, such as alkyloxy and perfluoroalkyl, are understood to have the same carbon number range, unless otherwise specified. If the length of the alkyl group is specified differently from above, the above definition of alkyl still applies in that it encompasses all types of alkyl moieties described above, and structural considerations regarding the minimum number of carbons for a given type of alkyl group still apply.

[0024] Alkyloxy (also known as alkoxy) refers to an alkyl group attached through an oxy (-O-) moiety (e.g., methoxy, ethoxy, propoxy, butoxy, 1,2-isopropoxy, cyclopentyloxy, cyclohexyloxy, and the like). These alkyloxy moieties may be substituted or unsubstituted as described below.

[0025] Halo or halide refers to a halogen, F, Cl, Br, or I, attached to an organic moiety by one bond.

[0026] As used herein, the term lactone includes both monolactones (eg, caprolactone) and dilactones (eg, lactide).

[0027] Haloalkyl refers to a saturated linear, cyclic or branched alkyl group, such as those defined above, in which at least one of the hydrogens is replaced by a halide selected from the group of F, Cl, Br, I, or mixtures thereof when more than one halo moiety is present. Fluoroalkyl is a specific subgroup of these moieties.

[0028] Perfluoroalkyl refers to a linear, cyclic or branched saturated alkyl group as defined above in which all hydrogens have been replaced by fluorines (eg, trifluoromethyl, perfluoroethyl, perfluoroisopropyl, perfluorocyclohexyl, and the like).

[0029] The term "hydroxyl-protected diphenylethylene" refers to diphenylethylene derivatized on at least one of its aromatic rings with a C1-C8 alkylene hydroxy moiety (-alkylene-OH), where the hydroxy moiety is functionalized with a protecting group that is not cleaved by an alkylalkali (e.g., sec-BuLi) and that allows for the formation of a hydroxy-protected diphenylethylene initiator adduct with an alkylalkali (e.g., sec-BuLi), for example with an acetal (e.g., THP protecting group) or a trialkylsilyl protecting group moiety (e.g., -Si(CH3)2-tertBu) (-alkylene-O-protecting group).

[0030] Copolymer of structure (A) The present invention, in one of its aspects, describes a random copolymer of structure (A), which comprises: The repeating unit of structure (I), in which R m1 is a C1-C8 alkyl and R1 is a benzyl-containing moiety of structure (V), where R benzis a substituent independently selected from H, C1-C4 alkyl, and C1-C4 alkoxy, L3 is C1-C4 alkylene, and "*" represents the point of attachment of the substituent to the repeat unit, and n1 indicates the number of the repeat unit in the copolymer, and further, the mole % of the repeat unit is from about 40 mole % to about 100 mole %; The repeating unit of structure (II), wherein R m2 is a C1-C8 alkyl; R2 is a moiety selected from C1-C20 linear alkyl, C3-C20 branched alkyl, and C5-C20 cyclic alkyl, a cyclohexyl alkylene moiety of structure (VI), an anthracenyl alkylene moiety of structure (VII), a naphthalenyl alkylene moiety of structure (VIII), and a biphenyl moiety of structure (VIV); where L4 and L5 are independently selected from C1-C4 alkylene, L6 and L7 are independently selected from a direct valence bond or a C1-C4 alkylene moiety; R cycl , R anth , R naph , R biph is a substituent independently selected from H, C1-C4 alkyl, and C1-C4 alkoxy, n2 represents the number of said repeat units in said copolymer, further, the mole % of said repeat units is from about 0 mole % to about 60 mole %, and further, the total mole % of repeat units in said copolymer of structures (I) and (II) repeat units is 100 mole %; • two end groups R3 and R4; Including, however, The terminal group R3 is derived from an anionic initiator and is a moiety of structure (IIIa) or is a moiety of structure (III), where L1 is a C1-C8 alkylene and R5 is H, an acetal protecting group, or a trialkylsilyl protecting group, R6 is a C1-C8 alkyl, and R e1 and R e2 is independently selected from H, C1-C8 alkyl, and C1-C8 alkoxy, and "*" represents the point of attachment of this end group to said copolymer of structure (A), and the end group R4 is a moiety derived from an anionic polymerization termination, where R4 is selected from the group consisting of H, C1-C8 alkyl, C1-C8 alkylcarbonyl (alkyl-C(=O)-), C1-C8 trialkylsilyl ((alkyl)3Si), C1-C8 dialkylsilyl ((alkyl)2HSi), C1-C8 monoalkylsilyl- ((alkyl)H2Si-), silane (-H3Si-), and benzyl-based moieties, or a moiety of formula (IV), where L R2 is a C2-C8 alkylene and R7 is H, an acetal protecting group, or a trialkylsilyl protecting group, R8 is selected from the group consisting of H, C1-C8 alkyl, C1-C8 alkylcarbonyl (alkyl-C(=O)-), C1-C8 trialkylsilyl ((alkyl)3Si), C1-C8 dialkylsilyl ((alkyl)2HSi), C1-C8 monoalkylsilyl- ((alkyl)H2Si-), silane (-H3Si-), and a benzyl-based moiety, and R e3 is selected from H, C1-C8 alkyl, and C1-C8 alkoxy, and "*" represents the point of attachment of the end group to the copolymer of structure (A), and further Both R3 and R4 cannot be simultaneously selected from the moieties of structure (III) and (IV), respectively; and R3 is a moiety of structure (III) or R4 is a moiety of structure (IV).

[0031] [ka] Another aspect of the inventive copolymer of Structure (A) is when it has Structure (A-1), where R4 is selected from the group consisting of H, C1-C8 alkyl, C1-C8 alkylcarbonyl (alkyl-C(=O)-), C1-C8 trialkylsilyl ((alkyl)3Si), C1-C8 dialkylsilyl ((alkyl)2HSi), C1-C8 monoalkylsilyl- ((alkyl)H2Si-), silane (-H3Si-), and benzylic moieties.

[0032] [ka] Another aspect of the inventive copolymer of Structure (A) is when it has Structure (A-2), where R8 is selected from the group consisting of H, C1-C8 alkyl, C1-C8 alkylcarbonyl (alkyl-C(=O)-), C1-C8 trialkylsilyl ((alkyl)3Si), C1-C8 dialkylsilyl ((alkyl)2HSi), C1-C8 monoalkylsilyl- ((alkyl)H2Si-), silane (-H3Si-), and benzylic moieties.

[0033] [ka] Another aspect of the inventive copolymers described herein are those in which the repeat units of structure (I) are 100 mole % of the repeat units and the repeat units of structure (II) are 0 mole %.

[0034] In another aspect of the inventive copolymer of structure (A), the repeat unit of structure (II) is present. In one aspect of this embodiment, the repeat unit of structure (II) is one in which R2 is a C1-C20 linear alkyl. In another aspect of this embodiment, the repeat unit of structure (II) is one in which R2 is a C3-C20 branched alkyl. In yet another aspect of this embodiment, the repeat unit of structure (II) is one in which R2 is a C5-C20 cyclic alkyl. In yet another aspect of this embodiment, the repeat unit of structure (II) is one in which R2 is a cyclohexyl alkylene moiety of structure (VI). In yet another aspect of this embodiment, the repeat unit of structure (II) is one in which R2 is an anthracenyl alkylene moiety of structure (VII). In yet another aspect, the repeat unit of structure (II) is one in which R2 is a naphthalenyl alkylene moiety of structure (VIII). In yet another aspect of this embodiment, the repeat unit of structure (II) is one in which R2 is a biphenyl moiety of structure (VIV).

[0035] Another aspect of the copolymers of the invention described herein is that Rm1 is C1-C4 alkyl.

[0036] Another aspect of the copolymers of the invention described herein is that R m1 is methyl.

[0037] Another aspect of the copolymers of the invention described herein is that R m2 is C1-C4 alkyl.

[0038] Another aspect of the copolymers of the invention described herein is that R m2 is methyl.

[0039] In another aspect of the copolymer of the invention of structure (A) described herein, R3 has structure (III) and L1 is a C1-C2 alkylene. In another aspect of this embodiment, R3 has structure (III) and L1 is methylene. In another aspect of this embodiment, R3 has structure (III) and R5 is H. In yet another aspect of this embodiment, R3 has structure (III) and R5 is an acetal protecting group. In yet another aspect of this embodiment, R3 has structure (III) and R5 is a trialkylsilyl protecting group. In yet another aspect of this embodiment, R3 has structure (III) and R6 is a C1-C6 alkyl. In yet another aspect of this embodiment, R3 has structure (III) and R6 is isobutyl. In yet another aspect of this embodiment, R3 has structure (III) and Re1 is H. In yet another aspect of this embodiment, R3 has the structure (III) and R e1 is C1-C8 alkyl. In yet another aspect of this embodiment, R3 has the structure (III) and R e1 is C1-C8 alkoxy. In yet another aspect of this embodiment, R3 has the structure (III) and R e2 is H. In yet another aspect of this embodiment, R3 has the structure (III) and R e2is C1-C8 alkyl. In yet another aspect of this embodiment, R3 has the structure (III) and R e2 is C1-C8 alkoxy.

[0040] In another aspect of the copolymer of the present invention having structure (A) described herein, R benz is H. In another aspect of this embodiment, R benz is C1-C4 alkyl. In another aspect of this embodiment, R benz is C1-C4 alkoxy.

[0041] In another aspect of the inventive copolymer of Structure (A) described herein, L3 is a C1-C3 alkylene. In another aspect of this embodiment, L3 is a C1-C2 alkylene. In yet another aspect of this embodiment, L3 is ethylene. In yet another aspect of this embodiment, L3 is methylene.

[0042] In yet another aspect of the copolymer of the invention of Structure (A) described herein, the copolymer has Structure (A-3), and in another aspect of this embodiment, R2 is a C1-C20 linear alkyl. In yet another aspect of this embodiment, R2 is a C3-C20 branched alkyl. In yet another aspect of this embodiment, R2 is a C5-C20 cyclic alkyl.

[0043] [ka] In another aspect of the inventive copolymer of structure (A) described herein, said copolymer has the structure (A-3a).

[0044] [ka] In another aspect of the inventive copolymer of structure (A) described herein, said copolymer has the structure (A-3b).

[0045] [ka] In another aspect of the inventive copolymer of structure (A) described herein, said copolymer has the structure (A-3c).

[0046] [ka] In another aspect of the inventive copolymer of structure (A) described herein, said copolymer has the structure (A-3d).

[0047] [ka] In another aspect of the inventive copolymer of Structure (A) described herein, the copolymer has Structure (A-4). In one aspect of this embodiment, R2 is a C1-C20 linear alkyl. In another aspect of this embodiment, R2 is a C3-C20 branched alkyl. In yet another aspect of this embodiment, R2 is a C5-C20 cyclic alkyl.

[0048] [ka] In another aspect of the inventive copolymer of structure (A) described herein, said copolymer has the structure (A-4a).

[0049] [ka] In another aspect of the inventive copolymer of structure (A) described herein, said copolymer has the structure (A-4b).

[0050] [ka] In another aspect of the inventive copolymer of structure (A) described herein, said copolymer has the structure (A-4c).

[0051] [ka] In another aspect of the inventive copolymer of structure (A) described herein, said copolymer has the structure (A-4d).

[0052] [ka] In another aspect of the inventive copolymer of Structure (A) described herein, the copolymer has Structure (A-5). In one aspect of this embodiment, R2 is a C1-C20 linear alkyl. In another aspect of this embodiment, R2 is a C3-C20 branched alkyl. In yet another aspect of this embodiment, R2 is a C5-C20 cyclic alkyl.

[0053] [ka] In another aspect of the inventive copolymer of structure (A) described herein, said copolymer has the structure (A-5a).

[0054] [ka] In another aspect of the inventive copolymer of structure (A) described herein, said copolymer has the structure (A-5b).

[0055] [ka] In another aspect of the inventive copolymer of structure (A) described herein, said copolymer has the structure (A-5c).

[0056] [ka] In another aspect of the inventive copolymer of structure (A) described herein, said copolymer has the structure (A-5d).

[0057] [ka] In another aspect of the inventive copolymer of structure (A) described herein, said copolymer has the structure (A-6).

[0058] [ka] In another aspect of the inventive copolymer of structure (A) described herein, said copolymer has the structure (A-7).

[0059] [ka] In another aspect of the inventive copolymer of structure (A) described herein, said copolymer has the structure (A-8).

[0060] [ka] In another aspect of the copolymer of the invention of structure (A) described herein, it has structure (A-2) where R4 has structure (IV) and R3 is a moiety of structure (IIIa) and L2 is a C2-C4 alkylene. In another aspect of this embodiment, L2 is 1,3-propylene. In yet another aspect of this embodiment, L2 is ethylene. In another aspect of this embodiment, R7 is H. In yet another aspect of this embodiment, R7 is an acetal protecting group. In yet another aspect of this embodiment, R7 is a trialkylsilyl protecting group. In another aspect of this embodiment, R8 is a C1-C4 alkyl. In yet another aspect of this embodiment, R8 is H. In yet another aspect of this embodiment, R e3 is H. In yet another aspect of this embodiment, R e3 is C1-C8 alkyl. In yet another aspect of this embodiment, R e3 In yet another aspect of this embodiment, R benz is H. In yet another aspect of this embodiment, R benz is C1-C4 alkyl. In yet another aspect of this embodiment, R benzis C1-C4 alkoxy.

[0061] [ka] In another aspect of the copolymer of the invention of Structure (A) described herein having Structure (A-2), it has the more specific Structure (A-9). In one aspect of this embodiment, R2 is a C1-C20 linear alkyl. In another aspect of this embodiment, R2 is a C3-C20 branched alkyl. In yet another aspect of this embodiment, R2 is a C5-C20 cyclic alkyl.

[0062] [ka] In another aspect of the inventive copolymer of structure (A) described herein having structure (A-2), it has the more specific structure (A-9a).

[0063] [ka] In another aspect of the inventive copolymer of structure (A) described herein having structure (A-2), it has the more specific structure (A-9b).

[0064] [ka] In another aspect of the inventive copolymer of structure (A) described herein having structure (A-2), it has the more specific structure (A-9c).

[0065] [ka] In another aspect of the inventive copolymer of structure (A) described herein having structure (A-2), it has the more specific structure (A-9d).

[0066] [ka] In another aspect of the copolymer of the invention of Structure (A) described herein having Structure (A-2), it has the more specific Structure (A-10). In one aspect of this embodiment, R2 is a C1-C20 linear alkyl. In another aspect of this embodiment, R2 is a C3-C20 branched alkyl. In yet another aspect of this embodiment, R2 is a C5-C20 cyclic alkyl.

[0067] [ka] In another aspect of the inventive copolymer of structure (A) described herein having structure (A-2), it has the more specific structure (A-10a).

[0068] [ka] In another aspect of the inventive copolymer of structure (A) described herein having structure (A-2), it has the more specific structure (A-10b).

[0069] [ka] In another aspect of the inventive copolymer of structure (A) described herein having structure (A-2), it has the more specific structure (A-10c).

[0070] [ka] In another aspect of the inventive copolymer of structure (A) described herein having structure (A-2), it has the more specific structure (A-10d).

[0071] [ka] In another aspect of the copolymer of the invention of Structure (A) described herein having Structure (A-2), it has the more specific Structure (A-11). In one aspect of this embodiment, R2 is a C1-C20 linear alkyl. In another aspect of this embodiment, R2 is a C3-C20 branched alkyl. In yet another aspect of this embodiment, R2 is a C5-C20 cyclic alkyl.

[0072] [ka] In another aspect of the inventive copolymer of structure (A) described herein having structure (A-2), it has the more specific structure (A-11a).

[0073] [ka] In another aspect of the inventive copolymer of structure (A) described herein having structure (A-2), it has the more specific structure (A-11b).

[0074] [ka] In another aspect of the inventive copolymer of structure (A) described herein having structure (A-2), it has the more specific structure (A-11c).

[0075] [ka] In another aspect of the inventive copolymer of structure (A) described herein having structure (A-2), it has the more specific structure (A-11d).

[0076] [ka] In another aspect of the inventive copolymers of structure (A) described herein, I has the structure (A-12).

[0077] [ka] In another aspect of the inventive copolymer of structure (A) described herein, I has the structure (13).

[0078] [ka] In another aspect of the inventive copolymers of structure (A) described herein, I has the structure (A-14).

[0079] [ka] In another aspect of the copolymer of the present invention having structure (A) described herein, it has an M of from about 500 to about 100,000. n In another aspect of this embodiment, it is from about 500 to about 20,000.

[0080] In another aspect of the inventive copolymer of structure (A) described herein, it has a polydispersity of from about 1.0 to about 1.2. In another aspect of this embodiment, it has a polydispersity of from 1.0 to about 1.1. In another aspect of this embodiment, it has a polydispersity of from 1.0 to about 1.07. In yet another aspect of this embodiment, it has a polydispersity of from 1.0 to about 1.05.

[0081] In another aspect of the copolymer of the present invention of Structure (A) described herein, which contains both repeat units of Structures (I) and (II), the repeat units of Structure (II) range from about 1 mol % to about 60 mol % of the total repeat units of Structures (I) and (II). In another aspect of this embodiment, the repeat units of Structure (II) range from about 5 mol % to about 50 mol % of the total repeat units of Structures (I) and (II). In yet another aspect of this embodiment, the repeat units of Structure (II) range from about 7 mol % to about 40 mol % of the total repeat units of Structures (I) and (II). In yet another aspect of this embodiment, the repeat units of Structure (II) range from about 9 mol % to about 40 mol % of the total repeat units of Structures (I) and (II). In yet another aspect of this embodiment, the repeating units of structure (II) range from about 10 mol % to about 30 mol % of the total repeating units of structures (I) and (II). In yet another aspect of this embodiment, the repeating units of structure (II) range from about 10 mol % to about 25 mol % of the total repeating units of structures (I) and (II). In another aspect of these embodiments, the repeating units of structure (I) have a more specific structure (Ia). In yet another aspect of these embodiments, the repeating units of structure (II) have a more specific structure (IIa). In yet another aspect of these embodiments, the repeating units of structure (II) have a more specific structure (IIb). In yet another aspect of these embodiments, the repeating units of structure (II) have a more specific structure (IIc). In yet another aspect of these embodiments, the repeating units of structure (II) have a more specific structure (IId).

[0082] Compositions containing copolymers of structure (A) Another aspect of the invention is a composition comprising a copolymer of structure (A) and substructures thereof as described herein, and an organic spin-casting solvent, said copolymer wherein end group (III) is present and R5 is H, or end group (IV) is present and R7 is H. In one aspect of this embodiment, it is a composition of these two components.

[0083] Solvents suitable for use in the compositions of the present invention comprising copolymers of structure (A) and its substructures described herein are any organic solvents used to spin cast materials such as DSA materials, photoresists, bottom antireflective coatings, or other types of organic coatings used in lithographic processing of semiconductor materials. In another aspect of the compositions of the present invention, the organic spin casting solvent is capable of dissolving the random copolymer and other additional optional components such as those described herein. The organic spin casting solvent may be a single solvent or a mixture of solvents.Suitable solvents are organic solvents, for example glycol ether derivatives, 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; glycol ether ester derivatives, 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; carboxylates of dibasic acids, such as diethyl oxylate and dimethyl malonate; dicarboxylates of glycols, such as ethylene glycol diacetate and propylene glycol diacetate; and hydroxycarboxylates, such as methyl lactate, ethyl lactate (EL), ethyl glycolate and ethyl 3-hydroxypropionate; ketone esters, such as methyl pyruvate or ethyl pyruvate; Mention may be made of alkyloxycarboxylic acid esters, such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate or methyl ethoxypropionate; ketone derivatives, such as methyl ethyl ketone, acetylacetone, cyclopentanone, cyclohexanone or 2-heptanone; ketone ether derivatives, such as diacetone alcohol methyl ether; ketone alcohol derivatives, such as acetol or diacetone alcohol; ketals or acetals, such as 1,3 dioxalane and diethoxypropane; lactones, such as butyrolactone; amide derivatives, such as dimethylacetamide or dimethylformamide, anisole and mixtures thereof.

[0084] Methods of Using Compositions Comprising Copolymers of Structure (A) Coating Formation Method Another aspect of the present invention is a method for forming a grafted coating of a copolymer on a substrate, comprising the steps of: i) forming a coating of a composition comprising the copolymer of Structure (A) according to any one of its aspects on a substrate; ii) heating the coating at a temperature of from about 90° C. to about 180° C. to remove the solvent to form a grafted coating of the copolymer; iii) heating the grafted coating of step ii) at a temperature of about 200° C. to about 250° C. to form a fully crosslinked or fully crosslinked and grafted copolymer coating; The method comprises:

[0085] Method for forming a grafted neutral layer coating Another aspect of the present invention is a method of forming a grafted neutral layer coating on a substrate, comprising the steps of: ia) forming a coating of a composition comprising a copolymer of structure (A) according to any one of its embodiments on a substrate; iia) heating the coating at a temperature of from about 90° C. to about 180° C. to remove the solvent and form a grafted coating; iiia) heating the grafted coating of step iia) at a temperature of about 200° C. to about 250° C. to form a fully grafted neutral layer coating; The method comprises:

[0086] Method for forming a self-assembled block copolymer coating on a neutral layer coating - Patents.com Another aspect of the present invention is a method for forming a self-assembled block copolymer coating on a neutral layer coating, comprising the steps of: ij) forming a neutral layer coating according to the method for forming a grafted neutral layer coating described above; iij) applying a block copolymer onto said neutral layer coating and annealing until induced self-assembly of the block copolymer coating occurs; The method comprises:

[0087] Graphoepitaxy-directed self-assembly of block copolymers used to form images Another aspect of the invention is a method for graphoepitaxy-guided self-assembly of a block copolymer coating used to form an image, comprising the steps of: ik) forming a neutral layer coating according to the method for forming a grafted neutral layer coating described above; iik) providing a coating of a photoresist coating over said neutral layer coating and forming a pattern in the photoresist coating; iiik) applying a block copolymer comprising an etch resistant block and a highly etchable block onto the photoresist pattern and annealing until induced self-assembly occurs; and ivk) etching the block copolymer, thereby removing highly etchable blocks of the copolymer overlying areas of the substrate and simultaneously forming a pattern in the substrate selectively in these areas; The method comprising:

[0088] In one aspect of this method, a pattern in the photoresist coating is formed by imaging lithography selected from the group consisting of e-beam, broadband, 193 nm immersion lithography, 13.5 nm EUV lithography, 193 nm deep UV lithography, 248 nm deep UV lithography, 365 nm UV lithography, and 436 nm UV lithography.

[0089] Chemo-epitaxy directed self-assembly of block copolymers used to form images - Patents.com Another aspect of the invention is a method for chemoepitaxy-directed self-assembly of block copolymer coatings used to form images, comprising the steps of: il) forming a neutral layer coating according to the method for forming a grafted neutral layer coating described above; iil) providing a coating of a photoresist coating over said neutral layer coating and forming a pattern in said photoresist coating, thereby forming areas of the neutral layer coating that are not covered by resist; iiil) treating and removing the uncovered neutral layer coating to form a pinning region; ivl) removing the photoresist to expose the untreated neutral layer coating to form a chemo-epitaxy pattern including neutral and pinned regions; vl) applying a block copolymer comprising an etch-resistant block and a highly etchable block onto the neutral layer coating and annealing until induced self-assembly occurs; and vil) etching the block copolymer, thereby removing highly etchable blocks of the copolymer overlying areas of a substrate and simultaneously forming a pattern in the substrate selectively in these areas; The method comprises:

[0090] In one aspect of this method, a pattern in the photoresist coating is formed by imaging lithography selected from the group consisting of e-beam, broadband, 193 nm immersion lithography, 13.5 nm EUV lithography, 193 nm deep UV lithography, 248 nm deep UV lithography, 365 nm UV lithography, and 436 nm UV lithography.

[0091] Another aspect of the present invention is the use of a polymer of structure (A) as described herein, or a composition as described herein, in any one of its embodiments, in a process for the preparation of a grafted or self-assembled coating on a substrate. EXAMPLES

[0092] chemicals All chemicals were obtained from Millipore-Sigma unless otherwise stated. 9-Anthracenemethyl methacrylate was obtained from Shanghai B&C. NMR was measured on a Bruker 400 MHz Avance III spectrometer in CD2Cl2. GPC was measured using an Agilent system.

[0093] All synthesis experiments were carried out in a N2 atmosphere. Lithography experiments were carried out as described herein. The molecular weights of the copolymers were measured using gel permeation chromatography.

[0094] Unless otherwise stated, 1 1 H NMR spectra were recorded on a Bruker Advanced III 400H Mz spectrometer in CD2Cl2.

[0095] Lithography experiments were performed using a TEL Clean ACT8 track. SEM pictures were taken using an Applied Materials NanoSEM_3D. Scanning electron micrographs are shown at 1 FOV magnification or 2 FOV magnification (field of view (FOV) = 5 μm using 1, 2 and 5 FOV).

[0096] Etching experiments were performed using standard isotropic oxygen etching conditions for self-assembled film block copolymers of methyl methacrylate and styrene.

[0097] Unless otherwise stated, molecular weight measurements (also known as M n Polydispersity) is 100Å, 500Å, 10 3 Å, 10 5 Å and 10 6 The analysis was carried out by gel permeation chromatography equipped with an Åμ-Ultrastyragel column (PSS Inc., Germany) using THF solvent as the eluent. Polystyrene polymer standards were used for calibration.

[0098] Here, the titrant "secbutylDPE-Li" is defined as the adduct of sec-butyllithium and 1,1'-diphenylethylene (DPE) prepared by adding an equimolar amount of sec-butyllithium to a 2 wt % solution of DPE in toluene.

[0099] The following are exemplary experimental descriptions. Unless otherwise stated, all polymers synthesized in this disclosure were subjected to molecular weight measurements (M n,GPC and M w,GPC ) and polydispersity index, 100 Å, 500 Å, 10 3 Å, 10 5 Å and 10 6 The polymers were characterized by gel permeation chromatography (PSS Inc., Germany) equipped with an Åμ-Ultrastyragel column, using THF solvent (1 mL / min) as eluent and polystyrene standards for calibration as references. The polymer composition and end functional groups were characterized by a 300 MHz NMR spectroscopy in CD2Cl2. 1 The thermal conductivity of the coatings was determined using H-NMR. Coatings were examined using blanket dielectric and metal coupons. The films were baked at the desired temperature and time and cleaned of excess material.

[0100] Synthesis of polymeric materials for testing Polymer synthesis example for reference: Synthesis of P(Sb-MMA)(26k-b-30k) P(Sb-MMA) (26K-b-30K) was synthesized using the same procedure as described in Example 2. The amount of initiator and monomer were varied to achieve the desired Mn and composition of PS and PMMA blocks. 20 g (0.192 mol) of styrene was polymerized by the quick addition of 0.55 mL (1.4 M solution) of sec-butyllithium. Then, 0.164 g (0.0007 mol) of 1,1'-diphenylethylene (DPE) in 2.5 ml of anhydrous toluene was added via sample into the reactor. The orange color of the reaction mixture changed to a dark brick red color, suggesting that the styryllithium active center was converted to a delocalized DPE-adducted carbanion. After stirring for 2 min, a small amount (2 mL) of the reaction mixture was taken for PS block molecular weight analysis. Then, methyl methacrylate (22.85 g, 0.23 mol) was added via ampoule. The reaction was quenched after 30 min with 1 mL of degassed methanol. The block copolymer was recovered by precipitation into excess isopropanol (5 times the volume of the polymer solution) containing 10% water, filtered, and dried under vacuum at 55° C. for 12 h to give 40 g of P(Sb-MMA) (94% yield) consisting of 46.9 mol % polystyrene blocks and 53.1 mol % polymethyl methacrylate blocks. 3 Å, 10 5 Å and 10 6 Gel permeation chromatography with an Åμ-Ultrastyragel column revealed an M of 45,048 g / mol for the first P(SDPE) block against a PS calibration standard. n (GPC) and M of 1.04 w / M n The molecular weight of the diblock copolymer obtained by GPC was M n,PS-b-PMMA = 46,978 g / mol and M w / M n =1.02.

[0101] Example 1: Synthesis of hydroxymethyl-terminated poly(benzyl methacrylate-co-[1,1'-biphenyl]-4-ylmethyl methacrylate) [1,1'-biphenyl]-4-yl methyl methacrylate [1,1'-biphenyl]-4-yl methacrylate (BPMMA, 3.76 g, 14.9 mmol) was weighed into a calibrated ampoule and dissolved in toluene (8.0 mL). Benzyl methacrylate (BnMA, 10.1 ml, 59.6 mmol) was added to the ampoule via syringe. The mixture was stirred under reduced pressure (100° C.) until toluene (8.0 ml) was removed from the monomer mixture. -6The flask was degassed to 35°C (mmHg). In the glove box, tetrahydropyran (THP) protected 3-(hydroxymethyl)-1,1-diphenylethylene (MTAG-8, 0.72 g, 2.45 mmol) was weighed into a vial (1.2 molar excess over s-BuLi) and dissolved in 3 mL of toluene. This solution was immediately titrated with dilute secbutylDPE-Li solution until an orange color persisted. The color of the solution faded and then turned green by the time it was added to the reactor. After closing the stopcock, the ampoule was removed from the glove box. Both the BnMA / BPMMA ampoule and the MTAG-8 ampoule were attached to a flask using glass joints and yellow grease, and the required amount of LiCl (5-fold excess over s-BuLi) was weighed and quickly added to the flask and closed with a three-way septum adapter, which was connected with rubber tubing to apply vacuum / argon. Vacuum was applied to the flask and the LiCl was dried using a heat gun. After 10 min, the flask was brought to room temperature and backfilled with argon. Under positive pressure, approximately 150 mL of anhydrous THF was transferred to the flask via cannula transfer. The temperature of the flask was reduced to -78°C using a dry ice / acetone bath. The LiCl / THF and the solution was titrated with s-BuLi (3 ml, 1.4 M) until a persistent lemon yellow / yellow color was obtained. After 5 min, the dry ice / acetone bath was removed and the flask was allowed to come to room temperature. It took 15-30 min for the yellow color to completely decay. After a colorless solution was obtained, the temperature of the flask was reduced to -78°C and the stopcock was opened to add the titrated MTAG-8 solution. The colorless mixture turned pale orange after the addition of MTAG-8. The required amount of s-BuLi (1.46 mL, 2.04 mmol, 1.4 M) to generate active MTAG-8 initiator was added using an airtight glass sill. As a result, the color changes from pale orange to dark red, which is the color of the activated MTAG-8 / Li initiator. After 2-3 min, the initiator solution and the BnMA / BPMMA mixture, which were stirred at 300 rpm, were added dropwise for 10 min. Growth was continued for an additional 110 min and then quenched with 2 mL of degassed methanol and allowed to come to room temperature.MeOH (80-100 ml) was added to the solution followed by pTSA (4.7 g, 10-fold excess). The reaction mixture was stirred overnight at room temperature. The mixture was precipitated into a large amount of methanol and the polymer was collected by suction filtration. The dry polymer was dissolved in EtOAc as a 10% solids solution and washed three times with 1 wt% ascorbic acid (aqueous solution) and then three times with deionized water. The organic mixture was precipitated into hexanes (8 parts by volume) and the precipitate was collected by suction filtration and dried in a vacuum oven at 60°C. P(BnMA-co-BPMMA)-DPE-CH2OH was obtained in quantitative yield.

[0102] Table 1 outlines the reaction conditions and characterization for BPMMA-containing copolymers Examples 1, 1a, and 1b (Scheme 1). Examples 1a and 1b used the same procedure as Example 1, but varied the amount of BPMMA used (Example 1a (2x), Example 1b (2.5x)). This was reflected in the amount of BPMMA incorporated into the polymer as a repeat unit in Table 1, as measured by proton NMR in CD2Cl2.

[0103] [ka] Scheme 1: Synthesis of hydroxymethyl-terminated poly(benzyl methacrylate-co-[1,1'-biphenyl]-4-ylmethyl methacrylate)

[0104] [Table 1]

[0105] Example 2 Synthesis of hydroxymethyl-terminated poly(benzyl methacrylate-co-cyclohexyl methacrylate) Cyclohexyl methacrylate (CHMA, 5 ml, 28.7 mmol) and benzyl methacrylate (BnMA, 14.6 ml, 86.1 mmol) were added to the ampoule via syringe, and the mixture was stirred under reduced pressure (100° C.) until toluene (8.0 ml) was removed from the monomer mixture. -6The flask was degassed to 35°C (mmHg). In the glove box, tetrahydropyran (THP) protected 3-(hydroxymethyl)-1,1-diphenylethylene (MTAG-8, 0.71 g, 2.4 mmol) was weighed into a vial (1.2 molar excess over s-BuLi) and dissolved in 3 mL of toluene. This solution was immediately titrated with dilute secbutylDPE-Li solution until an orange color persisted. The color of the solution faded and then turned green by the time it was added to the reactor. After closing the stopcock, the ampoule was removed from the glove box. Both the BnMA / BPMMA ampoule and the MTAG-8 ampoule were attached to a flask using glass joints and yellow grease, and the required amount of LiCl (5-fold excess over s-BuLi) was weighed and quickly added to the flask and closed with a three-way septum adapter, which was connected with rubber tubing to apply vacuum / argon. Vacuum was applied to the flask and the LiCl was dried using a heat gun. After 10 min, the flask was brought to room temperature and backfilled with argon. Under positive pressure, approximately 150 mL of anhydrous THF was transferred to the flask via cannula transfer. The temperature of the flask was reduced to -78°C using a dry ice / acetone bath. The LiCl / THF and the solution was titrated with s-BuLi (3 ml, 1.4 M) until a persistent lemon yellow / yellow color was obtained. After 5 min, the dry ice / acetone bath was removed and the flask was allowed to come to room temperature. It took 15-30 min for the yellow color to completely decay. After a colorless solution was obtained, the temperature of the flask was reduced to -78°C and the stopcock was opened to add the titrated MTAG-8 solution. The colorless mixture turned pale orange after the addition of MTAG-8. The required amount of s-BuLi (1.43 mL, 2.0 mmol, 1.4 M) to generate active MTAG-8 initiator was added using an airtight glass syringe. As a result, the color changes from pale orange to dark red, which is the color of the activated MTAG-8 / Li initiator. After 2-3 min, the initiator solution and the BnMA / BPMMA mixture, which were stirred at 300 rpm, were added dropwise for 10 min. Growth was continued for an additional 110 min and then quenched with 2 mL of degassed methanol and allowed to come to room temperature.MeOH (80-100 ml) was added to the solution followed by pTSA (3.8 g, 10-fold excess). The reaction mixture was stirred overnight at room temperature. The mixture was precipitated into a large amount of methanol and the polymer was collected by suction filtration. The dried polymer was dissolved in EtOAc as a 10% solids solution and washed three times with 1 wt% ascorbic acid (aqueous solution) and then three times with deionized water. The organic mixture was precipitated into hexanes (8 parts by volume) and the precipitate was collected by suction filtration and dried in a vacuum oven at 60°C. P(BnMA-co-BPMMA)-DPE-CH2OH was obtained in quantitative yield. Table 2 summarizes the reaction conditions used in Example 2 (Scheme 2) and the characterization of the resulting copolymers containing repeat units derived from CHMA.

[0106] [ka] Scheme 2: Synthesis of hydroxymethyl-terminated poly(benzyl methacrylate-co-cyclohexyl methacrylate)

[0107] [Table 2]

[0108] Example 3 Synthesis of hydroxymethyl-terminated poly(benzyl methacrylate-co-9-anthracenylmethyl methacrylate) 9-Anthracenylmethyl methacrylate (AMMA, 3.11 g, 11.3 mmol) was weighed into a calibrated ampoule and dissolved in toluene (6.0 mL). Benzyl methacrylate (BnMA, 17.1 ml, 100.9 mmol) was added into the ampoule via syringe. The mixture was freeze-thawed three times to degas the mixture. In a glove box, tetrahydropyran (THP) protected 3-(hydroxymethyl)-1,1-diphenylethylene (MTAG-8, 0.77 g, 2.42 mmol) was weighed into a vial (1.2 molar excess over s-BuLi) and dissolved in approximately 3-5 mL of toluene. The solution was immediately titrated with dilute secbutylDPE-Li solution until an orange color persisted. The color of the solution faded and then turned green by the time it was added to the reactor. After closing the stopcock, the ampule was removed from the glove box. Both the BnMA / AMMA and MTAG-8 ampules were attached to the flask using glass joints and yellow grease. The required amount of LiCl (5-fold excess over s-BuLi) was weighed and quickly added to the flask and closed with a 3-way septum adapter, which was connected with rubber tubing for vacuum / argon access. Vacuum was applied to the flask and the LiCl was dried using a heat gun. After 10 minutes, the flask was brought to room temperature and backfilled with argon. Under positive pressure, approximately 250 mL of anhydrous THF was transferred to the flask via cannula transfer. The temperature of the flask was reduced to -78°C using a dry ice / acetone bath. The LiCl / THF and the solution were titrated with s-BuLi (3 ml, 1.4 M) until a persistent lemon yellow / yellow color was obtained. After 5 minutes, the dry ice / acetone bath was removed and the flask was allowed to come to room temperature. It took 15-30 minutes for the yellow color to completely fade. After a colorless solution was obtained, the temperature of the flask was reduced to -78°C and the stopcock was opened to add the titrated MTAG-8 solution. The colorless mixture turned pale orange after the addition of MTAG-8. The required amount of s-BuLi (1.46 mL, 2.33 mmol, 1.4 M) to generate active MTAG-8 initiator was added using an airtight glass syringe.The resulting color changes from pale orange to dark red, the color of the active MTAG-8 / Li initiator. After 2-3 min, the initiator solution, stirring at 300 rpm, and the BnMA / AMMA mixture were added dropwise for 10 min. Growth was continued for an additional 110 min and then quenched with 2 mL of degassed methanol and brought to room temperature. MeOH (15 ml) was added to the solution followed by pTSA (2.23 g, 5.0-fold excess). The reaction mixture was stirred overnight at room temperature. The mixture was precipitated in a large amount of methanol and the polymer was collected by suction filtration. The dry polymer was dissolved in EtOAc as a 10% solids solution and washed three times with 1 wt % ascorbic acid (aqueous solution) and then three times with deionized water. The organic mixture was precipitated into hexanes (8 parts by volume) and the precipitate was collected by suction filtration and dried in a vacuum oven at 70°C. P(BnMA-co-AMMA)-DPE-CH2OH was obtained in quantitative yield. Table 3 outlines the reaction conditions and characterization of copolymers containing AMMA (Examples 3, 3a, 3b, and 3c (Scheme 3)). Examples 3a-3c used the same procedure as Example 3, but increased amounts of AMMA were used (Example 3a (3-fold), Example 3b (4.36-fold), Example 3c (4.11-fold)). This was reflected in the amount of BPMMA incorporated into the polymer as a repeat unit in Table 1, as measured by proton NMR in CD2Cl2.

[0109] [ka] Scheme 3: Synthesis of hydroxymethyl-terminated poly(benzyl methacrylate-co-[1,1'-biphenyl]-4-ylmethyl methacrylate)

[0110] [Table 3]

[0111] Preparation of polymer formulations: The polymers described herein were dissolved separately in PGMEA to prepare 1 wt% solutions. These solutions were filtered separately using nylon filters (Entegris, Billerica, MA). These solutions were separately coated on both metal (Cu, W) and SiO2 wafers at 1500 rpm, and then the wafers were baked at 230°C for 5 minutes. After baking, the wafers were washed with PGMEA for 2 minutes to remove ungrafted polymer from the wafers, which were then spun at "1,500 ppm" and spun dry, followed by baking at 110°C for 1 minute. Water contact angles were then measured to understand the grafting efficiency. The results are shown in Table 1. A second brush of polymer formulations containing hydroxy-terminated PS-OH or PMMA-OH was then prepared in PGMEA at 1 wt% solids content. The solutions were then spin-coated onto the pre-brushed metal and SiO2 substrates after filtering using a 0.25 micron nylon filter. After baking at various temperatures and times, these double-brushed substrates were washed to remove unreacted second part brushes. These double-brushed substrates were then examined by WCA and XPS to understand cross-grafting and to determine the efficiency of the first brush and its selectivity to the metal substrate.

[0112] Figure 3 shows A) P(BnMA-r-BPMA 25% )-OH(Mn:13K, brush FT:4.2nm±0.3, WCA:81.0±2.3) PS-b-PMMA, B)P(BnMA-r-CHMA 25% )-OH(Mn:23K, brush FT:3.8nm±0.3, WCA:79.4±0.5) PS-b-PMMA, C)P(BnMA-r-AMMA 20% Figure 1 shows 1 FOV SEM images of each fingerprint pattern on silicon wafer using PS-b-PMMA on 100-200-200-OH (Mn: approx. 7.0 K, brush FT: 7.9 nm ± 0.3, WCA: 80.8 ± 0.5). Process conditions: Si wafer, coat NLD, 200 °C / 30 min / N2 (polymer A, B & C, 230 °C), toluene soak for 15 min, N2 blow dry, PME-7167 Ctg65: L0 = 48 nm, FT = 50 nm, 270 °C / 1 h (N2).

[0113] While the disclosed and claimed invention has been described and illustrated with a certain degree of detail, it will be apparent that this disclosure is made by way of example only, and that those skilled in the art may resort to numerous variations in the conditions and sequence of steps without departing from the spirit and scope of the disclosed and claimed invention.

Claims

1. A random polymer of structure (A): Repeating units of structure (I), wherein R ｍ１ is C1-C8 alkyl, and R １ is the benzyl-containing moiety of structure (V), where R ｂｅｎｚ are substituents independently selected from H, C1-C4 alkyl, and C1-C4 alkoxy; L ３ is a C1-C4 alkylene, and "*" represents the point of attachment of the substituent to the repeat unit, and n1 indicates the number of this repeat unit in the polymer, and further, the mole % of this repeat unit is from 40 mole % to 100 mole %; Repeating units of structure (II), wherein R ｍ２ is C1-C8 alkyl, and R ２ is a moiety selected from C1-C20 linear alkyl, C3-C20 branched alkyl, and C5-C20 cyclic alkyl, a cyclohexyl alkylene moiety of structure (VI), an anthracenyl alkylene moiety of structure (VII), a naphthalenyl alkylene moiety of structure (VIII), and a biphenyl moiety of structure (VIV), wherein L ４ and L ５ are independently selected from C1-C4 alkylene; L ６ and L ７ is independently selected from a direct valence bond or a C1-C4 alkylene moiety; R ｃｙｃｌ , R ａｎｔｈ , R ｎａｐｈ , R ｂｉｐｈ is a substituent independently selected from H, C1-C4 alkyl, and C1-C4 alkoxy, n2 represents the number of this repeat unit in the polymer, further, the mole % of this repeat unit is from 0 mole % to 60 mole %, and further, the total mole % of repeat units in said polymer of structures (I) and (II) repeat units is 100 mole %; Two terminal groups R ３ and R ４ ; Including, however, Terminal group R ３ is derived from an anionic initiator and is a moiety of structure (IIIa) or a moiety of structure (III), wherein L １ is C1-C8 alkylene, and R ５ is H, an acetal protecting group, or a trialkylsilyl protecting group; R ６ is C1-C8 alkyl, and R ｅ１ and R ｅ２ are independently selected from H, C1-C8 alkyl, and C1-C8 alkoxy, and "*" represents the point of attachment of this end group to the polymer of structure (A); and R ４ is H, C1-C8 alkyl, C1-C8 alkylcarbonyl (alkyl-C(=O)-), C1-C8 trialkylsilyl ((alkyl) ３ Si), C1-C8 dialkylsilyl ((alkyl) ２ HSi), C1-C8 monoalkylsilyl-((alkyl)H ２ Si-), silane (-H ３ Si—), and a benzyl-based moiety, or a moiety of structure (IV), wherein L ２ is a C2-C8 alkylene, and R ７ is H, an acetal protecting group, or a trialkylsilyl protecting group; R ８ is H, C1-C8 alkyl, C1-C8 alkylcarbonyl (alkyl-C(=O)-), C1-C8 trialkylsilyl ((alkyl) ３ Si), C1-C8 dialkylsilyl ((alkyl) ２ HSi), C1-C8 monoalkylsilyl-((alkyl)H ２ Si-), silane (-H ３ Si—), and benzyl-based moieties, and R ｅ３ is selected from H, C1-C8 alkyl, and C1-C8 alkoxy, and "*" represents the point of attachment of the end group to the polymer of structure (A), and further Both R ３ and R ４ cannot be simultaneously selected from the moieties of structure (III) and structure (IV), respectively; and R ３ is a moiety of structure (III), or R ４ is a moiety of structure (IV), The random polymer. 【Chemistry 1】

2. Structure (A-1): 【Chemistry 2】 [In the formula, R ４ is H, C1-C8 alkyl, C1-C8 alkylcarbonyl (alkyl-C(=O)-), C1-C8 trialkylsilyl ((alkyl) ３ Si), C1-C8 dialkylsilyl ((alkyl) ２ HSi), C1-C8 monoalkylsilyl-((alkyl)H ２ Si-), silane (-H ３ Si—), and benzyl-based moieties. or having the structure (A-2): 【Transformation 3】 [In the formula, R ８ is H, C1-C8 alkyl, C1-C8 alkylcarbonyl (alkyl-C(=O)-), C1-C8 trialkylsilyl ((alkyl) ３ Si), C1-C8 dialkylsilyl ((alkyl) ２ HSi), C1-C8 monoalkylsilyl-((alkyl)H ２ Si-), silane (-H ３ Si—), and benzyl-based moieties.

2. The polymer of claim 1 having the formula:

3. 3. The polymer of claim 1 or 2, wherein the repeating units of structure (I) are 100 mole % of the repeating units and the repeating units of structure (II) are 0 mole %.

4. 3. The polymer of claim 1 or 2, wherein said repeat unit of structure (II) is present.

5. R ３ has the structure (III), and L １ is a C1-C2 alkylene, or R ４ has the structure (IV), and L ２ The polymer of claim 1 or 2, wherein is a C2 to C4 alkylene.

6. The polymer according to claim 1, having a structure selected from the group consisting of Structure (A-3), Structure (A-4), Structure (A-5), Structure (A-9), Structure (A-10), and Structure (A-11). 【Chemistry 4】 【Transformation 5】 【Transformation 6】 【Transformation 7】 【Transformation 8】 【Chemistry 9】

7. The polymer according to claim 1, having a structure selected from the group consisting of Structure (A-6), Structure (A-7), Structure (A-8), Structure (A-12), Structure (A-13), and Structure (A-14). 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】

8. 8. The polymer of any one of claims 1, 2, 6 and 7, comprising both repeat units of Structure (I) and (II), with the proviso that said repeat units of Structure (II) range from 1 mol % to 60 mol % of all repeat units of Structure (I) and (II).

9. 9. The polymer of claim 8, wherein said repeat unit of structure (I) has the more specific structure (Ia). 【Chemistry 16】

10. 9. The polymer of claim 8, wherein the repeat unit of structure (II) has a structure selected from more specific structure (IIa), more specific structure (IIb), more specific structure (IIc), and more specific structure (IId). 【Chemistry 17】 [Chemistry 18]

11. A method for spin-casting a polymer comprising the polymer of any one of claims 1, 2, 6 and 7 and an organic spin-casting solvent, wherein the polymer has an end group (III) and R ５ is H, or the terminal group (IV) is present and R ７ is H.

12. A method for forming a grafted coating of a polymer on a substrate, comprising the steps of: i) forming a coating of the composition of claim 11 on a substrate; ii) heating the coating at a temperature of from 90°C to 180°C to remove the solvent and form a grafted coating of the polymer; iii) heating the grafted coating of step ii) at a temperature of from 200°C to 250°C to form a fully crosslinked or fully crosslinked and grafted polymer coating; The method comprising:

13. 1. A method of forming a grafted neutral layer coating on a substrate, comprising the steps of: ia) forming a coating of the composition of claim 11 on a substrate; iia) heating the coating at a temperature of from 90°C to 180°C to remove the solvent and form a grafted coating; iiia) heating the grafted coating of step iia) at a temperature of 200°C to 250°C to form a fully grafted neutral layer coating; The method comprising:

14. 1. A method of forming a self-assembled block copolymer coating on a neutral layer coating, comprising the steps of: ij) forming a neutral layer coating according to claim 13; iij) applying a block copolymer onto the neutral layer coating and annealing until induced self-assembly of the block copolymer coating occurs; The method comprising:

15. 1. A method for graphoepitaxy-directed self-assembly of a block copolymer coating used to form an image, comprising the steps of: ik) forming a neutral layer coating according to claim 13; iik) providing a coating of a photoresist coating over said neutral layer coating and forming a pattern in the photoresist coating; iiik) applying a block copolymer comprising an etch-resistant block and a highly etchable block onto the photoresist pattern and annealing until directed self-assembly occurs; and ivk) etching the block copolymer, thereby removing highly etchable blocks of the copolymer overlying areas of a substrate and simultaneously forming a pattern in the substrate selectively in these areas; The method comprising:

16. 1. A method for chemo-epitaxy directed self-assembly of a block copolymer coating used for forming an image, comprising the steps of: il) forming a neutral layer coating on the substrate according to claim 13; iil) providing a coating of a photoresist coating over said neutral layer coating and forming a pattern in the photoresist coating, thereby forming areas of the neutral layer coating that are not covered with resist; iii) treating and removing the uncovered neutral layer coating to form a pinning region; ivl) removing the photoresist to expose the untreated neutral layer coating and form a chemo-epitaxy pattern comprising neutral and pinned regions; vl) applying a block copolymer comprising an etch-resistant block and a highly etchable block onto the neutral layer coating and annealing until directed self-assembly occurs; and vii) etching the block copolymer, thereby removing highly etchable blocks of the copolymer overlying areas of a substrate and simultaneously forming a pattern in the substrate selectively in these areas; The method comprising:

17. 10. Use of a polymer according to any one of claims 1, 2, 6 and 7 in a process for preparing a grafted or self-assembled coating on a substrate.

18. 12. Use of the composition according to claim 11 in the process of preparing a grafted or self-assembled coating on a substrate.

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