Development of novel neutral mats containing hydroxyl monomers to improve SIARC substrate compatibility for directed self-assembly of diblock copolymers

Abstract

Disclosed is a random copolymer having structure (A) comprising styrenic repeat units of structure (I), repeat units of structure (II) derived from 4-vinylbenzocyclobutene, repeat units of structure (III) derived from an alkyl acrylate or alkyl 2-methylenealkanoate, repeat units of structure (IV) derived from a hydroxy-substituted acrylate or 2-methylenealkanoate, and two end groups as shown in structure (A), one of which is H and the other of which is a methyl moiety substituted with Rr, Rrl and Rr2. Also disclosed is a composition comprising said random copolymer of structure (A) and an organic spin-casting solvent, as well as a process of using said composition in directed self-assembly processing. TIFF2025515638000026.tif51170

Description

[Technical field]

[0001] The present invention relates to a neutral layer mat composition 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, where feature critical dimensions (CD) on the order of nanoscale can be achieved. 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, the circuit dimensions and features in devices have been continually reduced. 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 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 include graphoepitaxy or chemoepitaxy guided 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), which can be transferred into the substrate via an etching process (e.g., plasma etching). In graphoepitaxy or chemoepitaxy, these guiding features can induce both pattern modification and pattern multiplication. In the case of unpatterned neutral layers, this produces repeating arrays of L / S or CH, for example. 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 on a layer of non-preferential or neutral material that is grafted or crosslinked at the polymer-substrate interface.

[0004] In the graphoepitaxy-induced self-assembly method, block copolymers self-assemble on substrates that have been pre-patterned using conventional lithography (ultraviolet, deep UV, e-beam, extreme ultraviolet (EUV) exposure sources) to form repeating topographical features such as line / space (L / S) or contact hole (CH) patterns. In one example of an L / S-induced self-assembly array, block copolymers can form self-aligned lamellar regions that can form parallel line-space patterns of different pitches in the trenches between the pre-patterned lines to enhance pattern resolution by dividing the spaces in the trenches between the 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 element 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 can include a monomer (e.g., methyl methacrylate) that is oxygen-rich, does not contain refractory elements, and can form a highly etchable block. The plasma etch gases used in the etching process that defines the self-assembled pattern are typically those used in processes used to manufacture integrated circuits (ICs). In this way, very fine patterns can be created 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 create a higher density of 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 higher density array of regions of etchable and etch-resistant domains, which when etched, gives a higher density 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, block copolymer self-assembly occurs on a surface with guide features that are regions of differing chemical affinity that have no or no significant topography on which to base the guided self-assembly process (in other words, non-guided topography). For example, the surface of a substrate can be patterned using conventional lithography (UV, deep UV, e-beam, EUV) to generate a line-and-space (L / S) pattern of surfaces of differing chemical affinity in which exposed regions, where the surface chemistry has been modified by radiation, 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 (DSA) 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 would disrupt the desired vertical alignment that can be used to achieve either pattern modification or pattern multiplication based on features generated by conventional lithography. Modification of selected small regions or pinning 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, can be hydrophobic, with a relatively large affinity for, for example, polystyrene block segments in a block copolymer of styrene and methylmethacrylate.

[0007] Directed self-assembly using PS-b-PMMA type block copolymers requires a neutral underlayer for chemoepitaxy growth of line-and-space patterns that can be functional on many different substrates. Crosslinkable terpolymers such as P(Sr-VBCB-r-MMA) (i.e., poly(styrene-co-4-vinylbenzocyclobutene-co-methylmethacrylate) have been used as crosslinkable neutral mat layer compositions in DSA processes. Although this terpolymer works effectively as a neutral layer on oxide and nitride-based substrates such as SiNyOx (silicon oxynitride) and SiN (silicon nitride), this terpolymer, due to its hydrophobic nature, causes severe de-wetting defects on SiARC (silicon antireflective coating) substrates, leading to defects in the subsequent DSA process. Therefore, there is a need to develop new crosslinkable neutral mat materials that are specifically suitable for SiARC substrates. [Brief description of the drawings]

[0008] [Figure 1] Typical NMR of P(Sr-VBCB-r-MMA-r-HEMA)-OH Example 1 [Diagram 2] Typical NMR of P(Sr-VBCB-r-MMA-r-PQMA)-OH Example 5 [Diagram 3] Defect rates of neutral layer coatings derived from P(Sr-VBCB-r-MMA-r-HEMA)-OH and P(Sr-VBCB-r-MMA-r-PQMA)-OH compared to reference materials [Figure 4] Evaluation of SEM images of neutral layer coatings on SiARCs [Diagram 5] Comparison of defects in self-assembled structures Examples 1 and 5 compared to Comparative Example 1 on ISX-302 [Figure 6] Evaluation of SEM images of self-assembled structures [Figure 7] Comparison of defects in self-assembled structures Examples 1 and 5 compared to Comparative Example 1 on ISX-304 [Prior art documents] [Patent documents]

[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 specific aspect of the present invention is an improved type of crosslinkable neutral tetrapolymers and pentapolymers that are compatible with SiARCs and SiOx, SiNyOx and SiN substrates. In one aspect, the novel tetrapolymers consist of styrene (S), 4-vinylbenzocyclobutene (VBCB), methyl methacrylate (MMA), and either 2-hydroxyethyl methacrylate (HEMA) or 4-hydroxyphenyl methacrylate (PQMA), initiated with either 4,4'-azobis(4-cyanopentanol) (AIBN-OH) or 4,4'-azobis(4-cyanovaleric acid) (AIBN-COOH). The S and MMA components provide the necessary neutrality to the polymer. The VBCB component allows the polymer to crosslink into an insoluble film when baked. The HEMA or PQMA component makes the polymer more compatible with SiARC substrates. The hydroxyl- or carboxylic acid-terminated end groups from the initiator graft the polymer onto the substrate and hold the polymer together when a high temperature bake crosslinks the polymer.

[0011] In a broader aspect, the present invention provides a random polymer having structure (A): Styrenic repeating units of structure (I), provided that R m1 is H or C1-C4 alkyl, R 1 is selected from H, C1-C8 alkyl, and C1-C4 alkyloxy, and n1 is the total number of said repeat units, and said repeat units range from about 10 mol % to about 60 mol % in said copolymer; A repeating unit of structure (II) derived from 4-vinylbenzocyclobutene, where R m2 is H or C1-C4 alkyl, R 2 is H or C1-C8 alkyl, and n2 is the total number of said repeat units; and said repeat units are from about 15 mol % to about 35 mol % in said copolymer; Repeating units of structure (III) derived from alkyl acrylate or alkyl 2-methylene alkanoate, where R m3 is H or C1-C4 alkyl, R 3 is a C1-C8 alkyl, and n3 is the total number of such repeat units, and such repeat units are present in the copolymer in an amount from about 15 mol % to about 55 mol %; from about 1 mol % to greater than 5 mol % of repeat units of structure (IV) derived from a hydroxy-substituted acrylate or 2-methylenealkanoate, where R m4 is H or C1-C4 alkyl, R I is C1-C8 alkyl, L 1is a spacer moiety selected from a C2-C12 alkylene spacer and a 1,4-phenylene spacer, wherein the alkylene spacer is selected from the group consisting of C2-C12 linear alkylene, C3-C12 branched alkylene, C3-C12 cyclic alkylene, and C5-C12 alicyclic alkylene, and there are at least two carbon atoms between the carbonyloxy moiety and the OH moiety, and these two moieties are individually attached to the alkylene spacer at different positions that are either primary or secondary carbons on the alkylene moiety, and the 1,4-phenylene spacer is one in which the carboxyloxy moiety and the OH moiety are in the 1,4 position relative to each other, and n4 is the total number of such repeat units; One is H and the other is Rr, Rr 1 and Rr 2 The two terminal groups shown in structure (A) are methyl moieties substituted with Rr 1 is C1-C8 alkyl, Rr 2 is a C1-C8 alkyl, a C1-C8 alkylene hydroxyl moiety (-alkylene-OH), a C1-C8 alkylene carboxylic acid moiety (-alkylene-CO 2 H), or a benzylic alcohol containing moiety of structure (B), where ni is an integer from 0 to 5, nia is an integer from 1 to 5, nib is an integer from 1 to 5, and "*" represents the point of attachment of the moiety, Rr is a cyano moiety (-CN) or a carbonylalkyl moiety (-C(=O)-Ri), where Ri is a C1-C8 alkyl or aryl moiety; Including, the sum of the individual mole percent of repeat units of structures (I), (II), (III) and (IV) is less than or equal to 100 mole percent of the total repeat units present in said copolymer; The random polymer is described.

[0012] [ka] Another aspect of the invention is a composition comprising one of these polymers and an organic spin-coat solvent.

[0013] Another aspect of the invention is a method of coating these compositions and thermally generating a crosslinked, neutral MAT layer and using this layer in lithographic DSA processing. In the context of this invention, a MAT layer is a crosslinked layer that is insoluble in any layer coated thereon and can be used as a DSA neutral or pinning layer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] 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 the term "comprises" as well as other verb forms such as "comprises" is not limiting. Also, the use of terms such as "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 aforementioned elements, including the use of a single element.

[0015] The term "C1-C4 alkyl" includes methyl and C2-C4 linear alkyl and C3-C4 branched alkyl moieties, such as methyl (-CH 3 ), ethyl (-CH 2 -CH 3 ), n-propyl (-CH 2 -CH 2 -CH 3), isopropyl (-CH(CH 3 ) 2 ), n-Butyl (-CH 2 -CH 2 -CH 2 -CH 3 ), tert-Butyl (-C(CH 3 ) 3 ), isobutyl (CH 2 -CH(CH 3 ) 2 , 2-Butyl (-CH(CH 3 )CH 2 -CH 3 Similarly, reference to C1-C12 includes methyl, C2-C12 linear, C3-C12 branched alkyl, C4-C12 cycloalkyl (e.g., cyclopentyl, cyclohexyl, etc.) or C5-C12 alkylenecycloalkyl (e.g., —CH 2 -Cyclohexyl, CH 2 -CH 2 -cyclopentyl, etc.

[0016] The term "C2-C12 alkylene" includes C2-C12 linear alkylene moieties (e.g., ethylene, propylene, etc.), C2-C12 branched alkylene moieties (e.g., -CH(CH 3 )-, -CH(CH 3 )-CH 2 -, etc.), C5 to C12 cyclic alkylene moieties (e.g., 1,4-cyclohexyl, 1,3-cyclopentyl, etc.), and C5 to C12 alicyclics (e.g., 2,6 adamantane-2,4-di-yl, adamantane-2,6-di-yl).

[0017] Diblock and triblock copolymers of styrenic repeat units and repeat units derived from alkyl 2-methylene alkanoates, useful as components in the compositions of the invention described herein, can be prepared by a variety of methods, such as 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, p 315 (Non-Patent Document 3); Encyclopedia of Polymer Science and Technology, 2014, Vol 7, p 625 (Non-Patent Document 4)).

[0018] 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 designate the building blocks of a random block copolymer, specifically, oligo(S-co-p-OS)-bP(MMA-co-DEGMEMA) (S=styrene, p-OS=para-octylstyrene, MMA=methyl methacrylate, DEGMEMA=di(ethylene glycol) methyl ether methacrylate) to designate the repeating units in this block copolymer where both blocks are random copolymers.

[0019] 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.

[0020] PGMEA and PGME are abbreviations for 1-methoxypropan-2-yl acetate and 1-methoxypropan-2-ol, respectively.

[0021] 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.

[0022] Unless otherwise indicated, "alkyl" refers to a hydrocarbon group that can be linear, branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, and similar groups), or cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, and similar groups), polycyclic (e.g., norbornyl, adamantyl, and similar groups). These alkyl moieties may be substituted or unsubstituted as described below. The term "alkyl" refers to such moieties, for example, having C1-C8 carbons. For structural reasons, it is understood that linear alkyls start at C1, while branched alkyls start at C3, and polycyclic alkyls start at C5. Furthermore, it is understood that moieties derived from alkyls described below, such as alkyloxy and perfluoroalkyl, have the same carbon number range, unless otherwise stated. If the length of an alkyl group is specified differently than set forth above, the above definition of alkyl is still valid 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.

[0023] 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, etc.) which may be substituted or unsubstituted as described below.

[0024] Halo or halide refers to a halogen, F, Cl, Br, or I, attached to an organic moiety by one bond.

[0025] As used herein, the term lactone includes both monolactones (eg, caprolactone) and dilactones (eg, lactide).

[0026] Haloalkyl refers to a linear, cyclic or branched saturated alkyl group as defined above in which at least one of the hydrogens is replaced by a halide selected from F, Cl, Br, I, or mixtures thereof when more than one halo moiety is present. Fluoroalkyl is a specific subgroup of these moieties.

[0027] Perfluoroalkyl refers to a linear, cyclic or branched saturated alkyl group as defined above in which all of the hydrogens have been replaced by fluorine (eg, trifluoromethyl, perfluoroethyl, perfluoroisopropyl, perfluorocyclohexyl, etc.).

[0028] Copolymer of structure (A) The present invention describes a random copolymer having the structure (A), Styrenic repeating units of structure (I), provided that R m1 is H or C1-C4 alkyl, R 1 is selected from H, C1-C8 alkyl, and C1-C4 alkyloxy, and n1 is the total number of said repeat units, and said repeat units range from about 10 mol % to about 60 mol % in said copolymer; A repeating unit of structure (II) derived from 4-vinylbenzocyclobutene, where R m2 is H or C1-C4 alkyl, R 2 is H or C1-C8 alkyl, and n2 is the total number of said repeat units, and said repeat units are from about 15 mol % to about 35 mol % in said copolymer; Repeating units of structure (III) derived from alkyl acrylate or alkyl 2-methylene alkanoate, where R m3 is H or C1-C4 alkyl, R 3 is a C1-C8 alkyl, and n3 is the total number of such repeat units, and such repeat units are present in the copolymer in an amount from about 15 mol % to about 55 mol %; A repeating unit of structure (IV) derived from a hydroxy-substituted acrylate or 2-methylene alkanoate, where n4 is the total number of repeating units, and R m4 is H or C1-C4 alkyl, R I is C1-C8 alkyl, L 1 is a spacer moiety selected from a C2-C12 alkylene spacer and a 1,4-phenylene spacer, wherein the alkylene spacer is selected from the group consisting of C2-C12 linear alkylene, C3-C12 branched alkylene, C3-C12 cyclic alkylene, and C5-C12 alicyclic alkylene, and there are at least two carbon atoms between the carbonyloxy moiety and the OH moiety, and these two moieties are individually bonded to the alkylene spacer at different positions that are either primary or secondary carbons on the alkylene moiety, and the 1,4-phenylene spacer is one in which the carboxyloxy moiety and the OH moiety are in the 1,4 position relative to each other; and this repeat unit is from about 1 mol % to about 5 mol %; One is H and the other is Rr, Rr 1 and Rr 2 The two terminal groups shown in structure (A) are methyl moieties substituted with Rr 1 is C1-C8 alkyl, Rr 2 is a C1-C8 alkyl, a C1-C8 alkylene hydroxyl moiety (-alkylene-OH), a C1-C8 alkylene carboxylic acid moiety (-alkylene-CO 2 H), or a benzylic alcohol containing moiety of structure (B), where ni is an integer from 0 to 5, nia is an integer from 1 to 5, nib is an integer from 1 to 5, and "*" represents the point of attachment of the moiety, Rr is a cyano moiety (-CN) or a carbonylalkyl moiety (-C(=O)-Ri), where Ri is a C1-C8 alkyl or aryl moiety; Including, The sum of the individual mole percent of repeat units of structures (I), (II), (III) and (IV) is less than or equal to 100 mole percent of all repeat units present in said copolymer.

[0029] [ka] In one aspect of the copolymer of structure (A) described herein, it is a copolymer whose repeat units consist of repeat units of structures (I), (II), (III) and (IV), the sum of which repeat units equals 100 mole % of the repeat units in the copolymer.

[0030] In another aspect of the copolymer of structure (A) described herein, L 1 is the C2 to C12 alkylene spacer.

[0031] In another aspect of the copolymer of structure (A) described herein, L 1 is a 1,4-phenylene moiety spacer.

[0032] L 1 In one aspect of the copolymer of Structure (A) described herein, wherein is the C2-C12 alkylene spacer, it has a composition of from about 13 mol % to about 48 mol % repeat units of Structure (I), from about 25 mol % to about 35 mol % repeat units of Structure (II), from about 15 mol % to about 55 mol % repeat units of Structure (III), from about 1 mol % to about 2 mol % repeat units of Structure (IV), and the sum of the individual mol % of repeat units of Structures (I), (II), (III) and (IV) equals 100 mol % of all repeat units in the copolymer.

[0033] In one aspect of the copolymer of Structure (A) described herein, in the repeat unit of Structure (IV), L 1is the alkylene spacer, the repeat unit being selected from those having any of Structure (IVa1), Structure (IVa2), Structure (IVa3), Structure (IVa4) or Structure (IVa5), wherein x is an integer from 1 to 11, x1 is an integer from 1 to 8, x2 is an integer from 1 to 8, x3 is an integer from 1 to 2, and x3a is an integer from 1 to 3; R x1 is C1-C4 alkyl, R x2 is C1-C4 alkyl, and in the repeat unit of structure (IVa5), the substituent R x4 or R x5 is OH, and further, the remaining other substituents in the repeat unit of structure (IVa5) are H. In another aspect of this embodiment, the repeat unit of structure (IV) has structure (IVa1). In another aspect of this embodiment, the repeat unit of structure (IV) has structure (IVa2). In another aspect of this embodiment, the repeat unit of structure (IV) has structure (IVa3). In another aspect of this embodiment, the repeat unit of structure (IV) has structure (IVa4). In another aspect of this embodiment, the repeat unit of structure (IV) has structure (IVa5). In another aspect of this embodiment, the repeat unit of structure (IV) has structure (IVa41). In another aspect of this embodiment, it has more specifically structure (IVa41). In another aspect of this embodiment, it has structure (IVa42). In another aspect of this embodiment, it has structure (IVa43). In another aspect of this embodiment, it has structure (IVa51). In another aspect of this embodiment, it has the structure (IVa52).

[0034] [ka] In one aspect of the repeat unit of structure (IVa1) depicted above, x is an integer from 2 to 11; in another aspect, x is an integer from 3 to 11; in another aspect, x is an integer from 4 to 11; in another aspect, x is an integer from 5 to 11; in another aspect, x is an integer from 6 to 11; in another aspect, x is an integer from 7 to 11; in another aspect, x is an integer from 8 to 11; in another aspect, x is an integer from 9 to 11; in another aspect, x is an integer from 10 to 11; in another aspect, x is 11; in another aspect, x is 10; in another aspect, x is 9; in another aspect, x is 8; in another aspect, x is 7; in another aspect, x is 6; in another aspect, x is 5; in another aspect, x is 4; in another aspect, x is 3; in another aspect, x is 2. In another aspect of these embodiments, R m4 is methyl.

[0035] In one aspect of the copolymer of structure (A) described herein, L 1 is a 1,4-phenylene spacer, the repeat units of structure (I) are from about 23 mol % to about 48 mol %, the repeat units of structure (II) are from about 25 mol % to about 35 mol %, the repeat units of structure (III) are from about 15 mol % to about 45 mol %, the repeat units of structure (IV) are from about 2 to about 5 mol %, and the sum of the individual mol % of repeat units of structures (I), (II), (III) and (IV) equals 100 mol % of all repeat units in said copolymer.

[0036] In one aspect of the copolymer of structure (A) described herein, L 1 is a C2-C12 alkylene spacer, and the repeating unit of structure (IV) has structure (IVa).

[0037] In one aspect of the copolymer of structure (A) described herein, L 1is a 1,4-phenylene spacer, and the repeat unit of structure (IV) has structure (IVb).

[0038] In one aspect of the copolymer of structure (A) described herein, R m1 and R m2 is H.

[0039] In one aspect of this embodiment of the copolymer of structure (A) described herein, R m3 is H.

[0040] In one aspect of this embodiment of the copolymer of structure (A) described herein, R m4 is H.

[0041] In one aspect of this embodiment of the copolymer of structure (A) described herein, R m3 is C1-C4 alkyl. In one particular aspect of this embodiment, R m3 is methyl.

[0042] In one aspect of this embodiment of the copolymer of structure (A) described herein, R m4 is C1-C4 alkyl. In one particular aspect of this embodiment, R m4 is methyl.

[0043] In one aspect of this embodiment of the copolymer of structure (A) described herein, R 1 is C1-C4 alkyl.

[0044] In one aspect of this embodiment of the copolymer of structure (A) described herein, R 1 is H.

[0045] In one aspect of this embodiment of the copolymer of Structure (A) described herein, the repeat unit of Structure (I) has Structure (Ia).

[0046] In one aspect of this embodiment of the copolymer of structure (A) described herein, R 2 is C1-C4 alkyl.

[0047] In one aspect of this embodiment of the copolymer of structure (A) described herein, R 2 is H. In one aspect of this embodiment, the repeat unit of structure (II) has structure (IIa).

[0048] In one aspect of this embodiment of the copolymer of structure (A) described herein, R 3 is C1-C4 alkyl.

[0049] In one aspect of this embodiment of the copolymer of structure (A) described herein, R 3 is methyl. In another aspect of this embodiment, the repeat unit of structure (III) has structure (IIIa).

[0050] In one aspect of this embodiment of the copolymer of structure (A) described herein, the repeat unit of structure (IV) has structure (IVc).

[0051] In one aspect of this embodiment of the copolymer of structure (A) described herein, the repeat unit of structure (IV) has structure (IVd).

[0052] [ka] In one aspect of this embodiment of the copolymer of structure (A) described herein, it has structure (A-1). In one aspect of this embodiment, Rr 1 In another aspect of this embodiment, Rr 2 is C1-C8 alkyl. In another aspect of this embodiment, Rr 2 is a C1-C8 alkylene hydroxy moiety. In another aspect of this embodiment, Rr 2 is a C1-C8 alkylene carboxylic acid. In another aspect of this embodiment, Rr 2is the benzylic alcohol-containing moiety of structure (B); in another aspect of this embodiment, it has the more specific structure (B-1). In one aspect of this embodiment, R is a cyano moiety (-CN). In another aspect of this embodiment, R is a carbonyl alkyl moiety (-C(=O)-Ri), where Ri is a C1-C8 alkyl or aryl moiety.

[0053] [ka] In one aspect of this embodiment of the copolymer of structure (A) described herein, it has structure (A-2). In one aspect of this embodiment, Rr 1 In another aspect of this embodiment, Rr 2 is C1-C8 alkyl. In another aspect of this embodiment, Rr 2 is a C1-C8 alkylene hydroxy moiety. In another aspect of this embodiment, Rr 2 In another aspect of this embodiment, Rr 2 is the benzylic alcohol-containing moiety of structure (B); in another aspect of this embodiment, it has the more specific structure (B-1). In one aspect of this embodiment, R is a cyano moiety (-CN). In another aspect of this embodiment, R is a carbonyl alkyl moiety (-C(=O)-Ri), where Ri is a C1-C8 alkyl or aryl moiety.

[0054] [ka] Another aspect of the present invention is a composition comprising any one of the copolymers of the present invention having structure (A) according to the embodiments described herein and an organic spin-casting solvent.

[0055] Another aspect of the invention is a copolymer comprising any one of the copolymers of the invention having the structure (A) and an organic spin-on casting solvent, L 1 is a C2-C12 alkylene spacer.

[0056] Another aspect of the invention is a method for producing a spin-cast copolymer comprising any one of the copolymers of the invention having the structure (A) and an organic spin-cast solvent, L 1 is a C2-C12 alkylene spacer, and Rr 2 is C1 to C8 alkyl.

[0057] One aspect of the invention is a method for preparing a spin-cast copolymer comprising any one of the copolymers of the invention having the structure (A) and an organic spin-cast solvent, L 1 is a C2-C12 alkylene spacer, and Rr 2 is either a C1-C8 alkylene hydroxy moiety, a C1-C8 alkylene carboxylic acid, or a benzylic alcohol containing moiety of structure (B).

[0058] Another aspect of the invention is a method for producing a spin-cast copolymer comprising any one of the copolymers of the invention having the structure (A) and an organic spin-cast solvent, L 1 is a 1,4-phenylene spacer.

[0059] Another aspect of the invention is a method for producing a spin-cast copolymer comprising any one of the copolymers of the invention having the structure (A) and an organic spin-cast solvent, L 1 is a 1,4-phenylene spacer, and Rr 2 is C1 to C8 alkyl.

[0060] Another aspect of the invention is a method for producing a spin-cast copolymer comprising any one of the copolymers of the invention having the structure (A) and an organic spin-cast solvent, L 1 is a 1,4-phenylene spacer, and Rr 2 is either a C1-C8 alkylene hydroxy moiety, a C1-C8 alkylene carboxylic acid, or a benzylic alcohol-containing moiety of structure (B).

[0061] Spin-casting solvents for compositions containing the copolymers of the present invention Suitable solvents for use as organic spin-casting solvents are any solvents capable of dissolving the compounds of the present invention that are used to spin-cast materials such as photoresists, bottom anti-reflective coatings or other types of organic coatings for lithographic processing of semiconductor materials.Non-limiting examples. In another aspect of the novel composition, the organic spin-casting solvent is capable of dissolving the compounds of the present invention. 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 hydroxycabonates. Examples of suitable solvents include carboxylates such as methyl lactate, ethyl lactate (EL), ethyl glycolate, and ethyl 3-hydroxypropionate; ketone esters such as methyl pyruvate or ethyl pyruvate; alkyloxy carboxylates 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. In one aspect of this embodiment, the solvent may be PGMEA and mixtures of PGMEA and PGME. In one aspect of this embodiment, the solvent is PGMEA.

[0062] Methods of Using the Compositions of the Invention Another aspect of the invention is a method for forming a crosslinked coating of a copolymer, or a grafted and crosslinked coating of a copolymer, comprising the steps of: i) forming a coating on a substrate using any one of the compositions described herein comprising a copolymer of structure (A); ii) heating the coating at a temperature of from about 90° C. to about 180° C. to remove the solvent and form a crosslinked or grafted and crosslinked coating of the copolymer; iii) heating the crosslinked or grafted and crosslinked coating of step ii) to about 200° C. to about 250° C. to form a fully crosslinked or fully crosslinked and grafted copolymer coating; The method includes:

[0063] Another aspect of the present invention is a method for forming a crosslinked neutral coating or a grafted and crosslinked neutral coating on a substrate, comprising the steps of: ia) forming a coating on a substrate using any one of the compositions described herein comprising a copolymer of structure (A); iia) heating the coating at a temperature of from about 90° C. to about 180° C. to remove the solvent and form a crosslinked or grafted and crosslinked coating; iiia) heating the crosslinked coating of step iid) at a temperature of about 200° C. to about 250° C. to form a fully crosslinked or fully crosslinked and grafted neutral coating; The method comprises:

[0064] Another aspect of the present invention is a method for forming a crosslinked neutral coating on a substrate, comprising the steps of: ib) a copolymer of structure (A) and an organic spin-casting solvent, 2 forming a coating of any one of the compositions described herein onto a substrate, wherein iib) heating the coating at a temperature of from about 90° C. to about 180° C. to remove the solvent and form a crosslinked or grafted and crosslinked coating; iiib) heating the crosslinked or grafted and crosslinked coating of step iif) at a temperature of about 200° C. to about 250° C. to form a fully crosslinked neutral coating; The method comprises:

[0065] Another aspect of the present invention is a method for forming a grafted and crosslinked neutral coating on a substrate, comprising the steps of: ic) a copolymer of structure (A) and an organic spin-casting solvent, 2 is either a C1-C8 alkylene hydroxy moiety, a C1-C8 alkylene carboxylic acid, or a benzylic alcohol containing moiety of structure (B); iic) heating the coating at a temperature of from about 90° C. to about 180° C. to remove the solvent and form a grafted and crosslinked coating; iiic) heating the crosslinked coating of step iic) at a temperature of about 200° C. to about 250° C. to form a fully grafted and crosslinked neutral coating; The method comprises:

[0066] Another aspect of the present invention is a method for forming a self-assembled block copolymer coating on a neutral coating, comprising the steps of: id) forming a neutral coating using any one of the methods described herein using a composition comprising any one of the copolymers of structure (A); iid) applying a block copolymer onto the neutral coating and annealing until induced self-assembly of the block copolymer occurs; The method comprises:

[0067] Another aspect of the invention is a method for graphoepitaxy-directed self-assembly of a block copolymer coating used to form an image, comprising the steps of: ie) forming a neutral coating using any one of the methods described herein using a composition comprising any one of the copolymers of structure (A); iie) providing a coating of a photoresist coating over said neutral coating and forming a pattern in said photoresist coating; iiie) 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 ive) etching the block copolymer to remove highly etchable blocks of the copolymer covering some areas of the substrate and at the same time selectively forming a pattern in the substrate in these areas; The method comprises:

[0068] In another aspect of the method comprising steps ie) to ive), a pattern in the photoresist coating is formed by imaging lithography selected from the group consisting of e-beam, broadband, 193 nm immersion, 193 nm dry, 13.5 nm, 248 nm, 365 nm, and 436 nm lithography.

[0069] 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: if) forming a neutral coating using any one of the methods described herein using a composition comprising any one of the copolymers of structure (A); iif) providing a coating of a photoresist coating over said neutral coating and forming a pattern in said photoresist coating, thereby forming areas of the neutral coating not covered by said resist; iiif) treating said uncovered neutral coating to remove it and form a pinning region; ivf) removing the photoresist to expose the untreated neutral coating and form a chemo-epitaxy pattern including neutral and pinned regions; vf) applying a block copolymer comprising an etch-resistant block and a highly etchable block onto the neutral coating and annealing until induced self-assembly occurs; and vif) etching said block copolymer to remove highly etchable blocks of copolymer covering some areas of the substrate and at the same time selectively forming a pattern in the substrate in these areas; The method comprises:

[0070] In another aspect of the method including steps if) through vif), the pattern in the photoresist coating is formed by imaging lithography selected from the group consisting of e-beam, broadband, 193 nm immersion, 193 nm dry, 13.5 nm, 248 nm, 365 nm, and 436 nm lithography.

[0071] Another aspect of the present invention is the use of a random polymer having structure (A) as described herein, or a composition comprising said random copolymer having structure (A) as described herein, to form a coating on a substrate. EXAMPLES

[0072] Chemicals and characterization equipment Unless otherwise indicated, chemicals were obtained from Millipore-Sigma Corporation (St. Louis, Mo.).

[0073] The SiARCs used in these examples were JSR SiARCs ISX-302 and JSR SiARCs ISX-302 ISX-304, commercially available from JSR Micro Inc., 1280 N Matilda Blvd., Sunnyvale, Calif. 94089.

[0074] 1 H NMR spectra were recorded using a Bruker Advance III 400HMz spectrometer (solvents such as CDCl 3 was used).

[0075] 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 either 5 FOV magnification or 100 FOV magnification (field of view (FOV) = 5 μm with 1, 2, 4 and 10 FOV).

[0076] Unless otherwise specified, molecular weight determination (also known as M n Polydispersity) was measured using THF solvent at 100 Å, 500 Å, and 10 3 Å, 10 5 Å and 10 6 The gel permeation chromatography was performed using a 100 Å, 500 Å, 10 μ-Ultrastyragel column. Polystyrene polymer standards were used for calibration. GPC was performed at 100 Å, 500 Å, 10 3 Å, 10 5 Å and 10 6 The first P(SDPE) block had an M of 45,048 g / mol, measured using an Agilent gel permeation chromatography system equipped with an Åμ-Ultrastyragel column, relative to a PS calibration standard. n (GPC) and M of 1.04 w / M n Gel Permeation Chromatography: 1 mg / mL in THF solution was injected using 0.1 μL into a polystyrene calibrated GPC tool with 1 mL / min THF flow.

[0077] Synthesis of test polymer materials Reference block copolymer synthesis example 1 Synthesis of P(Sb-MMA)(62k-b-25k) P(Sb-MMA) (62K-b-25K) was synthesized using the same procedure as in Example 2. The amount of initiator and the amount of monomer were varied to achieve the desired Mn and composition of the PS and PMMA blocks. Briefly, 20 g (192 mmol) of styrene was polymerized with 4.38 mL (1.4 M solution) of sec-butyllithium. Then, 0.07 g (0.38 mmol) of 1,1'-diphenylethylene (DPE) in 2.5 ml of anhydrous toluene was added to the reactor via an ampoule. 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-added carbanion. After stirring for 2 min, a small amount (2 mL) of the reaction mixture was removed for PS block molecular weight analysis. Then, methyl methacrylate (8.10 g, 81 mmol) was added via an ampoule. The reaction was stopped 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 at 55° C. under vacuum for 12 h. 26.5 g of P(Sb-MMA) consisting of 70.1 mol % polystyrene blocks and 29.9 mol % polymethyl methacrylate blocks was obtained (94% yield). The diblock copolymer molecular weight obtained from GPC is Mn, PS-b-PMMA=86,518 g / mol and Mw / Mn=1.01.

[0078] Reference block copolymer solution (Ref SOL 1) Reference Block Copolymer Synthesis Example 1 was dissolved in PGMEA to give a 1.7 wt % solution and filtered through a 0.2 micron PTFE filter. This solution was used in the neutrality experiments conducted to evaluate both the inventive neutral layer and the inventive non-polar pinned layer, as described below.

[0079] Summary of neutral layer experiment results according to the present invention Here are specific examples of the disclosed crosslinkable neutral tetrapolymers that have been found to be compatible with SiARCs as well as SiOx, SiNyOx, and SiN substrates. These novel tetrapolymers, consisting of styrene (S), 4-vinylbenzocyclobutene (VBCB), methyl methacrylate (MMA), and either 2-hydroxyethyl methacrylate (HEMA) or 4-hydroxyphenyl methacrylate (PQMA), initiated with either 2,2'-azobis(2-methylpropionitrile) (AIBN), 4,4'-azobis(4-cyanopentanol) (AIBN-OH), or 4,4'-azobis(4-cyanovaleric acid) (AIBN-COOH), were prepared to address both the defectivity and the challenges found in neutral layers formed from terpolymers. Improvements in the composition of NLD-175 to P(Sr-VBCB-r-MMA-r-HEMA)-OH [i.e., hydroxyl-terminated poly(styrene-co-4-vinylbenzo-b-cyclobutene-co-methylmethacrylate-co-2-hydroxyethylmethacrylate)] and P(Sr-VBCB-r-MMA-r-PQMA)-OH [i.e., hydroxyl-terminated poly(styrene-co-4-vinylbenzo-b-cyclobutene-co-methylmethacrylate-co-4-hydroxyphenylmethacrylate)] gave crosslinkable neutral mats with fewer coating defects. The S component gives the polymer the necessary hydrophobicity. The VBCB hydrophobic component allows the polymer to crosslink and produce an insoluble film when baked. The MMA component gives the polymer the necessary hydrophilicity for neutrality. The current results show that %HEMA or %PQMA consisting of 1-5% give good compatibility with SiARC. The HEMA and PQMA components make the polymer more hydrophilic and compatible with SiARC. The hydroxyl or carboxylic acid terminated end groups from the free radical initiators help the polymer chains to graft onto the substrate when the VBCB crosslinks upon heating. These groups contribute to the overall hydrophilicity of the polymer and may disrupt the neutrality of the film for diblock copolymers.

[0080] First, the crosslinked film was examined for film retention using a dip test and neutrality using a fingerprint test. The novel tetrapolymer-based solution was spin-coated and baked on the wafer. The freshly formed film was immersed in EBR solvent and then rinsed. Film thickness measurements before and after the dip test determine film retention. Diblock copolymer Comparative Example 1 was coated from solution on BCP (PME-979) and annealed on the novel tetrapolymer-based film to verify neutrality for fingerprint appearance. This non-preference for either block of the diblock copolymer allows for self-assembly of BCP into contact holes. The coating was then analyzed for defects using an in-house SEM, which showed an improved coating with minor defects.

[0081] Example 1: Synthesis of poly(styrene-co-4-vinylbenzocyclobutene-co-methyl methacrylate-co-2-hydroxyethyl methacrylate)-hydroxyl terminated (feed ratio 48 / 35 / 15 / 2) Styrene (22.62 g, 217 mmol), 4-vinylbenzocyclobutene (8.84 g, 67.9 mmol), methyl methacrylate (15.86 g, 15.8 mmol), 2-hydroxyethyl methacrylate (1.18 g, 0.91 mmol), 4,4'-azobis(4-cyanopentanol) (1.50 g, 5.96 mmol), and 2-butanone (75 g) were added to a flask and mixed under nitrogen for 30 minutes. The mixture was heated in an 85°C oil bath for 16 hours. The mixture was cooled to room temperature and diluted with THF and precipitated in IPA. The polymer was collected and redissolved in THF to a 15% solids solution and precipitated in IPA. The polymer was collected and dried in a vacuum oven. The polymer was dissolved as a 10% solids solution in EtOAc, washed four times with DI water, and precipitated in IPA. The polymer was collected by vacuum filtration, pulled dry under air, and dried overnight in a vacuum oven at 70° C. 24.1 g (50.0%) white powder, GPC: 11,241 g / mol Mn, 23,167 g / mol Mw, 2.06 PDI.

[0082] Example 2: Synthesis of poly(styrene-co-4-vinylbenzocyclobutene-co-methyl methacrylate-co-2-hydroxyethyl methacrylate)-hydroxyl terminated (feed ratio 33 / 30 / 35 / 2) Styrene (30.64 g, 294 mmol), 4-vinylbenzocyclobutene (34.82 g, 267 mmol), methyl methacrylate (31.24 g, 312 mmol), 2-hydroxyethyl methacrylate (2.32 g, 17.8 mmol), 4,4'-azobis(4-cyanopentanol) (0.99 g, 3.92 mmol), and 2-butanone (150 g) were added to the flask and mixed under nitrogen for 30 minutes. The mixture was heated in an 85°C oil bath for 16 hours. The mixture was cooled to room temperature and diluted with THF and precipitated in IPA. The polymer was collected and redissolved in THF to a 15% solids solution and precipitated in IPA. The polymer was collected and dried in a vacuum oven. The polymer was dissolved as a 10% solids solution in EtOAc, washed four times with DI water, and precipitated in IPA. The polymer was collected by vacuum filtration, pulled dry under air, and dried overnight in a vacuum oven at 70° C. 44.4 g (44.6%) white powder, GPC: 20,225 g / mol Mn, 46,045 g / mol Mw, 2.28 PDI.

[0083] Example 3: Synthesis of poly(styrene-co-4-vinylbenzocyclobutene-co-methyl methacrylate-co-2-hydroxyethyl methacrylate)-hydroxyl terminated (feed ratio 28 / 25 / 45 / 2) Styrene (26.40 g, 254 mmol), 4-vinylbenzocyclobutene (29.47 g, 226 mmol), methyl methacrylate (40.79 g, 407 mmol), 2-hydroxyethyl methacrylate (2.36 g, 18.1 mmol), 4,4'-azobis(4-cyanopentanol) (0.99 g, 3.92 mmol), and 2-butanone (150 g) were added to the flask and mixed under nitrogen for 30 minutes. The mixture was heated in an 85°C oil bath for 16 hours. The mixture was cooled to room temperature and diluted with THF and precipitated in IPA. The polymer was collected and redissolved in THF to a 15% solids solution and precipitated in IPA. The polymer was collected and dried in a vacuum oven. The polymer was dissolved as a 10% solids solution in EtOAc, washed four times with DI water, and precipitated in IPA. The polymer was collected by vacuum filtration, pulled dry under air, and dried overnight in a vacuum oven at 70° C. 47.3 g (47.5%) white powder, GPC: 21,644 g / mol Mn, 46,731 g / mol Mw, 2.16 PDI.

[0084] Example 4: Synthesis of poly(styrene-co-4-vinylbenzocyclobutene-co-methyl methacrylate-co-2-hydroxyethyl methacrylate)-hydroxyl terminated (feed ratio 13 / 30 / 55 / 2) Styrene (6.07 g, 58.3 mmol), 4-vinylbenzocyclobutene (17.52 g, 135 mmol), methyl methacrylate (24.70 g, 247 mmol), 2-hydroxyethyl methacrylate (1.17 g, 0.90 mmol), 4,4'-azobis(4-cyanopentanol) (0.54 g, 2.16 mmol), and 2-butanone (75 g) were added to the flask and mixed under nitrogen for 30 minutes. The mixture was heated in an 85°C oil bath for 16 hours. The mixture was cooled to room temperature and diluted with THF and precipitated in IPA. The polymer was collected and redissolved in THF to a 15% solids solution and precipitated in IPA. The polymer was collected and dried in a vacuum oven. The polymer was dissolved as a 10% solids solution in EtOAc, washed four times with DI water, and precipitated in IPA. The polymer was collected by vacuum filtration, pulled dry under air, and dried overnight in a vacuum oven at 70° C. 24.3 g (48.8%) white powder, GPC: 26,761 g / mol Mn, 43,866 g / mol Mw, 1.64 PDI.

[0085] Example 5: Synthesis of poly(styrene-co-4-vinylbenzocyclobutene-co-methyl methacrylate-co-4-hydroxyphenyl methacrylate) - hydroxyl-terminated (feed ratio 48 / 35 / 15 / 2) Styrene (43.37 g, 416 mmol), 4-vinylbenzocyclobutene (39.53 g, 304 mmol), methyl methacrylate (13.03 g, 130 mmol), 4-hydroxyphenyl methacrylate (3.09 g, 17.3 mmol), 4,4'-azobis(4-cyanopentanol) (0.99 g, 3.92 mmol), and 2-butanone (150 g) were added to the flask and mixed under nitrogen for 30 minutes. The mixture was heated in an 85°C oil bath for 16 hours. The mixture was cooled to room temperature and diluted with THF and precipitated in IPA. The polymer was collected and redissolved in THF to a 15% solids solution and precipitated in IPA. The polymer was collected and dried in a vacuum oven. The polymer was dissolved as a 10% solids solution in EtOAc, washed four times with DI water, and precipitated in IPA. The polymer was collected by vacuum filtration, pulled dry under air, and dried overnight in a vacuum oven at 70° C. 38.4 g (38.6%) white powder, GPC: 22,482 g / mol Mn, 40,376 g / mol Mw, 1.80 PDI.

[0086] Example 6: Synthesis of poly(styrene-co-4-vinylbenzocyclobutene-co-methyl methacrylate-co-4-hydroxyphenyl methacrylate) - hydroxyl-terminated (feed ratio 33 / 30 / 35 / 2) Styrene (30.22 g, 290 mmol), 4-vinylbenzocyclobutene (34.35 g, 264 mmol), methyl methacrylate (30.82 g, 308 mmol), 4-hydroxyphenyl methacrylate (3.13 g, 17.6 mmol), 4,4'-azobis(4-cyanopentanol) (1.48 g, 5.86 mmol), and 2-butanone (150 g) were added to the flask and mixed under nitrogen for 30 minutes. The mixture was heated in an 85°C oil bath for 16 hours. The mixture was cooled to room temperature and diluted with THF and precipitated in IPA. The polymer was collected and redissolved in THF to a 15% solids solution and precipitated in IPA. The polymer was collected and dried in a vacuum oven. The polymer was dissolved as a 10% solids solution in EtOAc, washed four times with DI water, and precipitated in IPA. The polymer was collected by vacuum filtration, pulled dry under air, and dried overnight in a vacuum oven at 70° C. 48.6 g (48.9%) white powder, GPC: 21,056 g / mol Mn, 37,204 g / mol Mw, 1.77 PDI.

[0087] Example 7: Synthesis of poly(styrene-co-4-vinylbenzocyclobutene-co-methyl methacrylate-co-4-hydroxyphenyl methacrylate) - hydroxyl-terminated (feed ratio 30 / 30 / 35 / 5) Styrene (26.94 g, 259 mmol), 4-vinylbenzocyclobutene (33.68 g, 259 mmol), methyl methacrylate (30.22 g, 302 mmol), 4-hydroxyphenyl methacrylate (7.68 g, 43.1 mmol), 4,4'-azobis(4-cyanopentanol) (1.48 g, 5.86 mmol), and 2-butanone (150 g) were added to the flask and mixed under nitrogen for 30 minutes. The mixture was heated in an 85°C oil bath for 16 hours. The mixture was cooled to room temperature and diluted with THF and precipitated in IPA. The polymer was collected and redissolved in THF to a 15% solids solution and precipitated in IPA. The polymer was collected and dried in a vacuum oven. The polymer was dissolved as a 10% solids solution in EtOAc, washed four times with DI water, and precipitated in IPA. The polymer was collected by vacuum filtration, pulled dry under air, and dried overnight in a vacuum oven at 70° C. 51.0 g (51.4%) white powder, GPC: 23,315 g / mol Mn, 38,666 g / mol Mw, 1.66 PDI.

[0088] Example 8: Synthesis of poly(styrene-co-4-vinylbenzocyclobutene-co-methyl methacrylate-co-4-hydroxyphenyl methacrylate) - hydroxyl-terminated (feed ratio 23 / 30 / 45 / 2) Styrene (10.57 g, 102 mmol), 4-vinylbenzocyclobutene (17.24 g, 132 mmol), methyl methacrylate (19.88 g, 199 mmol), 4-hydroxyphenyl methacrylate (1.57 g, 8.8 mmol), 4,4'-azobis(4-cyanopentanol) (0.74 g, 2.93 mmol), and 2-butanone (75 g) were added to the flask and mixed under nitrogen for 30 minutes. The mixture was heated in an 85°C oil bath for 16 hours. The mixture was cooled to room temperature and diluted with THF and precipitated in IPA. The polymer was collected and redissolved in THF to a 15% solids solution and precipitated in IPA. The polymer was collected and dried in a vacuum oven. The polymer was dissolved as a 10% solids solution in EtOAc, washed four times with DI water, and precipitated in IPA. The polymer was collected by vacuum filtration, pulled dry under air, and dried overnight in a vacuum oven at 70° C. 24.9 g (50.1%) white powder, GPC: 20,979 g / mol Mn, 35,723 g / mol Mw, 1.70 PDI.

[0089] Comparative Example 1: Synthesis of poly(styrene-co-4-vinylbenzocyclobutene-co-methyl methacrylate)-hydroxyl terminated (feed ratio 30 / 30 / 40) Styrene (28.0 g, 0.27 mol), 4-vinylbenzocyclobutene (35.0 g, 0.27 mol), methyl methacrylate (35.9 g, 0.36 mol), 4,4'-azobis(4-cyanopentanol) (0.99 g, 3.92 mmol) and 2-butanone (150 g) were added to the flask and mixed under nitrogen for 30 minutes. The mixture was heated in an 85° C. oil bath for 16 hours. The mixture was cooled to room temperature, diluted two-fold with THF and precipitated in isopropanol. The polymer was collected, redissolved in THF to a 15% solids solution and precipitated in isopropanol. The polymer was collected and dried overnight in a vacuum oven at 70° C. 26 g (26%) white powder, GPC: 26,113 g / mol Mn, 43,631 g / mol Mw, 1.67 PDI.

[0090] Characterization Table 1 summarizes the polymer properties of the polymers prepared in Examples 1 to 8. Figure 1 shows a representative example of the H1-NMR spectrum of the hydroxyl-terminated [P(Sr-VBCB-r-MMA-r-HEMA)-OH] polymer (Example 1), poly(styrene-co-4-vinylbenzocyclobutene-co-methyl methacrylate-co-4-hydroxyphenyl methacrylate), and Figure 2 shows a representative example of the NMR spectrum of the poly(styrene-co-4-vinylbenzocyclobutene-co-methyl methacrylate-co-4-hydroxyphenyl methacrylate)-hydroxy-terminated [P(Sr-VBCB-r-MMA-r-PQMA)-OH] polymer (Example 5), respectively.

[0091] [Table 1]

[0092] A coating of JSR SiARC ISX-302 or ISX-304 was prepared by coating on a silicon wafer and N 2 The wafer was baked at 220° C. / 90 sec in a 300° C. oven. The wafer was separated into smaller coupon pieces and fixed onto a Si wafer.

[0093] Neutral Layer Test Formulation Preparation and Coating: Test solutions were prepared by dissolving the polymers of Examples 1-8 and Comparative Example 1 in PGMEA to give 0.3 wt% solutions and filtering them through a 0.2 micron PTFE filter. These solutions were coated onto SiARC substrates, JSR SiARC ISX-302 and ISX-304, and baked at 250°C / 2 min in N2, and SOL1 (BCP) was coated and baked at 260°C / 15 min in air. The naming of each solution reflects the naming of the example, so SOL1 to SOL8 are the solutions prepared from Examples 1-8, and SOL COMP1 is the sample prepared from Comparative Example 1.

[0094] Figure 3 shows the novel mats coated on JSR SiARCs ISX-302 and ISX-304. Clearly, dewetting defects were observed in the neutral layer films formed from SOL COMP1 on both SiARCs. In contrast, surprisingly, these coating defects were not observed in the inventive neutral layer films coated from SOL1 and SOL8, which were prepared using the inventive neutral layer polymers containing HEMA or PQMA as hydroxy-functionalized repeat units produced with AIBN-OH and thus having OH end groups.

[0095] These coupons were evaluated for coating defects using an SEM tool as dewet spots, black spots, or white spots, as shown in Figure 4. SEM images with white spots were rated as dewet defects. SEM images with bright white spots were rated as slight defects. SEM images with barely discernible white spots were rated as very slight defects. SEM images with no discernible spots were rated as no defects.

[0096] Similarly, FIG. 5 shows that when block copolymer coatings were coated from Ref SOL1 onto neutral mats coated onto JSR SiARC ISX-302 and annealed, collapse of the self-assembled morphology was only observed in the comparative neutral layer coated from SOL COMP1, and surprisingly not in the neutral coatings on JSR SiARC ISX-302 formed from the inventive polymers in SOL1 and SOL5, respectively.

[0097] Figure 6 shows that SEM images with >90% contact hole features were rated as good C / H (A). SEM images with 50-89% contact hole features were rated as partial C / H (B). SEM images with 0-49% contact hole features were rated as poor C / H (C).

[0098] FIG. 7 shows that when block copolymer coatings were coated from Ref SOL1 onto neutral mats coated onto JSR SiARC ISX-304 and annealed, the self-assembled morphologies observed were comparable between SOL COMP1 and the neutral coatings on JSR SiARC ISX-304 formed from the inventive polymers in SOL1 and SOL5, respectively.

[0099] 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 having a structure (A), Styrenic repeating units of structure (I), where R ｍ１ is H or C1-C4 alkyl, R １ is selected from H, C1-C8 alkyl, and C1-C4 alkyloxy, and n1 is the total number of said repeat units, and said repeat units range from about 10 mol % to about 60 mol % in said copolymer; A repeating unit of structure (II) derived from 4-vinylbenzocyclobutene, where R ｍ２ is H or C1-C4 alkyl, R ２ is H or C1-C8 alkyl, and n2 is the total number of said repeat units, and said repeat units are from about 15 mol % to about 35 mol % in said copolymer; Repeating units of structure (III) derived from alkyl acrylate or alkyl 2-methylene alkanoate, where R ｍ３ is H or C1-C4 alkyl, R ３ is a C1-C8 alkyl, n3 is the total number of such repeat units, and such repeat units are from about 15 mol % to about 55 mol % in the copolymer; Repeating units of structure (IV) derived from hydroxy-substituted acrylates or 2-methylene alkanoates, where R ｍ４ is H or C1-C4 alkyl, R Ｉ is C1-C8 alkyl; L １ is a spacer moiety selected from a C2-C12 alkylene spacer and a 1,4-phenylene spacer, wherein said alkylene spacer is selected from the group consisting of C2-C12 linear alkylene, C3-C12 branched alkylene, C3-C12 cyclic alkylene, and C5-C12 alicyclic alkylene, and there are at least two carbon atoms between the carbonyloxy moiety and the OH moiety, and these two moieties are individually attached to the alkylene spacer at different positions that are either primary or secondary carbons on the alkylene moiety, and said 1,4-phenylene spacer is one in which the carbonyloxy moiety and the OH moiety are in the 1,4 position relative to each other, n4 is the total number of such repeat units, and said repeat units are from about 1 mol % to about 5 mol % in said copolymer; One is H and the other is Rr, Rr １ and Rr ２ The two terminal groups shown in structure (A) are methyl moieties substituted with Rr １ is C1-C8 alkyl; Rr ２ is a C1-C8 alkyl, a C1-C8 alkylene hydroxy moiety (-alkylene-OH), a C1-C8 alkylene carboxylic acid moiety (-alkylene-CO ２ H), or a benzylic alcohol containing moiety of structure (B), where ni is an integer ranging from 0 to 5, nia is an integer ranging from 1 to 5, nib is an integer ranging from 1 to 5, and "*" represents the point of attachment of the moiety; Rr is a cyano moiety (-CN) or a carbonylalkyl moiety (-C(=O)-Ri), where Ri is a C1-C8 alkyl or aryl moiety; Including, The random polymer wherein the sum of the individual mole percentages of repeat units of structures (I), (II), (III) and (IV) is less than or equal to 100 mole percentage of the total repeat units present in said copolymer. 【Chemistry 1】

2. 2. The copolymer of claim 1, consisting of repeating units of structures (I), (II), (III) and (IV), the sum of which is 100 mole percent.

3. L １ is the C2 to C12 alkylene spacer.

4. L １ The copolymer of claim 1 or 2, wherein: is the 1,4-phenylene moiety spacer.

5. A copolymer according to any one of claims 1 to 3, said repeat units of structure (I) being from about 13 mol % to about 48 mol %; said repeat units of structure (II) being from about 25 mol % to about 35 mol %; from about 15 mol % to about 55 mol % of said repeat units of structure (III); said repeat units of structure (IV) being from about 1 mol % to about 2 mol %, and L １ is the C2 to C12 alkylene spacer, and the sum of the individual mole percentages of repeat units of structures (I), (II), (III) and (IV) equals 100 mole percent of all repeat units in the copolymer; The copolymer.

6. 5. A copolymer according to any one of claims 1, 2 and 4, said repeat units of structure (I) being from about 23 mol % to about 48 mol %; said repeat units of structure (II) being from about 25 mol % to about 35 mol %; said repeat units of structure (III) being from about 15 mol % to about 45 mol %; said repeat units of structure (IV) being from about 2 to about 5 mole percent, and L １ is a 1,4-phenylene spacer, and further wherein the sum of the individual mole percentages of repeat units of structures (I), (II), (III) and (IV) equals 100 mole percent of all repeat units in said copolymer; The copolymer.

7. 7. The copolymer according to claim 1, wherein in the repeating unit of structure (IV), L １ is the alkylene spacer and is selected from any of Structure (IVa1), Structure (IVa2), Structure (IVa3), Structure (IVa4), or Structure (IVa5), x is an integer from 1 to 11, x1 is an integer from 1 to 8, x2 is an integer from 1 to 8, x3 is an integer from 1 to 2, and x3a is an integer from 1 to 3; R ｘ１ is C1-C4 alkyl, R ｘ２ is C1-C4 alkyl, and in the repeat unit of structure (IVa5), the substituent R ｘ４ Or R ｘ５ and the remaining other substituents in the repeat unit of structure (IVa5) are H. 【Chemistry 2】

8. 8. The copolymer of claim 7, wherein said repeat unit of structure (IV) has structure (IVa1).

9. 8. The copolymer of claim 7, wherein said repeat unit of structure (IV) has structure (IVa2):

10. 8. The copolymer of claim 7, wherein said repeat unit of structure (IV) has structure (IVa3):

11. 8. The copolymer of claim 7, wherein said repeat unit of structure (IV) has structure (IVa4).

12. 12. The copolymer of claim 7 or 11, wherein said repeat unit of structure (IV) has structure (IVa41). 【Chemistry 3】

13. 12. The copolymer of claim 7 or 11, wherein said repeat unit of structure (IV) has structure (IVa42). 【Chemistry 4】

14. 12. The copolymer of claim 7 or 11, wherein said repeat unit of structure (IV) has structure (IVa43). 【Chemistry 5】

15. 8. The copolymer of claim 7, wherein said repeat unit of structure (IV) has structure (IVa5).

16. 15. The copolymer of claim 14, wherein the repeat unit of structure (IV) has structure (IVa51) or structure (IVa52). 【Chemistry 6】

17. The copolymer of any one of claims 1 to 5, 7 and 8, wherein the repeat unit of structure (IV) has structure (IVa). 【Chemistry 7】

18. The copolymer of any one of claims 1 to 4 and 6, wherein the repeat unit of structure (IV) has structure (IVb). 【Chemistry 8】

19. R ｍ１ and R ｍ２ The copolymer of any one of claims 1 to 18, wherein is H.

20. R ｍ３ The copolymer of any one of claims 1 to 19, wherein is H.

21. R ｍ４ The copolymer of any one of claims 1 to 20, wherein is H.

22. R ｍ３ The copolymer of any one of claims 1 to 19 and 21, wherein is a C1 to C4 alkyl.

23. R ｍ４ 23. The copolymer of any one of claims 1 to 20 and 22, wherein is a C1 to C4 alkyl.

24. R ｍ３ The copolymer of any one of claims 1 to 19, 21 and 23, wherein is methyl.

25. R ｍ４ The copolymer according to any one of claims 1 to 20 and 22 to 24, wherein is methyl.

26. R １ The copolymer of any one of claims 1 to 25, wherein is a C1 to C4 alkyl.

27. R １ The copolymer of any one of claims 1 to 25, wherein is H.

28. 28. The copolymer of claim 27, wherein the repeat unit of structure (I) has structure (Ia). 【Chemistry 9】

29. R ２ The copolymer of any one of claims 1 to 28, wherein is C1 to C4 alkyl.

30. R ２ The copolymer of any one of claims 1 to 29, wherein is H.

31. 31. The copolymer of claim 30, wherein the repeat unit of structure (II) has structure (IIa). 【Chemistry 10】

32. R ３ The copolymer of any one of claims 1 to 31, wherein is a C1 to C4 alkyl.

33. R ３ The copolymer of any one of claims 1 to 32, wherein is methyl.

34. 34. The copolymer of claim 33, wherein the repeat unit of structure (III) has structure (IIIa): 【Chemistry 11】

35. The copolymer of any one of claims 1 to 5, 7 and 28 to 34, wherein the repeat unit of structure (IV) has structure (IVc). 【Chemistry 12】

36. The copolymer of any one of claims 1 to 4, 6 and 28 to 34, wherein the repeat unit of structure (IV) has structure (IVd). 【Chemistry 13】

37. The copolymer of any one of claims 1 to 5, 7, and 28 to 34, wherein the copolymer has the structure (A-1): 【Chemistry 14】

38. R １ The copolymer of claim 37, wherein is methyl.

39. R ２ is a C1 to C8 alkyl.

40. R ２ is a C1-C8 alkylene hydroxy moiety.

41. R ２ is a C1 to C8 alkylene carboxylic acid.

42. R ２ 40. The copolymer of claim 37 or 38, wherein: is the benzylic alcohol-containing moiety of structure (B).

43. The copolymer of claim 42, wherein structure (B) has structure (B-1). 【Chemistry 15】

44. The copolymer of any one of claims 37 to 43, wherein Rr is a cyano moiety (-CN).

45. The copolymer of any one of claims 37 to 43, wherein Rr is a carbonylalkyl moiety (-C(=O)-Ri), where Ri is a C1 to C8 alkyl or aryl moiety.

46. The copolymer of any one of claims 1-4, 6, 28-34, and 36, wherein the copolymer has the structure (A-2): 【Chemistry 16】

47. R １ The copolymer of claim 46, wherein is methyl.

48. R ２ is a C1 to C8 alkyl.

49. R ２ is a C1-C8 alkylene hydroxy moiety.

50. R ２ is a C1 to C8 alkylene carboxylic acid.

51. R ２ is the benzylic alcohol-containing moiety of structure (B).

52. The copolymer of claim 51, wherein structure (B) has structure (B-1): 【Chemistry 17】

53. 53. The copolymer of any one of claims 46 to 52, wherein Rr is a cyano moiety (-CN).

54. 53. The copolymer of any one of claims 46 to 52, wherein Rr is a carbonylalkyl moiety (-C(=O)-Ri), where Ri is a C1 to C8 alkyl or aryl moiety.

55. A composition comprising a copolymer according to any one of claims 1 to 54 and an organic spin-casting solvent.

56. In the copolymer, L １ 56. The composition of claim 55, wherein is the alkylene spacer.

57. In the copolymer, L １ is the alkylene, and Rr ２ is said C1 to C8 alkyl.

58. In the copolymer, L １ is the alkylene, and further, Rr ２ is a C1-C8 alkylene hydroxy moiety (-alkylene-OH), a C1-C8 alkylene carboxylic acid moiety (-alkylene-CO ２ 56. The composition of claim 55, wherein said benzylic alcohol-containing moiety is selected from the group consisting of (A), (B), (C), (D), (E), and (F).

59. In the copolymer, L １ The composition of claim 55, wherein is the 1,4-phenylene spacer.

60. In the copolymer, L １ is the 1,4-phenylene spacer, and further, Rr ２ is said C1 to C8 alkyl.

61. In the copolymer, L １ is the 1,4-phenylene spacer, and further, Rr ２ is a C1-C8 alkylene hydroxy moiety (-alkylene-OH), a C1-C8 alkylene carboxylic acid moiety (-alkylene-CO ２ 56. The composition of claim 55, wherein the benzylic alcohol-containing moiety of structure (B) is:

62. 1. A method for forming a crosslinked or grafted and crosslinked coating of a copolymer on a substrate, comprising the steps of: i) forming a coating of the composition of any one of claims 55 to 61 on a substrate; ii) heating the coating at a temperature of from about 90° C. to about 180° C. to remove the solvent and form a crosslinked or grafted and crosslinked coating of the copolymer; iii) heating the crosslinked or grafted and crosslinked coating of step ii) to about 200° C. to about 250° C. to form a fully crosslinked or fully crosslinked and grafted copolymer coating; A method comprising:

63. 1. A method for forming a crosslinked or grafted and crosslinked neutral coating on a substrate, comprising the steps of: ia) forming a coating of the composition according to any one of claims 55 to 61 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 crosslinked or grafted and crosslinked coating; iiia) heating the crosslinked coating of step iid) at a temperature of about 200° C. to about 250° C. to form a fully crosslinked neutral coating; The method comprising:

64. 1. A method for forming a crosslinked neutral coating on a substrate, comprising the steps of: ib) forming a coating of the composition of claim 57 or 60 on a substrate; iib) heating the coating at a temperature of from about 90° C. to about 180° C. to remove the solvent and form a crosslinked or grafted and crosslinked coating; iiib) heating the crosslinked or grafted and crosslinked coating of step iif) at a temperature of about 200° C. to about 250° C. to form a fully crosslinked neutral coating; The method comprising:

65. 1. A method for forming a grafted and crosslinked neutral coating on a substrate, comprising the steps of: ic) forming a coating of the composition of claim 58 or 61 on a substrate; iic) heating the coating at a temperature of from about 90° C. to about 180° C. to remove the solvent and form a grafted and crosslinked coating; iiiic) heating the crosslinked coating of step iic) at a temperature of about 200° C. to about 250° C. to form a fully grafted and crosslinked neutral coating; The method comprising:

66. 1. A method of forming a self-assembled block copolymer coating on a neutral coating comprising the steps of: id) forming a neutral coating according to any one of claims 62 to 65, iid) applying a block copolymer onto the neutral coating and annealing until induced self-assembly of the block copolymer coating occurs; The method comprising:

67. 1. A method for graphoepitaxy-directed self-assembly of a block copolymer coating used to form an image, comprising the steps of: ie) forming a neutral coating according to any one of claims 62 to 65, iii) providing a coating of a photoresist coating over said neutral coating and forming a pattern in said photoresist coating; iii) 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 iv) etching the block copolymer to remove highly etchable blocks of the copolymer covering some areas of the substrate and at the same time selectively forming a pattern in the substrate in these areas; The method comprising:

68. 68. The method of claim 67, wherein the pattern in the photoresist coating is formed by imaging lithography selected from the group consisting of e-beam, broadband, 193 nm immersion, 193 nm dry, 13.5 nm, 248 nm, 365 nm and 436 nm lithography.

69. A method for chemoepitaxy-directed self-assembly of a block copolymer coating used to form an image, comprising the steps of: if) forming a neutral coating on the substrate according to any one of claims 62 to 65, iif) providing a coating of a photoresist coating over the neutral coating and forming a pattern in the photoresist coating, thereby forming areas of the neutral coating not covered by the resist; iiif) treating said uncovered neutral coating to remove it and form a pinning region; ivf) removing the photoresist to expose the untreated neutral coating and form a chemo-epitaxy pattern including neutral and pinned regions; vf) applying a block copolymer comprising an etch-resistant block and a highly etchable block onto the neutral coating and annealing until induced self-assembly occurs; and vif) etching said block copolymer to remove highly etchable blocks of the copolymer covering some areas of the substrate and at the same time selectively forming a pattern in the substrate in these areas; The method comprising:

70. 70. The method of claim 69, wherein the pattern in the photoresist coating is formed by imaging lithography selected from the group consisting of e-beam, broadband, 193 nm immersion, 193 nm dry, 13.5 nm, 248 nm, 365 nm and 436 nm lithography.

71. Use of a random polymer according to any one of claims 1 to 54 or of a composition according to any one of claims 55 to 61 for forming a coating on a substrate.

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