Hydrophobic, crosslinkable pinning underlayer with improved dry etching ability for patterning induced self-assemblies of PS-B-PMMA type block copolymers

Abstract

The present invention relates to novel random copolymers comprising repeating units of structures (I), (II) and (III), wherein R 1 and R 2 are independently C1-C4 alkyl, and x and y are independently R 1 and R 2 are independently an integer ranging from 0 to 3; R 3 is C1-C4 alkyl, and R 4 is selected from C2-C4 primary alkyl or arene-containing moieties selected from the group consisting of substituted or unsubstituted biphenyl moieties, substituted or unsubstituted phenyl moieties, and substituted or unsubstituted benzyl-based moieties. Another aspect of the invention is a composition comprising the random copolymer and an organic spin-casting solvent. Yet another aspect of the invention is the use of a coating of the composition to form a patterned pinned MAT for use in directed self-assembly. TIFF2024519063000018.tif38170

Description

Technical Field

[0001] The present invention relates to a novel styrenic polymer, a novel composition, and a method of using the novel composition for aligning microdomains of an inductively self-assembled block copolymer (BCP). The composition and method are useful in the manufacture of electronic devices.

Background Art

[0002] Induced self-assembly (DSA) of block copolymers is a useful method for generating even smaller patterned shapes for the fabrication of microelectronic devices that can achieve limiting dimensions (CD) of shapes on the order of nanoscale. Induced self-assembly methods are desirable for extending the resolving capabilities of microlithography techniques. Conventional lithography strategies may use ultraviolet (UV) light to expose a photoresist layer coated on a substrate or layered substrate through a mask. Positive or negative photoresists are useful, and these may also contain heat-resistant elements such as silicon to enable dry development using conventional integrated circuit (IC) plasma processing techniques. In positive photoresists, UV radiation passing through the mask triggers a photochemical reaction in the photoresist, making the exposed area removable with a developer solution or by conventional IC plasma processing. Conversely, in negative photoresists, UV radiation passing through the mask makes the radiation-exposed area difficult to remove with a developer solution or by conventional IC plasma processing. Integrated circuit patterns, such as gates, vias, or interconnects, are then etched into the substrate or layered substrate, and the remaining photoresist is removed. Conventional lithography exposure processes have limitations on the graphic dimensions of integrated circuit patterns. Further reduction of pattern dimensions is difficult to achieve using radiation exposure due to limitations related to aberrations, focus, proximity effects, the minimum achievable exposure wavelength, and the maximum achievable numerical aperture. Due to the need for large-scale integration, the circuit dimensions and graphics of devices have been continuously reduced. In the past, the final resolution of the graphic depended on the wavelength of light used to expose the photoresist, which itself has limitations. Induced assembly techniques such as graphoepitaxy and chemoepitaxy using block copolymer imaging are highly desirable techniques used to enhance resolution while reducing CD variation. These techniques can be used to enhance conventional UV lithography techniques or to enable even higher resolution and CD control in strategies using EUV, electron beam, deep UV, or immersion lithography.Induced self-assembly block copolymers comprise blocks of etching-resistant copolymer units and blocks of easily etchable copolymer units, which, when coated, aligned, and etched on a substrate, provide areas of very high-density patterns. In the graphoepitaxy-induced self-assembly method, the block copolymer is pre-patterned using conventional lithography (e.g., ultraviolet, deep UV, electron beam, extreme ultraviolet (EUV) exposure sources) and self-assembles around a substrate on which repeating topographic patterns such as line / space (L / S) or contact hole (CH) patterns are formed. In an example of an L / S-induced self-assembly array, the block copolymer can form self-aligned lamellar regions, which can form parallel line-space patterns of different pitches in the trenches between each pre-patterned line, thereby enhancing pattern resolution by dividing the space in the trenches between each topographic line into finer patterns. For example, a microphase-separable diblock copolymer containing a carbon-rich block resistant to plasma etching (e.g., styrene, or containing some other atoms such as Si, Ge, or Ti) and a block that is highly plasma-etchable or removable can provide high-resolution pattern definition. Examples of highly etchable blocks may include monomers that are oxygen-rich, free of heat-resistant elements, and capable of forming highly etchable blocks, such as methyl methacrylate. The plasma etching gas used in the etching process to define the self-assembly pattern is typically the same gas used in processes for manufacturing integrated circuits (ICs). In this way, extremely fine patterns can be generated in a typical IC substrate compared to those that can be defined by conventional lithography techniques, thus achieving pattern multiplication.Similarly, graphoepitaxy can generate denser patterns such as contact holes. In this case, appropriate block copolymers align themselves through induced self-assembly around the array of contact holes or posts defined by conventional lithography, thus forming a denser array of etchable and etch-resistant domains, which, when etched, yields a denser array of contact holes. As a result, graphoepitaxy has the potential to provide both pattern refinement and pattern multiplication.

[0003] In chemoepitaxy or pinned chemoepitaxy (also known as chemoepitaxy), the self-assembly of block copolymers is formed around a surface that has regions of different chemistry but lacks or has little to no topography to induce the self-assembly process. For example, the surface of a substrate can be patterned using conventional lithography (e.g., UV, deep UV, electron beam, EUV) to produce surfaces of different chemistry in a line-and-space (L / S) pattern, where exposed regions, whose surface chemistry has been altered by irradiation, are alternated with unexposed regions that do not show chemical changes. These regions do not provide topographic differences but provide surface chemical differences or pinning that induce the self-assembly of block copolymer segments. Specifically, the induced self-assembly of block copolymers, each having block segments containing etchable repeating units (e.g., styrene repeating units) and fast-etchable repeating units (e.g., methyl methacrylate repeating units), will enable the precise placement of etchable and highly etchable block segments on a pattern. This technique allows for the precise placement of these block copolymers and subsequent pattern transfer to a substrate after plasma or wet etching. Chemo-epitaxy has the advantage of being fine-tuned by changes in chemical differences to help improve line edge roughness and CD control, enabling pattern adjustment. Other types of patterns, such as repeating contact hole (CH) arrays, can also be pattern-tuned using chemoepitaxy.

[0004] The neutral layer is a layer on or on the surface of a treated substrate that has no affinity for any of the block segments of the block copolymer used for induced self-assembly. The neutral layer is useful in the graphoepitaxy method of induced self-assembly of block copolymers because it allows for proper placement or orientation of the block polymer segments for induced self-assembly, resulting in proper placement of etch-resistant block polymer segments and highly etchable block polymer segments on the substrate. For example, on a surface containing line-and-space patterns defined by conventional radiolithography, the neutral layer allows the block segments to be oriented so that they are perpendicular to the surface of the substrate, an orientation that is ideal for both pattern adjustment and pattern multiplication, depending on the length of the block segments in the block copolymer relative to the length between lines defined by conventional lithography. If the substrate interacts too strongly with one of the block segments, this 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, which can be used to achieve either pattern adjustment or pattern multiplication based on the figure produced by conventional lithography. Modifying selected small areas or pinning the substrate to strengthen the interaction between these and one of the blocks of the block copolymer, and leaving the remainder of the substrate coated with a pinned MAT layer, can be useful for aligning the domains of the block copolymer in a desired direction, which forms the basis of pinned chemoepitaxy or graphoepitaxy used for pattern multiplication. This MAT layer is a crosslinked layer that is insoluble in any layer coated on its surface and can be used as a DSA neutral or pinned layer.

[0005] Compositions containing standard crosslinkable styrene-based pinned MAT layer materials have high plasma etching resistance due to their high aromatic hydrocarbon content and do not allow for simple patterning using dry etching processes that result in the development of pre-patterns useful for induced self-assembly. Specifically, a problem associated with dry etching of standard crosslinkable styrene-based pinned MAT DSA underlayers useful for pattern doubling of pre-patterns formed by dry 193nm lithography, 193nm immersion lithography, or extreme ultraviolet (EUV) lithography is that the high etching resistance of these standard MAT materials used for either pattern doubling or adjustment degrades the preferred topographic design of the pre-pattern by generating non-uniformity of the critical dimensions of block copolymer domains, leading to DSA defects such as bridging and dislocations, as well as edge placement errors. Problems associated with dry etching of crosslinkable polystyrene underlayers in 193i lithography (193nm immersion lithography) degrade the preferred topographic design of the pre-pattern and generate DSA defects, such as bridges involving the bottom anti-reflective coating, substrate, and standard styrene-based pinned MAT layer compositions. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] US8,835,581 [Patent Document 2] US9,181,449 [Patent Document 3] US9,093,263 [Patent Document 4] US8691925 [Patent Document 5] US20140335324A1 [Patent Document 6] US2016-0122579A1 [Non-patent literature]

[0007] [Non-Patent Document 1] Erik W.Edwards et. al.,Macromolecules 2007,40,p 90-96 [Overview of the project]

[0008] For chemoepitaxy-induced self-assembly processes, a series of novel polystyrene copolymers containing small amounts of polar copolymers were synthesized to enable the easy fabrication of hydrophobic, crosslinkable MAT underlayers for DSA pre-pattern development. Specifically, several terpolymers were developed containing styrene and 4-vinylbenzocyclobutene-derived repeating units, as well as repeating units derived from polar alkyl methacrylates or methacrylate esters of the arene moieties. The dry-etch properties of these novel terpolymers are tuned depending on the presence and concentration of these polar alkyl methacrylates or arene-containing methacrylates. These new hydrophobic, crosslinkable MAT underlayers exhibit controlled pre-pattern topography and favorably influence PS-b-PMMA block copolymer assemblies for line-multiplying DSA process flows, with more uniform domain sizes of PS and PMMA blocks.

[0009] One aspect of the present invention is a random copolymer comprising repeating units of structures (I), (II), and (III), wherein R1 and R2 are independently C1-C4 alkyl groups, x and y are independently the number of R1 and R2 groups, which are independently integers from 0 to 3, R3 is a C1-C4 alkyl group, and R4 is selected from C2-C10 primary alkyl groups or from a moiety containing an arene selected from the group consisting of substituted or unsubstituted biphenyl moieties, substituted or unsubstituted phenyl moieties, and substituted or unsubstituted benzyl moieties, and m, n, and o are the number of repeating units of structures (I), (II), and (III), respectively, wherein the molar percentage of repeating units of structure (I) is The mol% ranges from approximately 60 mol% to approximately 95 mol%, the mol% of the repeating units of structure (II) ranges from approximately 5 mol% to approximately 25 mol%, and the mol% of the repeating units of structure (III) ranges from approximately 2 mol% to approximately 18 mol%, where the sum of the mol% of these repeating units is less than 100 mol% if other different repeating units are present, or equal to 100 mol% if only the repeating units of structures (I), (II), and (III) are present; furthermore, the random copolymer has polydispersity in the range of approximately 1.25 to approximately 1.80 and has an Mw in the range of approximately 30,000 to approximately 45,000 Daltons; and the random copolymer does not contain reactive end groups including benzyl alcohol-containing moieties.

[0010] [ka] Another aspect of the present invention is a composition comprising this random copolymer and an organic spin-casting solvent.

[0011] Another aspect of the present invention is the use of a coating of this composition for the formation of patterned pinned MATs for induced self-assembly. Figure 1 shows one possible chemoepitaxy scheme that can be used when a crosslinked pinned MAT layer formed with the composition comprising the novel random copolymer is used. [Brief explanation of the drawing]

[0012] [Figure 1] An example of a suitable chemoepitaxy-induced self-assembly scheme using a crosslinked pinned MAT layer formed from the novel random copolymer, the repeating units comprising repeating units of structures (I), (II), and (III). [Figure 2] Reference Comparative Example 1, which does not exhibit neutrality with respect to PS-b-PMMA, and novel material examples 1, 2, and 3 series (1-3 using n-butyl methacrylate monomer at different concentrations) exhibiting similar behavior. Conditions: Coating of Examples 1-3 and Comparative Example 1, baked at 250°C / 30 minutes / N2; coating of neutral brush 1, baked at 250°C / 30 minutes / N2, EBR washing for 2 minutes, dry bake; coating of block copolymer 1, ctg50@35nm, annealed at 250°C / 30 minutes / N2. [Figure 3] Comparison of etching rate and normalized etching rate. Improvement of bulk etching in Examples 1, 2, and 3 compared to Comparative Example 1. Conditions: ACT12: 110°C / 1 min, 250°C / 30 min (N2). Trion etcher: Pressure = 70 mT; Top / Bottom (W) = 50 / 50; O2 (sccm) = 50. [Figure 4] Comparison of etching rate and normalized etching rate. Improvement of bulk etching in Examples 1, 2, 11, and 12 compared to Comparative Example 1. Conditions: ACT12: 110°C / 1 min, 250°C / 30 min (N2). Trion etcher: Pressure = 70 mT; Top / Bottom (W) = 50 / 50; O2 (sccm) = 50. [Figure 5] Lithography performance at P90nm. Example 3 yields a larger post-development inspection (ADI) CD than pinned MAT layers from Examples 1 and 2 or Comparative Example 1. [Figure 6] Lithography performance at P90nm. Example 3 results in a larger post-etch inspection (AEI) CD than Example 1 and Example 2 or Comparative Example 1. [Figure 7] DSA process window of the polymer as a pinning guide; comparison between Comparative Example 1 and Example 1, Example 2 and Example 3. [Figure 8] Average CD and 3σ of DSA lines formed using Comparative Example 1 and Examples 1, 2 and 3. [Figure 9] Examples of guide and non-guide DSA lines formed and used for CD evaluation.

Mode for Carrying Out the Invention

[0013] It should be understood that both the foregoing general description and the following detailed description are illustrative and explanatory, and do not limit the invention described in the claims. In this application, the use of the singular form includes the plural form, and unless specifically stated otherwise, the singular form means "at least one", and the use of "or" means "and / or". Furthermore, the description of "comprising" and the use of other verb forms such as "comprised of" are not limiting. Also, the description of "element" or "component" includes both elements and components containing one structural unit and elements or components containing more than one structural unit, unless specifically stated otherwise. Unless otherwise indicated, the conjunction "and" used herein is intended to be inclusive, while the conjunction "or" is not intended to be exclusive. For example, the phrase "or alternatively" is intended to be exclusive. The description of "and / or" used herein refers to any combination of the aforementioned elements, including the use of a single element.

[0014] The chapter titles used herein are for the purpose of organizing the document and should not be interpreted as limiting the subject matter. While not limiting, all documents or parts of documents cited herein, including patents, patent applications, articles, books, and professional texts, are considered to have their entire contents included herein for all purposes. In the event of any discrepancy between the definition of a term in one or more of the documents cited herein and the definition of a term in this application, the definition in this application shall prevail.

[0015] In this specification, "alkyl" means a hydrocarbon group that may be a linear or branched hydrocarbon group (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl and similar) or a cyclic hydrocarbon group (e.g., cyclohexyl, cyclopropyl, cyclopentyl and similar).

[0016] "Alkyloxy" refers to the previously defined alkyl group bonded via the oxy (-O-) moiety (e.g., methoxy, ethoxy, propoxy, butoxy, 1,2-isopropoxy, cyclopentyloxy, cyclohexyloxy, and similar compounds).

[0017] "Fluoroalkyl" refers to the previously defined linear, cyclic, or branched saturated alkyl groups in which hydrogen is partially or completely replaced by fluorine (e.g., trifluoromethyl, perfluoroethyl, 2,2,2-trifluoroethyl, perfluoroisopropyl, perfluorocyclohexyl, and analogues).

[0018] "Fluoroalkyloxy" refers to the fluoroalkyl group defined above, which is bonded via an oxy (-O-) group (e.g., trifluoromethyloxy, perfluoroethyloxy, 2,2,2-trifluoroethoxy, perfluorocyclohexyloxy, and analogues).

[0019] In this specification, when referring to alkyl, alkyloxy, fluoroalkyl, and fluoroalkyloxy parts using a possible range of carbon atoms starting from C1, for example, in non-limiting examples, when we say "C1-C10 alkyl" or "C1-C10 fluoroalkyl," this range includes primary alkyls, linear alkyls (also known as n-alkyls), secondary alkyls, alkyloxys, fluoroalkyls, and fluoroalkyloxys starting from C1, but only specifies branched alkyls, branched alkyloxys, cycloalkyls, cycloalkyloxys, branched fluoroalkyls, and cyclic fluoroalkyls starting from C3.

[0020] The term "primary alkyl" refers to a part of a substituent where the bonding site is a primary carbon, and the remainder of this substituent, other than the bonding site, may be H (also known as methyl), a linear alkyl moiety (e.g., n-alkyl), a branched alkyl, or a cycloalkyl. Specific non-limiting examples include methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, n-pentyl, 2-methylpentyl, 3-methylpentyl, n-hexyl, 2-methylhexyl, n-heptyl, 2-methylheptane, 3-methylheptane, n-octyl, (cyclohexyl)methyl(CH2-cyclohexyl), and (cyclopentyl)methyl(CH2-cyclopentyl). Another detail of C1-C10 primary alkyls is that these primary alkyls have a total of C1-C10 carbon atoms.

[0021] In this specification, the term "alkylene" refers to a hydrocarbon group that may be linear, branched, or cyclic and has two bonding sites (e.g., methylene, ethylene, 1,2-isopropylene, 1,4-cyclohexylene, and analogues). In this case as well, when specifying a possible range of carbon atoms, for example, as an unrestricted example, C1-C20, this range includes linear alkylenes beginning with C1 (or methyl), but only specifies branched alkylenes or branched cycloalkylenes beginning with C3. The term alkylene also includes unsubstituted alkylenes (also known as linear, branched, or cyclic alkylenes with only one hydrogen atom) and substituted alkylenes (also known as linear, branched, or cyclic alkylenes containing these substituents other than hydrogen), where these substituted alkylenes are those in which one or more hydrogen atoms are replaced by substituents selected from aryl groups, halides, C1-C20 alkyls, or C1-C20 alkyloxys.

[0022] In this specification, the expression "arene-containing moiety" refers to a monofunctional group containing an arene selected from substituted or unsubstituted benzyl moieties, substituted or unsubstituted biphenyl moieties, and substituted or unsubstituted phenyl moieties. In this regard, "unsubstituted" requires the presence of only hydrogen atoms, while "substituted" requires the presence of at least one substituent selected from halides, C1-C20 alkyl groups, fluoroalkyl groups, perfluoroalkyl groups, and C1-C20 alkyloxy groups, or combinations thereof.

[0023] In this specification, the term "aryl" refers to an aromatic hydrocarbon moiety having one bond, which may be a polycyclic aromatic moiety having one bond, such as a monobenzene moiety (e.g., phenyl), naphthalene, anthracene, pyrene, and analogues, or a chain of multiple benzene rings having one bond (e.g., 1,4-biphenyl). The term "aryl" also includes the above moieties which are either unsubstituted aryls (in other words, those with only hydrogen substituents) or substituted aryls whose substituents are selected from halides, C1-C20 alkyls, or C1-C20 alkyloxys.

[0024] "Lo" is the block copolymer bulk repeat period as defined in Erik W. Edwards et al., Macromolecules 2007, 40, pp. 90-96 (Non-Patent Literature 1).

[0025] When two connecting parts are adjacent to each other and both are described as having a monovalence bond, this description represents a single connecting part that has a monovalence bond (for example, when both connecting parts L1 and L2 are referred to as having a monovalence bond, this represents a single connecting part that has a monovalence bond).

[0026] One aspect of the present invention is a random copolymer in which the repeating units comprise repeating units of structures (I), (II), and (III), where R1 and R2 are independently C1-C4 alkyls, x and y are independently the number of R1 and R2, and are independently integers from 0 to 3, R3 is a C1-C4 alkyl, and R4 is selected from C2-C10 primary alkyls or from a moiety containing an arene selected from the group consisting of substituted or unsubstituted biphenyl moieties, substituted or unsubstituted phenyl moieties, and substituted or unsubstituted benzyl moieties, and m, n, and o are the number of repeating units of structures (I), (II), and (III), respectively, provided that structure (I) The mol% of the repeating units ranges from approximately 60 mol% to approximately 95 mol%, the mol% of the repeating units of structure (II) ranges from approximately 5 mol% to approximately 25 mol%, the mol% of the repeating units of structure (III) ranges from approximately 2 mol% to approximately 18 mol%, and the sum of the mol% of these repeating units is less than 100 mol% if other different repeating units are present, or equal to 100 mol% if only the repeating units of structures (I), (II), and (III) are present, and furthermore, the random copolymer has a polydispersity of approximately 1.25 to approximately 1.80, and has an Mw in the range of approximately 30,000 to approximately 45,000 Daltons, and the random copolymer does not contain reactive end groups including benzyl alcohol-containing moieties. In one other aspect of this embodiment, the random copolymer essentially consists of repeating units of structures (I), (II), and (III). In yet another aspect of this embodiment, the random copolymer consists of repeating units of structures (I), (II), and (III), where the total mol% of repeating units (I), (II), and (III) is equal to 100 mol%.

[0027] [ka] In one other aspect of the aforementioned random copolymer, the repeating units of structure (III) range from approximately 2.5 mol% to approximately 20 mol%. In another aspect of this embodiment, the repeating units range from approximately 2.5 mol% to approximately 16 mol%. In yet another aspect of this embodiment, the repeating units range from approximately 3 mol% to approximately 15 mol%.

[0028] In one other aspect of the aforementioned random copolymer, the repeating units of structure (II) range from approximately 6 mol% to approximately 23 mol%. In another aspect of this embodiment, the repeating units range from approximately 7 mol% to approximately 20 mol%. In yet another aspect of this embodiment, the repeating units range from approximately 7 mol% to approximately 15 mol%.

[0029] In one other aspect of the aforementioned random copolymer, the repeating units of structure (I) range from approximately 62 mol% to approximately 93 mol%. In another aspect of this embodiment, these repeating units range from approximately 60 mol% to approximately 90 mol%.

[0030] In another aspect of the aforementioned random copolymer, the repeating units of structure (I) range from approximately 60 mol% to approximately 90 mol%, the repeating units of structure (II) range from approximately 7 mol% to approximately 20 mol%, and the repeating units of structure (III) range from approximately 3 mol% to approximately 15 mol%.

[0031] In one of the other aspects of the aforementioned random copolymer, y is 0.

[0032] In one of the other aspects of the aforementioned random copolymer, x is 0.

[0033] In one of the other aspects of the aforementioned random copolymer, x and y are 0.

[0034] In another aspect of the aforementioned random copolymer, R3 is CH3.

[0035] In one of the other aspects of the above random copolymer, R4 is a C2-C10 primary alkyl. In another aspect of this embodiment, R4 is a C2-C9 primary alkyl. In another aspect of this embodiment, R4 is a C2-C8 primary alkyl. In yet another aspect of this embodiment, R4 is a C2-C7 primary alkyl. In yet another aspect of this embodiment, R4 is a C3-C7 primary alkyl. In yet another aspect of this embodiment, R4 is a C3-C6 primary alkyl. In yet another aspect of this embodiment, R4 is a C4-C6 primary alkyl. In yet another aspect of this embodiment, R4 is a C4-C5 primary alkyl. In another aspect of this embodiment, R4 is n-butyl.

[0036] In one other aspect of this random copolymer, R4 is a C2-C6 primary alkyl group. In another aspect of this embodiment, R4 is a C2-C5 primary alkyl group. In yet another aspect of this embodiment, R4 is a C2-C4 primary alkyl group. In yet another aspect of this embodiment, R4 is a C2-C3 primary alkyl group. In one other aspect, R4 is n-propyl. In yet another aspect of this embodiment, R4 is ethyl.

[0037] In one other aspect of the aforementioned random copolymer, R4 is an arene-containing moiety. In one aspect of this embodiment, R4 is a benzyl moiety. In another aspect of this embodiment, R4 is benzyl.

[0038] In one other aspect of the aforementioned random copolymer, R4 is a moiety containing an arene. In one other aspect of this embodiment, R4 is a moiety containing a phenyl. In one other aspect of this embodiment, this is a substituted phenyl. In one other aspect of this embodiment, R4 is a phenyl.

[0039] In one other aspect of the aforementioned random copolymer, R4 is a moiety containing an arene. In another aspect of this embodiment, R4 is biphenyl. In another aspect of this embodiment, this is a substituted biphenyl moiety. In yet another aspect, this is an unsubstituted biphenyl. In yet another aspect, R4 is [1,1'-biphenyl-4-yl].

[0040] In another aspect of the aforementioned random copolymer, the repeating units have structures (Ia), (IIa), and (IIIa) as follows:

[0041] [ka] In another aspect of this embodiment, the repeating units of structure (Ia) are present in amounts from about 60 mol% to about 90 mol%, the repeating units of structure (IIa) are present in amounts from about 5 mol% to about 25 mol%, and the repeating units of structure (IIIa) are present in amounts from about 2 mol% to about 18 mol%.

[0042] In yet another aspect of this embodiment, the repeating units of structure (Ia) are present in amounts from approximately 75 mol% to approximately 90 mol%, the repeating units of structure (IIa) are present in amounts from approximately 5 mol% to approximately 15 mol%, and the repeating units of structure (IIIa) are present in amounts from approximately 2 mol% to approximately 18 mol%.

[0043] In one of the other aspects of the random copolymer described herein, the repeating unit has the following structures (Ia), (IIa), and (IIIa-1):

[0044] [ka] In another aspect of this embodiment, the repeating units of structure (Ia) are present in amounts from approximately 60 mol% to approximately 90 mol%, the repeating units of structure (IIa) are present in amounts from approximately 5 mol% to approximately 25 mol%, and the repeating units of structure (IIIa-1) are present in amounts from approximately 2 mol% to approximately 18 mol%.

[0045] In yet another aspect of this embodiment, the repeating units of structure (Ia) are present in amounts from approximately 60 mol% to approximately 90 mol%, the repeating units of structure (IIa) are present in amounts from approximately 5 mol% to approximately 25 mol%, and the repeating units of structure (IIIa-1) are present in amounts from approximately 2 mol% to approximately 18 mol%.

[0046] In another aspect of the aforementioned random copolymer, the repeating units have the following structures (Ia), (IIa), and (IIIb):

[0047] [ka] In another aspect of this embodiment, the repeating units of structure (Ia) are present in amounts from approximately 60 mol% to approximately 90 mol%, the repeating units of structure (IIa) are present in amounts from approximately 5 mol% to approximately 25 mol%, and the repeating units of structure (IIIb) are present in amounts from approximately 2 mol% to approximately 18 mol%. In yet another aspect of this embodiment, the repeating units of structure (Ia) are present in amounts from approximately 65 mol% to approximately 85 mol%, the repeating units of structure (IIa) are present in amounts from approximately 5 mol% to approximately 15 mol%, and the repeating units of structure (IIIb) are present in amounts from approximately 10 mol% to approximately 18 mol%.

[0048] In another aspect of the aforementioned random copolymer, the repeating units have the following structures (Ia), (IIa), and (IIIc).

[0049] [ka] In another aspect of this embodiment, the repeating units of structure (Ia) are present in amounts from approximately 60 mol% to approximately 90 mol%, the repeating units of structure (IIa) are present in amounts from approximately 5 mol% to approximately 25 mol%, and the repeating units of structure (IIIc) are present in amounts from approximately 2 mol% to approximately 18 mol%.

[0050] In yet another aspect of this embodiment, the repeating units of structure (Ia) are present in amounts from approximately 65 mol% to approximately 85 mol%, the repeating units of structure (IIa) are present in amounts from approximately 5 mol% to approximately 15 mol%, and the repeating units of structure (IIIc) are present in amounts from approximately 10 mol% to approximately 18 mol%.

[0051] In one of the other embodiments of the random copolymer described herein, the repeating units have the following structures (Ia), (IIa), and (IIId).

[0052] [ka] In another aspect of this embodiment, the repeating units of structure (Ia) are present in amounts from approximately 60 mol% to approximately 90 mol%, the repeating units of structure (IIa) are present in amounts from approximately 5 mol% to approximately 25 mol%, and the repeating units of structure (IIId) are present in amounts from approximately 2 mol% to approximately 18 mol%.

[0053] In yet another aspect of this embodiment, the repeating units of structure (Ia) are present in amounts from approximately 65 mol% to approximately 80 mol%, the repeating units of structure (IIa) are present in amounts from approximately 5 mol% to approximately 15 mol%, and the repeating units of structure (IIId) are present in amounts from approximately 10 mol% to approximately 18 mol%.

[0054] Another aspect of the present invention is a novel composition comprising the random copolymer and an organic spin-casting solvent.

[0055] In another aspect, the novel composition comprises yet another additive, such as a surfactant, a leveling agent, or a stabilizer. In one aspect of this embodiment, it includes a surfactant as an additive to facilitate coating.

[0056] In another aspect of the novel composition, the organic spin-casting solvent is capable of dissolving the random copolymer and any additional components as described above. This organic spin-casting solvent may be a single solvent or a mixture of several solvents. Suitable solvents are organic solvents, including, 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 hydroxyglycerides. Examples include methyl lactate, ethyl lactate (EL), ethyl glycolate, and ethyl 3-hydroxypropionate; ketone esters, such as methyl pyruvate or ethyl pyruvate; 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 methyl diacetone alcohol 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.

[0057] In one other aspect of the novel composition, the random copolymer constitutes about 0.1% to about 2% by weight of the total weight of the composition, including the organic spin-casting solvent. In another aspect, it constitutes about 0.1% to about 1% by weight. In yet another aspect, it constitutes about 0.2% to about 0.5% by weight. In yet another aspect, it constitutes about 0.2% to about 0.3% by weight.

[0058] Another aspect of the present invention is a method for forming a crosslinked copolymer layer on a substrate using the novel compositions described herein, the following steps: a) A step of forming a coating of the novel composition described herein on a substrate; b) A step of heating the coating at a temperature in the range of about 90°C to about 180°C to remove the solvent; c) Heating the coating at a temperature in the range of approximately 200°C to approximately 350°C to form a crosslinked copolymer coating layer or pinned MAT layer; The method includes the above.

[0059] Another aspect of the present invention, which also utilizes the novel compositions described herein, is a chemoepitaxy-induced self-assembly method for block copolymer layers used to form an image, the following steps: a-1) A step of coating the substrate with a graftable neutral layer polymer precursor to form a coat layer 1; b-1) A step of heating the coating layer 1 at a temperature between 90°C and 180°C to remove the solvent; c-1) After step b-1), heat the coating layer 1 to a temperature of about 200°C to about 350°C, preferably up to about 330°C, to induce grafting; d-1) After step c-1), the coating layer 1 is treated with an organic solvent to remove the ungrafted neutral layer polymer, leaving an insoluble grafted neutral layer on the substrate; e-1) A step of coating the grafted neutral layer with a negative-type photoresist layer; f-1) A negative pattern is formed in the photoresist layer, thereby forming a grafted neutral layer with areas covered by the photoresist and areas that are not covered, wherein the pattern in the photoresist includes both small nanometer-sized repeating patterns and larger areas where the photoresist was removed during the imaging process, which does not include the repeating nanometer-sized patterns; g-1) Etching and removing the neutral layer regions that were not covered in step f-1), thereby leaving the exposed substrate in these regions; h-1) After step g-1), the photoresist is peeled off from the substrate, leaving the patterned substrate. In this patterned substrate, the areas of the substrate that were not covered with photoresist in step f-1) do not contain the grafted neutral layer, and the areas covered with photoresist in step f-1) retain the grafted neutral layer; i-1) A step of coating the patterned substrate with the novel composition described herein to form a coat layer 2; j-1) A step of heating the coating layer 2 at a temperature of approximately 90°C to approximately 180°C to remove the solvent; k-1) The coating layer 2 is heated at a temperature of approximately 200°C to approximately 350°C for approximately 1 to approximately 10 minutes to leave an insoluble crosslinked pinned MAT layer on the substrate in a region that does not contain the grafted neutral layer, thereby producing a substrate having both a pinned MAT layer region and a neutral layer region; l-1) A step of applying a coating of a block copolymer comprising an etchable styrene-based block and a highly etchable aliphatic block onto the substrate comprising a patterned neutral layer and a pinned MAT layer to produce a substrate comprising a patterned neutral layer and a patterned pinned MAT layer; m-1) The block copolymer layer is annealed until induced self-assembly occurs in the small nanometer-sized repeating pattern of the substrate, but vertical orientation of the block copolymer domains does not occur in the larger region including the pinned MAT layer; step; o-1) Etching the block copolymer to remove highly etchable blocks of the copolymer and form a repeating nanometer-sized pattern in the region where induced self-assembly of the block copolymer occurred on the substrate in step m-1); The method includes the above.

[0060] The chemoepitaxy-induced self-assembly method for block copolymer layers used to form an image, using the novel compositions described herein, is as follows: a-2) A coating of a neutral layer polymer precursor is formed, wherein the neutral layer polymer precursor is crosslinkable or crosslinkable and graftable onto a substrate; b-2) A step of heating the crosslinkable neutral polymer layer precursor coating, or the crosslinkable and graftable precursor coating, at a temperature of 90°C to 180°C to remove the solvent; c-2) A step of heating the crosslinkable neutral layer polymer precursor coating, or the crosslinkable and graftable coating precursor coating, at a temperature of 200°C to 330°C to form a crosslinked neutral layer, or a crosslinked and grafted neutral layer; d-2) A step of applying a negative-type photoresist layer coating onto the crosslinked neutral layer or the crosslinked and grafted neutral layer; e-2) A negative pattern is formed in the photoresist layer to form regions where a crosslinked neutral layer or a crosslinked and grafted neutral layer is covered by the photoresist, and regions where a crosslinked neutral layer or a crosslinked and grafted neutral layer is not covered by the photoresist, wherein the pattern in the photoresist consists of small nanometer repeating patterns and larger regions where the photoresist is removed during the image formation process, and which do not contain repeating nanometer-sized patterns; f-2) Etching with plasma to remove the neutral layer region not covered in step e-2), thereby removing the crosslinked neutral layer or the crosslinked and grafted neutral layer, leaving the exposed substrate in the region not covered in step e-2); g-2) After step f-2), the photoresist is peeled off the substrate, leaving the patterned substrate, wherein the areas of the substrate left uncovered by the photoresist in step e-2) do not contain a crosslinked neutral layer or a crosslinked and grafted neutral layer, and the areas covered by the photoresist in step f2) retain a crosslinked neutral layer or a crosslinked and grafted neutral layer; h-2) The step of coating the patterned substrate with the novel composition described herein to form a coat layer 3; i-2) A step of heating the coating layer 3 at a temperature of approximately 90°C to approximately 180°C to remove the solvent; j-2) The coat layer 3 is heated at a temperature in the range of about 200°C to about 350°C, preferably for about 1 to about 10 minutes, to form an insoluble crosslinked pinned MAT layer on the substrate in a region that does not contain the grafted neutral layer, thereby producing a substrate that includes both the pinned MAT layer region and the neutral layer region; k-2) A step of applying a coating of a block copolymer comprising an etchable styrene-based block and a highly etchable aliphatic block onto the substrate comprising a patterned neutral layer and a pinned MAT layer; l-2) Anneal the block copolymer until induced self-assembly occurs in the small nanometer-sized repeating pattern of the substrate, but vertical orientation of the block copolymer domains does not occur in the larger region containing the grafted pinned MAT layer; step; m-2) Etching the block copolymer to remove highly etchable blocks of the copolymer and form a repeating nanometer-sized pattern in the region where induced self-assembly of the block copolymer occurred in step l-2); Includes.

[0061] The chemoepitaxy-induced self-assembly method for block copolymer layers used to form an image, using the novel compositions described herein, is as follows: a-3) The step of forming a film by forming a coating of the novel composition described herein on a substrate, b-3) A step of baking the film at a temperature of approximately 200°C to approximately 350°C for approximately 1 to approximately 10 minutes to form an insoluble crosslinked pinned MAT layer. c-3) A step of applying a positive or negative photoresist layer to the crosslinked pinned MAT layer, d-3) A negative image or a positive image is formed in the negative or positive photoresist layer, thereby forming a region where the crosslinking pinning layer is covered with photoresist and a region where the crosslinking pinning layer is not covered with photoresist, step e-3) Etching is performed using plasma to remove the crosslinked pinned MAT layer in the region not covered in step d-3), and to form a patterned crosslinked pinned MAT layer, leaving the crosslinked pinned MAT layer in the region that was covered in step d-3). f-3) A step of coating the patterned crosslinked pinned MAT layer with a neutral layer coating, g-3) The neutral layer coating is cured and the uncured neutral layer is removed by washing with a solvent to form a neutral induction layer in the area of ​​the substrate not covered by the patterned crosslinked pinned MAT layer, thereby forming a chemoepitaxy induction layer on the substrate, step h-3) A step of coating the chemoepitaxy induction layer with a block copolymer solution to form a block copolymer coating. i-3) Annealing the block copolymer coating to form an induced self-assembly film of the block copolymer on the chemoepitaxy induction layer, j-3) Etching the block copolymer to remove highly etchable blocks of the copolymer, thereby forming a repeating nanometer-sized pattern in the region where induced self-assembly of the block copolymer occurred on the substrate in step h-3), Includes.

[0062] In one of the other aspects of the chemoepitaxy process described herein, including steps a-1) to o-1), steps a-2) to m-2), or steps a-3) to j-3), the bake time in the pinned MAT layer bake process j-1), j-2), or b-3) may be varied between about 2 minutes and about 7 minutes in one embodiment, and between about 2 minutes and about 5 minutes in one embodiment.

[0063] In one other aspect of the chemoepitaxy process, the crosslinked pinned MAT layer in step c), k-1), j-2), or b-3) has a thickness of about 5 nm to about 20 nm. In another aspect, it has a thickness of about 7 nm to about 14 nm.

[0064] In one aspect of the chemoepitaxy process comprising steps a-1) to o-1), a-2) to m-2), or a-3) to j-3), the substrate is described below as being preferable. For example, a semiconductor substrate such as silicon can be used. Another example is that the substrate is a metal. Yet another example is that the substrate is a metal oxide. Yet another example is that this is SiN. Yet another example is that this is an organic coating such as a bottom anti-reflective coating (BARC).

[0065] In one aspect of the chemoepitaxy process comprising steps a-1) to o-1), a-2) to m-2), or a-3) to j-3), the block copolymer comprising an etchable styrene-based block and a highly etchable aliphatic-based block is described below. In one aspect of this embodiment, this is a block copolymer of styrene and methyl methacrylate.

[0066] In one aspect of the chemoepitaxy process comprising steps a-1) to o-1), steps a-2) to m-2), or steps a-3) to i-3), the annealing of the block copolymer coating may be carried out at a temperature of about 230°C to about 260°C for about 5 minutes to about 30 minutes, respectively, in steps m-1), l-2), or i-3).

[0067] In one aspect of the chemoepitaxy process comprising steps a-1) to o-1), a-2) to m-2), or a-3) to j-3), the self-assembled block copolymer domains are used to provide a selective barrier against etching into the substrate, and this selectivity in etching can be conferred by either different reactivity of the assembled block domains to chemical etchants used to etch the substrate, or different reactivity to a plasma etching step. One example is when one block is a plasma etching-resistant block and the other is highly etchable by plasma. Selective etching into the substrate by the self-assembled block copolymer can be used to provide an image into the substrate. This image can then be used to manufacture a fine electronic device by defining a structure in a particular layer used in a method for manufacturing a memory or logic device.

[0068] In another aspect of the chemoepitaxy process, including steps a-3) to j-3), the patterned crosslinked pinned MAT layer in step c-3) can be coated with a negative or positive resist, imaged and developed, and the resulting patterned resist is used as an etching barrier for generating the patterned crosslinked pinned MAT layer.

[0069] In one aspect of the chemoepitaxy process, including steps a-1) to o-1), a-2) to m-2), or a-3) to j-3), the etching step can be carried out, for example, using plasma or by chemical etching. In the case of positive resists, the tones are reversed to obtain a negative rather than a positive image by using an organic solvent for development instead of a TMAH-based developer. The radiation used to form the photoresist pattern can also be selected from electron beams, broadband, 193 nm immersion lithography, and 13.5 nm, 193 nm, 248 nm, 365 nm, and 436 nm radiation.

[0070] Another aspect of the present invention is the use of the copolymer or composition described above for coating a substrate, preferably in a chemoepitaxy process.

[0071] While not theoretically constrained, generally speaking, if a substrate has a more suitable interfacial energy for one domain of a lamellar-forming diblock copolymer than for the other, the interaction between the substrate and the suitable domain will orient the lamellae parallel to the substrate in the thin film, rather than perpendicularly. This parallel shape of the thin film has three typical structures, e.g., asymmetric, symmetric, and hole-island structures, depending on the BCP film thickness and the interfacial energy between the BCP domains and the surrounding environment (e.g., air or N2). On a substrate grafted with polystyrene (PS), coated with BCP, and annealed in an N2 atmosphere, the PS domains and PMMA domains have the same interfacial energy. As a result, both PS and PMMA domains can be arranged in an orientation parallel to the substrate surface.

[0072] In the large areas where the neutral layer is exfoliated in the above process, the layer of the novel copolymer is crosslinked on the exposed substrate. This crosslinked layer generates an unexpectedly strong, dense, and homogeneous pinned MAT layer, which can be used to avoid defect formation in these large areas that would occur in the case of diblock lamellar-forming block copolymers of styrene blocks (or other etchable polymer blocks with similar polarity to the novel crosslinked layer formed from the novel copolymer described herein) and aliphatic blocks (or other etchable polymer blocks with different polarity from the styrene blocks). The formation of such an unexpectedly strong pinned MAT layer consistently generates a surface that is highly desirable for consistent parallel lamellar orientation of the block copolymer across the entire large area having the crosslinked pinned MAT layer formed from the novel copolymer described herein. These parallel lamellar orientations result in a block copolymer coating that provides consistent etching rates across the entire area during pattern etching, along with its orientational uniformity. This uniformity of etching of the block copolymer coating over a wide area prevents the formation of defect regions with inconsistent etching rates. This would occur if the block copolymer coating formed self-assembled island or hole structure shapes during self-assembly. Such shapes would occur on the substrate in the case of a given coating of a lamellar-forming diblock copolymer having a given Lo, which would otherwise form either an asymmetric or symmetric structure with parallel lamellar orientation of the block copolymer domains over good pinning areas. Therefore, in the crosslinked pinned MAT layer formed from the novel styrene-based polymer, a remarkably strong and homogeneous pinned MAT layer is formed, resulting in the consistent formation of parallel lamellar formations over large areas that do not contain nanometer-sized repeating patterns such as lines and spaces or trenches.

[0073] In the chemoepitaxy process described herein using the novel composition, the block copolymer used in combination with the novel composition, which can form a pinned MAT layer, can be any block copolymer that can form domains through self-assembly. Microdomains are formed by blocks of the same type that tend to self-associate. Typically, block copolymers used for this purpose are polymers in which repeating units derived from monomers are arranged in blocks that differ in composition, structure, or both, and which are capable of phase separation and domain formation. These blocks have different properties, such as one block being removed while the other remains on the surface and can thus be used to provide a pattern on the surface. Therefore, the blocks can be selectively removed by plasma etching, solvent etching, developer etching with an aqueous alkaline solution, etc. In organic monomer-based block copolymers, one block can be made of polyethers, including poly(alkylene oxides) such as poly(ethylene oxide), poly(ethylene oxide), poly(propylene oxide), poly(butylene oxide), and mixtures thereof, as well as poly(alkylene oxides), which also include polydienes; other blocks can be made of different monomers, including poly((meth)acrylate), polystyrene, polyester, polyorganosiloxane, polyorgano-Germane, and / or mixtures thereof. Each of these blocks in the polymer chain can contain one or more repeating units derived from the monomer. Different types of block copolymers can be used depending on the required pattern and the type of method used. For example, these may include diblock copolymers, triblock copolymers, terpolymers, or multiblock copolymers. Each block of these block copolymers may itself be composed of a homopolymer or copolymer.Different types of block copolymers can also be used for self-assembly, such as tree-like block copolymers, hyperbranched block copolymers, grafted block copolymers, organic diblock copolymers, organic multiblock copolymers, linear block copolymers, star-shaped block copolymers, amphiphilic inorganic block copolymers, amphiphilic organic block copolymers, or mixtures consisting of at least different types of block copolymers.

[0074] Each block of the organic block copolymer may contain repeating units derived from monomers such as C2-C30 olefins, (meth)acrylate monomers derived from C1-C30 alcohols, and inorganic monomers, including those based on Si, Ge, Ti, Fe, and Al. Monomers based on C2-C30 olefins can constitute highly etching-resistant blocks on their own or in combination with one other olefinic monomer to form such blocks. Specific examples of this type of olefinic monomer include ethylene, propylene, 1-butene, 1,3-butadiene, isoprene, dihydropyran, norbornene, maleic anhydride, styrene, 4-hydroxystyrene, 4-acetoxystyrene, 4-methylstyrene, alpha-methylstyrene, or mixtures thereof. Examples of highly etchable units can be derived from (meth)acrylate monomers, such as (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, hydroxyethyl (meth)acrylate, or mixtures thereof.

[0075] Examples that help illustrate one type of block copolymer containing highly etchable repeating units would be polystyrene blocks containing only repeating units derived from styrene, and other types of highly etchable polymethyl methacrylate blocks containing only repeating units derived from methyl methacrylate. Together, these form the block copolymer poly(styrene-b-methyl methacrylate), where b refers to the block.

[0076] Non-limiting examples of block copolymers useful for the chemoepitaxy process described herein, including regions of a patterned neutral layer and regions of the patterned novel crosslinked pinned MAT layer, include poly(styrene-β-vinylpyridine), poly(styrene-β-butadiene), poly(styrene-β-isoprene), poly(styrene-β-methyl methacrylate), poly(styrene-β-alkenyl aromatics), poly(isoprene-β-ethylene oxide), poly(styrene-β-(ethylene-propylene)), and poly(ethylene oxide-β-caprolactone). Examples include poly(butadiene-b-ethylene oxide), poly(styrene-bt-butyl(meth)acrylate), poly(methyl methacrylate-bt-butyl methacrylate), poly(ethylene oxide-b-propylene oxide), poly(styrene-b-tetrahydrofuran), poly(styrene-b-isoprene-b-ethylene oxide), poly(styrene-b-dimethylsiloxane), poly(methyl methacrylate-b-dimethylsiloxane), or combinations containing at least one of the above block copolymers. All of these polymeric materials have in common the presence of at least one block rich in repeating units that is resistant to etching techniques typically used in the manufacture of IC devices, and at least one block that is rapidly etched under the same conditions. This allows the induced self-assembled polymer to be pattern-transferred onto a substrate, resulting in either pattern modification or pattern multiplication.

[0077] In the chemoepitaxy process described herein, the molecular weight characteristics suitable for block copolymers are weight-average molecular weight (M) ranging from approximately 3,000 to approximately 500,000 g / mol. w ) and number-average molecular weight (M) from approximately 1,000 to approximately 60,000. n ) and polydispersity (M) from about 1.01 to about 6 or from 1.01 to about 2 or from 1.01 to about 1.5 w / M n ) is the molecular weight M w and M n Both can be measured, for example, by gel transmission chromatography using a general calibration method calibrated against a polystyrene standard. This ensures that the polymer block has sufficient mobility to self-assemble, either spontaneously when applied to a given surface, by using purely thermal treatment, or via a thermal process assisted by allowing solvent vapors to be absorbed into the polymer framework to enhance the flow of segments so that self-assembly occurs.

[0078] Suitable solvents for dissolving these block copolymers for film formation may vary depending on the requirements for the solubility of the block copolymer. Examples of solvents for block copolymer assembly include propylene glycol monomethyl ether acetate (PGMEA), ethoxyethyl propionate, anisole, ethyl lactate, 2-heptanone, cyclohexanone, amyl acetate, n-butyl acetate, methyl n-amyl ketone (MAK), gamma-butyrolactone (GBL), toluene and analogues, and combinations thereof. In one embodiment, particularly useful casting solvents include propylene glycol monomethyl ether acetate (PGMEA), gamma-butyrolactone (GBL), or combinations thereof.

[0079] The block copolymer composition may include an inorganic polymer; additives such as small molecules, inorganic molecules, surfactants, photoacid generators, thermoacid generators, quenchers, curing agents, crosslinking agents, chain expanders and similars; and additional components and / or additives selected from the group of combinations including at least one of the above, wherein one or more of the above additional components and / or additives co-assemble with the block copolymer to form a block copolymer assembly.

[0080] The block copolymer composition is applied to a patterned substrate including a region of a patterned neutral layer, and the region of the patterned novel copolymer pinned MAT layer is defined on the surface by conventional lithography as described above, where the neutral layer surface is formed by the material described above, and the pinned MAT layer is formed by the composition containing the novel copolymer described herein. Upon application and solvent removal, the block copolymer self-assembles, induced by the specific pattern formed on the neutral layer by conventional lithography, via the patterned chemical differences on the substrate surface generated by the conventional lithography process. Depending on the relative pitch between the pattern and the microphase separation distance after standard IC processing for pattern transfer, pattern modification with the same resolution can be achieved, and / or pattern multiplication can also be achieved if multiphase boundaries are formed between the figures defined by conventional lithography.

[0081] The application of block copolymers by spin technology (including spin-drying) may be sufficient to form self-inductive block copolymer assemblies. Other methods of self-inductive domain formation may occur during application, baking, annealing, or a combination of one or more of these operations. Thus, oriented block copolymer assemblies are prepared by the above methods, which have microphase-separated domains containing cylindrical microdomains or lamellar domains oriented perpendicular to the neutral surface. Generally, the microphase-separated domains are lamellar domains oriented perpendicular to the neutral surface, which provide a line / space pattern parallel to the block copolymer assembly. It is desirable that the thus oriented domains be thermally stable under subsequent processing conditions. Therefore, a layer of block copolymer assembly containing a useful diblock copolymer, such as poly(styrene-β-methyl methacrylate), can be coated and optionally baked and / or annealed to give the substrate surface domains that are formed on the neutral surface and remain perpendicular thereto, providing highly etchable and highly etchable regions, which can then be further pattern-transferred into the substrate layer. The induced self-assembled block copolymer pattern is transferred into the underlying substrate using known techniques. In one example, wet or plasma etching can be used in conjunction with optional UV exposure. Wet etching can be performed using acetic acid. Standard plasma etching processes such as oxygen-containing plasmas may be used; additionally, argon, carbon monoxide, carbon dioxide, CF4, and CHF3 may be present in the plasma.

[0082] In the present invention, the initial negative or positive-tone photoresist pattern used for forming an induced self-assembly pattern can be defined by using either a negative or positive-type photoresist that can be imaged using any conventional lithography technique, such as electron beam, ion beam, X-ray, EUV (13.5 mm), broadband, or UV (450 nm-10 nm) exposure, or immersion lithography, in a negative-tone or positive-tone development process. In one embodiment, the present invention is particularly useful for 193 nm image-like exposure using either dry lithography or immersion lithography. For 193 nm lithography, commercially available positive-type 193 nm photoresists, such as AZ AX2110P (available from EMD Performance Materials Corp, Somerville, NJ), Shin-Etsu Chemical Co., Ltd.'s photoresists, JSR Micro from Nippon Synthetic Rubber Co., Ltd., and other photoresists available from Fujifilm, TOK, etc., can be used. These photoresists can be developed after exposure and after post-exposure baking using an aqueous alkaline developer containing tetramethylammonium hydroxide to produce positive-tone patterns, or developed using organic solvents such as methyl n-amyl ketone (MAK), n-butyl acetate, or anisole to produce negative-tone patterns. Alternatively, commercially available negative-tone photoresists may be used for 193 nm exposure as well.

[0083] The substrates useful for the novel coatings and chemoepitaxy processes described herein are any required for the manufacture of IC devices. For example, the substrate is a wafer coated with a layer of high-carbon-content silicon or titanium-containing ARC (highly etchable to oxygen plasma), which allows for the transfer of patterns of patterned block copolymers into these coatings. Suitable substrates include, but are not limited to, silicon, silicon substrates coated with metal surfaces, copper-coated silicon wafers, copper, aluminum, polymer resins, silicon dioxide, metals, doped silicon dioxide, silicon nitride (SiN), silicon carbide, tantalum, polysilicon, ceramics, aluminum / copper mixtures, glass, coated glass; gallium arsenide; and other such Group III / V compounds. These substrates may be coated with anti-reflective coatings. The substrate may contain any number of layers made from the aforementioned materials.

[0084] In the present invention, various processes including pinned chemoepitaxy can be used to achieve induced self-assembly of the block copolymer using the novel styrene-based polymer composition along with known neutral layers described in US8,835,581 (Patent Document 1), US9,181,449 (Patent Document 2), US9,093,263 (Patent Document 3), US8691925 (Patent Document 4), US20140335324A1 (Patent Document 5), US2016-0122579A1 (Patent Document 6), or US14 / 885,328 (Patent Document 7). The contents of these patent documents are included in their entirety in this specification. This pattern can then be further transferred onto a substrate. In this method, various high-resolution figures can be pattern-transferred onto a substrate to achieve pattern adjustment, pattern multiplication, or both.

[0085] As will be described more specifically in the examples, it has been confirmed that when a composition containing the novel random copolymer described herein is used as a pinning underlayer in a chemoepitaxy process, the composition enables pre-pattern design flexibility. Conventional pinning MAT layers containing a high content of non-polar aromatic hydrocarbon monomers have slow etching rates, which causes residue problems during pre-pattern generation in chemoepitaxy. The novel material disclosed herein will eliminate residue due to its easy etching ability and, as a result, the homogeneous assembly of line-and-space CD of block copolymer domains.

[0086] Crosslinkable polystyrene pinned MATs are used to develop pre-patterns for L / S DSA. While copolymers of styrene and vinylbenzocyclobutene were effectively used in the LiNe flow process for DSA for patterning, the crosslinked underlayers are difficult to etch while trimming the pattern after resist patterning and DSA pattern transfer. Due to the slow etching rate, such copolymers consisting of completely hydrophobic styrene-based repeating units make patterning difficult and lead to poor topography. Alternative pinned materials were fabricated by adding acrylate monomers, resulting in faster etching rates and improved topography. This novel material also exhibits improved edge placement errors and results in an improved BCP structure with minimal CD difference between guided and unguided lines. [Examples]

[0087] Lithography exposure was performed using an ASML NXT1950i (ASML Veldhoven, De Run 65015504 DR, Veldhoven, The Netherlands). Etching experiments were performed using a LAM Kiyo E5 (4650 Cushing Parkway Fremont, CA 94538 USA). Spin coating and development of the films and patterns were performed using a SCREEN SOKUDO Duo truck (SCREEN Semiconductor Solutions Co., Ltd., 1-1 Tenjin Kitamachi, 4-chome, Horikawa-dori Teranouchi-agaru, Kamigyo-ku, Kyoto, Japan) or a TEL ACT-12 (Tokyo Electron Limited, 107-6325, Akasaka Biz Tower, 5-3-1 Akasaka, Minato-ku, Tokyo). The photoresist pattern was removed using AQUASPIN manufactured by SCREEN (SCREEN Semiconductor Solutions Co., Ltd., 1-1 Tenjin-Kita-cho, 4-chome, Horikawa-dori Teranouchi-agaru, Kamigyo-ku, Kyoto, Japan). Scanning electron microscope images were obtained using a Hitachi H-5000 (Hitachi High Technologies America Inc., 10 North Martingale Road, Suite 500, Schaumburg, Illinois 60173-2295).

[0088] Synthesis of block copolymers and neutral brushes Neutral underlayer synthesis example 1: Synthesis of P(S-co-PMMA) brush-type neutral layer polymer A 2000 ml flask equipped with a condenser, temperature controller, heating mantle, and mechanical stirrer was set up. 400 g (3.84 mol) of styrene (S), 401 g (4 mol) of methyl methacrylate (MMA), 9.44 g (0.016 mol) of nitroxide initiator, and 534 g of anisole were added to the flask. The mechanical stirrer was switched on and set to approximately 120 rpm. The reaction solution was then degassed by vigorously bubbling nitrogen into the solution at room temperature for approximately 30 minutes. After 30 minutes of degassing, the heating mantle was switched on, and the temperature controller was set to 140°C. The stirred reaction mixture was maintained at this temperature for 20 hours. After this time, the heating mantle was switched off, and the reaction solution was allowed to cool to approximately 40°C. The reaction mixture was then poured into 13 L of isopropanol, with mechanical stirring during the addition. During this addition, polymer precipitated. The precipitated polymer was collected by filtration. The collected polymer was dried in a vacuum furnace at 40°C. Approximately 500 grams of polymer were obtained. This dried polymer was dissolved in 1500 g of THF and then filtered through a 0.2 μm nylon filter. The filtered solution was then precipitated again in a stirred solution of 13 L of methanol, the precipitated polymer was collected, and dried under vacuum at 40°C as described above. In this way, 400 grams (48% yield) of polymer were obtained after drying. This polymer has a molecular weight of approximately 15k M w It also had a polydispersity (PDI) of 1.5.

[0089] Synthesis of Block Copolymer 1 (Anionic Copolymer of Styrene and Methyl Methacrylate) P(Sb-MMA)(21K-b-24K) was synthesized using the same procedure as in the previous example. Briefly, 20 g (0.192 mol) of styrene was polymerized with 0.68 mL (1.4 M solution) of sec-butyllithium. Then, 0.196 g (0.0011 mol) 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 reddish-brick color. This suggested that the styryllithium active center was converted to a delocalized DPE-added carbanion. After stirring for 2 minutes, 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 an ampoule. This reaction was stopped after 30 minutes with 1 mL of degassed methanol. The block copolymer was recovered by precipitation in excess isopropanol (five times the amount of polymer solution) containing 10% water, filtered, and dried under vacuum at 70°C for 12 hours to obtain 40 g of P(Sb-MMA) (yield 94%).

[0090] Comparative Example 1: Synthesis of Comparative Polymer 1 (Copolymer of Styrene and 4-Vinylbenzocyclobutene) 660.3 g of styrene (≥99%, stabilized with 4-tert-butylcatechol) was weighed into a 3 L volume four-neck flask equipped with a condenser, temperature controller, and mechanical stirrer, and fixed to a heating mantle. 65 g of vinylbenzocyclobutene (VBCB), 11.23 g of azobisisobutyronitrile (AIBN), and 900 g of 2-butanone (MEK) were added to the flask. The reaction solution was degassed by vigorously bubbling nitrogen into it at room temperature for about 30 minutes using mechanical stirring. The reaction was then heated to 80°C under nitrogen for 20 hours, and then cooled to 40°C. The reaction mixture was then precipitated in isopropanol, filtered, and dried in a vacuum furnace. Mw 18,500 g / mol, PD 1.8.

[0091] Synthesis of novel copolymers The novel copolymers (Examples 1-13) were prepared in yields of 60% to 70% by radical copolymerization of polystyrene and 4-vinylbenzocyclobutene (VBCB) with polar methacrylate monomers listed in Tables 1 and 2, which are more readily plasma-etched due to their relatively high oxygen atom content. However, the introduction of these polar methacrylate monomers into these copolymers reduces the hydrophobicity of the polymers, resulting in reduced pinning strength. Tables 1 and 2 detail the characteristics of these novel copolymers and the layers they form, which offer the best compromise between desirable hydrophobicity retention and improved etchability. For comparison, these tables also show data for Comparative Example 1, a copolymer of ethylene and 4-vinylbenzocyclobutene, which has higher plasma etching resistance and reduced etchability due to its lack of oxygen atoms.

[0092] Example 1: Synthesis of Copolymer 1 0.86 g of styrene (≥99%, stabilized with 4-tert-butylcatechol) was weighed into a round-bottom flask along with 4.56 g of vinylbenzocyclobutene (VBCB), 2.13 g of butyl methacrylate (99%, stabilized with monomethyl etherhydroquinone), 0.41 g of azobisisobutyronitrile (AIBN), and 100 g of anisole. The flask was closed with a three-way stopper, briefly degassed, and flushed with argon. The mixture was frozen in a liquid nitrogen bath under vacuum and thawed three times to remove residual water and impurities. The reaction was then heated to 73°C under nitrogen for 18 hours. The reaction mixture was then precipitated in isopropanol, filtered, and dried overnight in a vacuum oven. See Table 1 for composition and molecular weight.

[0093] Example 2: Synthesis of Copolymer 2 41.68 g of styrene (≥99%, stabilized with 4-tert-butylcatechol) was weighed into a round-bottom flask along with 6.51 g of vinylbenzocyclobutene (VBCB), 7.11 g of butyl methacrylate (99%, stabilized with monomethyl etherhydroquinone), 0.41 g of azobisisobutyronitrile (AIBN), and 100 g of anisole. The flask was closed with a three-way stopper, briefly degassed, and flushed with argon. The mixture was frozen in a liquid nitrogen bath under vacuum and thawed three times to remove residual water and impurities. The reaction was then heated to 73°C under nitrogen for 18 hours. The reaction mixture was then precipitated in isopropanol, filtered, and dried overnight in a vacuum oven.

[0094] Example 3: Synthesis of Copolymer 3 40.62 g of styrene (≥99%, stabilized with 4-tert-butylcatechol) was weighed into a round-bottom flask along with 4.56 g of vinylbenzocyclobutene (VBCB), 10.66 g of butyl methacrylate (99%, stabilized with monomethyl etherhydroquinone), 0.41 g of azobisisobutyronitrile (AIBN), and 100 g of anisole. The flask was closed with a three-way stopper, briefly degassed, and flushed with argon. The mixture was frozen in a liquid nitrogen bath under vacuum and thawed three times to remove residual water and impurities. The reaction was then heated to 73°C under nitrogen for 18 hours. The reaction mixture was then precipitated in isopropanol, filtered, and dried overnight in a vacuum oven. See Table 1 for composition and molecular weight.

[0095] Example 4: Synthesis of Copolymer 4 43.23 g of styrene (≥99%, stabilized with 4-tert-butylcatechol) was weighed into a round-bottom flask along with 4.56 g of vinylbenzocyclobutene (VBCB), 7.11 g of n-butyl methacrylate (99%, stabilized with monomethyl etherhydroquinone), 0.41 g of azobisisobutyronitrile (AIBN), and 100.21 g of anisole. The flask was closed with a three-way stopper, briefly degassed, and flushed with argon. The mixture was frozen in a liquid nitrogen bath under vacuum and thawed three times to remove residual water and impurities. The reaction was then heated to 73°C under nitrogen for 17 hours. The reaction mixture was then precipitated in isopropanol, filtered, and dried overnight in a vacuum oven. See Table 1 for composition and molecular weight.

[0096] Example 5: Synthesis of Copolymer 5 39.07 g of styrene (≥99%, stabilized with 4-tert-butylcatechol) was weighed into a round-bottom flask along with 6.53 g of vinylbenzocyclobutene (VBCB), 10.65 g of n-butyl methacrylate (99%, stabilized with monomethyl etherhydroquinone), 0.41 g of azobisisobutyronitrile (AIBN), and 100 g of anisole. The flask was closed with a three-way stopper, briefly degassed, and flushed with argon. The mixture was frozen in a liquid nitrogen bath under vacuum and thawed three times to remove residual water and impurities. The reaction was then heated to 73°C under nitrogen for 17 hours. The reaction mixture was then precipitated in isopropanol, filtered, and dried overnight in a vacuum oven. See Table 1 for composition and molecular weight.

[0097] Example 6: Synthesis of Copolymer 6 36.50 g of styrene (≥99%, stabilized with 4-tert-butylcatechol) was weighed into a round-bottom flask along with 9.77 g of vinylbenzocyclobutene (VBCB), 10.67 g of n-butyl methacrylate (99%, stabilized with monomethyl etherhydroquinone), 0.41 g of azobisisobutyronitrile (AIBN), and 100 g of anisole. The flask was closed with a three-way stopper, briefly degassed, and flushed with argon. The mixture was frozen in a liquid nitrogen bath under vacuum and thawed three times to remove residual water and impurities. The reaction was then heated to 73°C under nitrogen for 17 hours. The reaction mixture was then precipitated in isopropanol, filtered, and dried overnight in a vacuum oven. See Table 1 for composition and molecular weight.

[0098] Example 7: Synthesis of Copolymer 7 33.86 g of styrene (≥99%, stabilized with 4-tert-butylcatechol) was weighed into a round-bottom flask along with 13.08 g of vinylbenzocyclobutene (VBCB), 10.66 g of n-butyl methacrylate (99%, stabilized with monomethyl etherhydroquinone), 0.41 g of azobisisobutyronitrile (AIBN), and 100 g of anisole. The flask was closed with a three-way stopper, briefly degassed, and flushed with argon. The mixture was frozen under vacuum in a liquid nitrogen bath, thawing three times, to remove residual water and impurities. The reaction was then heated under nitrogen at 73°C for 17 hours. The reaction mixture was then precipitated in isopropanol, filtered, and dried overnight in a vacuum oven. See Table 1 for composition and molecular weight.

[0099] Example 8: Synthesis of Copolymer 8 46.87 g of styrene (≥99%, stabilized with 4-tert-butylcatechol) was weighed into a round-bottom flask along with 4.58 g of vinylbenzocyclobutene (VBCB), 2.66 g of benzyl methacrylate (99%, stabilized with monomethyl etherhydroquinone), 0.41 g of azobisisobutyronitrile (AIBN), and 101.21 g of anisole. The flask was closed with a three-way stopper, briefly degassed, and flushed with argon. The mixture was frozen in a liquid nitrogen bath under vacuum and thawed three times to remove residual water and impurities. The reaction was then heated to 73°C under nitrogen for 17 hours. The reaction mixture was then precipitated in isopropanol, filtered, and dried overnight in a vacuum oven. See Table 1 for composition and molecular weight.

[0100] Example 9, Synthesis of Copolymer 9 43.24 g of styrene (≥99%, stabilized with 4-tert-butylcatechol) was weighed into a round-bottom flask along with 4.57 g of vinylbenzocyclobutene (VBCB), 8.83 g of benzyl methacrylate (99%, stabilized with monomethyl etherhydroquinone), 0.41 g of azobisisobutyronitrile (AIBN), and 102.21 g of anisole. The flask was closed with a three-way stopper, briefly degassed, and flushed with argon. The mixture was frozen in a liquid nitrogen bath under vacuum and thawed three times to remove residual water and impurities. The reaction was then heated to 73°C under nitrogen for 17 hours. The reaction mixture was then precipitated in isopropanol, filtered, and dried overnight in a vacuum oven. See Table 1 for composition and molecular weight.

[0101] Example 10 Synthesis of Copolymer 3 40.63 g of styrene (≥99%, stabilized with 4-tert-butylcatechol) was weighed into a round-bottom flask along with 4.56 g of vinylbenzocyclobutene (VBCB), 13.22 g of benzyl methacrylate (99%, stabilized with monomethyl etherhydroquinone), 0.41 g of azobisisobutyronitrile (AIBN), and 101.25 g of anisole. The flask was closed with a three-way stopper, briefly degassed, and flushed with argon. The mixture was frozen in a liquid nitrogen bath under vacuum and thawed three times to remove residual water and impurities. The reaction was then heated to 73°C under nitrogen for 17 hours. The reaction mixture was then precipitated in isopropanol, filtered, and dried overnight in a vacuum oven. See Table 1 for composition and molecular weight.

[0102] Example 11: Synthesis of Copolymer 11 40.62 g of styrene (≥99%, stabilized with 4-tert-butylcatechol) was weighed into a round-bottom flask along with 4.56 g of vinylbenzocyclobutene (VBCB), 10.66 g of butyl methacrylate (99%, stabilized with monomethyl etherhydroquinone), 0.41 g of azobisisobutyronitrile (AIBN), and 100 g of anisole. The flask was closed with a three-way stopper, briefly degassed, and flushed with argon. The mixture was frozen under vacuum in a liquid nitrogen bath, thawing three times, to remove residual water and impurities. The reaction was then heated under nitrogen at 73°C for 18 hours. The reaction mixture was then precipitated in isopropanol, filtered, and dried overnight in a vacuum oven. See table for composition and molecular weight.

[0103] Example 12 Synthesis of Copolymer 12 41.68 g of styrene (≥99%, stabilized with 4-tert-butylcatechol) was weighed into a round-bottom flask along with 6.51 g of vinylbenzocyclobutene (VBCB), 5.71 g of ethyl methacrylate (99%, stabilized with monomethyl etherhydroquinone), 0.41 g of azobisisobutyronitrile (AIBN), and 100 g of anisole. The flask was closed with a three-way stopper, briefly degassed, and flushed with argon. The mixture was frozen under vacuum in a liquid nitrogen bath, thawing three times, to remove residual water and impurities. The reaction was then heated under nitrogen at 73°C for 18 hours. The reaction mixture was then precipitated in isopropanol, filtered, and dried overnight in a vacuum oven. See table for composition and molecular weight.

[0104] Example 13 Synthesis of Copolymer 13 40.62 g of styrene (≥99%, stabilized with 4-tert-butylcatechol) was weighed into a round-bottom flask along with 4.56 g of vinylbenzocyclobutene (VBCB), 8.56 g of ethyl methacrylate (99%, stabilized with monomethyl etherhydroquinone), 0.41 g of azobisisobutyronitrile (AIBN), and 100 g of anisole. The flask was closed with a three-way stopper, briefly degassed, and flushed with argon. The mixture was frozen in a liquid nitrogen bath under vacuum and thawed three times to remove residual water and impurities. The reaction was then heated to 73°C under nitrogen for 18 hours. The reaction mixture was then precipitated in isopropanol, filtered, and dried overnight in a vacuum oven. See table for composition and molecular weight.

[0105] [Table 1]

[0106] Lithography and chemoepitaxy processing Figure 1 shows the processing method used for the novel pinned MAT layer composition described herein and for the comparative layer of comparative polymer 1. Specifically, it shows a LiNe flow DSA for a line-and-space multiplication scheme. The conditions used for pre-pattern development and DSA were as follows: a 13 nm thick SiN on silicon was used as the substrate, and the following crosslinkable pinned materials, namely Comparative Example 1 and Example 1, Example 2, or Example 3, were coated to a thickness of 8 nm and cured in N2 at 315°C for 5 minutes to form a crosslinked pinned MAT layer. Lithography of this pinned MAT layer was performed by using AIM-5484 PTD photoresist (JSR Micro, Inc. 1280 N. Mathilda Ave. Sunnyvale, CA940890), coating it to a thickness of 95 nm, and then exposing it with an ASML 1970i (iArF scanner) to form a photoresist pattern exposing the underlying crosslinked pinned MAT layer. The trim etching conditions involved using N2O2 etching chemistry for plasma etching to remove crosslinked pinning material in areas not covered by the patterned photoresist.

[0107] Preparation of compound: The dried copolymers, neutral layer 1, and block copolymer 1 prepared in the above examples (Examples 1 to 13) and Comparative Example 1 were individually weighed into small vials and dissolved in PGMEA at a concentration of 2% by weight. These vials were left on a shaker overnight and then filtered through a PTFE syringe filter.

[0108] Evaluation of crosslinking and neutrality of formulations for forming a pinned MAT layer: The formulations containing the different copolymers described above (Examples 1-13 and Comparative Example 1) were individually coated onto Si wafers at a spin velocity sufficient to obtain a film thickness of approximately 8 nm. These wafers were then baked under nitrogen at 250°C for 1 hour, followed by cleaning with EBR solvent for 2 minutes to form the pinned MAT layer to be evaluated. To determine film loss, these film thicknesses were measured by ellipsometry before and after EBR cleaning.

[0109] To determine neutrality, the MAT pinning layer was evaluated by coating with a formulation containing Examples 1-13 or Comparative Example 1, baking at 250°C for 30 minutes under nitrogen, then washing with EBR solvent (AZ EBR solvent, EMD PM Branchburg, 70 Meister Ave, Somerville, NJ08876) for 2 minutes, baking at a low temperature for drying, and then coating with a neutral polymer formulation (neutral layer 1). To determine if there was any film growth, the film thickness was measured before and after coating with the neutral layer. The film was then coated with a formulation containing block copolymer 1 to form a 35 nm film, which was then annealed at 250°C for 30 minutes under nitrogen. The film was then imaged with CDSEM to determine the structure of BCPs for neutrality evaluation. All tested polymers showed only a small amount of BCP arrangement or no arrangement at all, suggesting that the polymers are non-neutral.

[0110] Photoresist exfoliation was performed using Orgasolv STR 301 (BASF, 100 Park Avenue Florham Park, NJ 07932, USA). The resulting patterned crosslinked pinned MAT layer was then coated with a composition containing a neutral brush (neutral brush 1), baked at 250°C for 30 minutes, and subsequently washed with RER600 (RER 600, Fujifilm, 200 Summit Lake Drive Valhalla, NY 10595) for 30 minutes to form a pattern containing a neutral layer region and a pinned MAT layer region. This pattern was then coated with a composition containing block copolymer 1, baked at 250°C for x minutes to form a baked film with a thickness of 35 nm, and then annealed at 250°C to induce induced self-assembly of the block copolymer domains.

[0111] Table 2 shows a comparison of coatings obtained using the novel copolymers with polar methacrylate monomers introduced between 3 mol% and 15 mol%. These properties include film thickness before and after cleaning, k-value at 193 nm, and WCA (water contact angle). This table shows that all of the novel polymers, Examples 1 to 13, had similar WCA and k-values ​​to Comparative Example 1, which is a copolymer of styrene and 4-vinylbenzocyclobutene. This similarity suggested that these materials would have pinning properties similar to Comparative Example 1, despite the considerable oxygen content imparted by the introduction of polar methacrylate monomers that can promote plasma etching. Therefore, the novel copolymers containing polar methacrylate monomers (Examples 1 to 13) can be coated to form novel hydrophobic crosslinkable underlayer pinning MAT materials for polystyrene domains in PS-b-PMMA DSA, due to the minimal changes in water contact angle and k-value shown in Table 2.

[0112] [Table 2]

[0113] Figure 2 shows a comparison between a coating prepared from Reference Comparative Example 1, which does not exhibit neutrality for coatings of styrene-methyl methacrylate block copolymer (PS-b-PMMA), and coatings prepared from novel materials in the Examples 1, 2, and 3 series (1-3, containing polar n-butyl methacrylate monomer at different concentrations) that exhibit similar behavior.

[0114] The addition of 15 mol% n-butyl methacrylate results in a 10% improvement in etching rate compared to that observed in Comparative Example 1, which is a copolymer of styrene and 4-vinylbenzocyclobutene. This gives an improved topography of the pinned stripes, resulting in more vertical sidewalls compared to the standard, thereby reducing the influence of sidewalls on DSA performance. The DSA process with the polymer with 15% n-BuMA added after N2 / O2 plasma etching for PMMA removal shows minimal size difference between guided and unguided lines.

[0115] Trim etching or dry etching showed improvements of 4–15% compared to the standard pinned MAT layer derived from Comparative Example 1.

[0116] Therefore, adjustable dry etching resistance for pinned MAT layers was achieved depending on the composition of the polar comonomers in the novel copolymer Examples 1 to 13.

[0117] Reduced the use of PMMA spaced CDs and more uniform polystyrene lined CDs across various litho pitches.

[0118] Crosslinking potential and non-neutrality testing for Examples 1, 2, and 3: These copolymers were baked under nitrogen at 250°C for 30 minutes, and their crosslinkability was tested using thin films of approximately 8 nm. The film thickness was measured, and the films were then immersed in a PGMEA solvent. The results showed that these polymers formed good crosslinkable films and remained stable even after immersion in PGMEA, indicating crosslinking (Table 2).

[0119] Specifically, crosslinking immersion tests were performed on MAT pinning layers formed from copolymer examples 1 to 10 or formulations containing comparative example 1 by coating them onto Si, then baking them (250°C / 30 minutes / N22 minutes), and subsequently washing them with EBR70 / 30.

[0120] These copolymers were crosslinked to form the MAT layers to be tested, and then a neutral underlayer (neutral layer 1, consisting of methyl methacrylate and styrene, a hydroxyl-terminated copolymer of PS 50 mol%) was brushed via baking and washing. The crosslinked MAT pinning layers formed from copolymer Examples 1-13 did not react with this brushed neutral material because they lacked functional groups for reaction, and it was expected that the MAT pinning layers formed from formulations including Examples 1-13 would not contain neutral grafts on their surfaces. This was confirmed by coating and baking diblock copolymers to develop the vertical fingerprint shape of the block copolymer domains. All of these copolymers did not exhibit a fingerprint shape, but rather a parallel shape. This suggests that their surfaces are hydrophobic and can selectively pinch the polystyrene domains of the PS-b-PMMA diblock copolymer.

[0121] Comparison of etching speeds: The polymer was dissolved in PGMEA and coated onto an 8-inch Si wafer to a thickness of approximately 100 nm. The wafer was soft-baked at 110°C for 1 minute, followed by annealing under nitrogen at 250°C for 30 minutes. The bulk etching rate of the polymer film was determined by O2 (50 sccm) plasma etching from 0 to 60 seconds (increments of 10 seconds). Film thickness was determined by ellipsometry.

[0122] Table 3 shows a comparison of the normalized etching rates of MAT pinning layers formed from formulations containing polar methacrylate monomers (Examples 1 to 13) compared to a reference material (Comparative Example 1), which is a copolymer of styrene and 4-vinylbenzocyclobutene and does not contain polar methacrylate monomers.

[0123] These etching rates were determined by providing the bulk etching rate in nm / second from the graphed film thickness gradient with respect to etching time. The etching rates were then normalized by dividing them by the etching rate of the reference material (Comparative Example 1). The normalized etching rates are shown in Table 3.

[0124] Figure 3 shows a comparison of etching rates and normalized etching rates, illustrating the improvement in bulk etching rates of the Examples 1 to 13 series compared to Comparative Example 1 (Conditions: ACT12: 110°C / 1 min, 250°C / 30 min (N2), Trion Etcher: Pressure = 70 mT; Top / Bottom (W) = 50 / 50; O2 (sccm) = 50).

[0125] As shown in Figure 3, the etching rate improves with the addition of polar components to the novel copolymer in the Examples 1 to 13 series. This is due to the increased rate of decomposition of the polar portion compared to the aromatics during etching. The etching rate can be further improved by increasing the ratio of polar portion to non-polar portion in the polymer.

[0126] The etching rate and normalized etching rate were also determined for the comparative sample after annealing under nitrogen at 250°C for 60 minutes, as shown in Figure 4. This showed a similar improvement in etchability compared to Comparative Example 1, which was a copolymer of styrene and 4-vinylbenzocyclobutene. (Conditions: ACT12: 110°C / 1 min, 250°C / 30 min (N2), Trion Etcher: Pressure = 70 mT; Top / Bottom (W) = 50 / 50; O2 (sccm) = 50).

[0127] Figure 4 shows the etching rates of the reference material compared to the example and comparative examples. As can be seen in the graph, the addition of polar moieties increases the etching rate compared to the reference material, and a subsequent increase in the ratio of polar moieties to non-polar moieties further enhances this. However, the structure of the polar monomer has a significant effect on the etching rate. The addition of similar amounts of different polar compounds leads to very different etching rates, namely, a comparison of the etching rates between Example 2 and Comparative Example 2. A summary of the normalized etching rates for each synthesized copolymer versus Comparative Example 1 is shown in Table 1.

[0128] Table 3 shows the normalized etching rates of novel copolymers Examples 1 to 12 containing polar methacrylate monomers, compared to Comparative Example 1, which is a copolymer of styrene and 4-vinylbenzocyclobutene.

[0129] [Table 3]

[0130] DSA Process Window Evaluation: The DSA process window was inspected on patterned SiN wafers to evaluate various combinations of pitch and etching dose. DSA prepatches were fabricated for DSA via lithography using the LiNe flow process shown in Figure 1. Briefly, SiN (13 nm) was coated onto the Si wafer, followed by a crosslinkable PS mat at 8 nm, and then baked at 315°C for 5 minutes under nitrogen. Guidelines were formed by imaging AIM-5484PTD photoresist (95 nm) with ASML 1970i, followed by exfoliation with N2O2 trim etch and STR Orgasolv, and IPA cleaning to form a 90 nm pitch guide pattern of the relevant xPS material. A formulation containing neutral layer polymer 1 (neutral brush) was coated onto the wafer, baked at 250°C for 30 minutes, and excess was washed off with RER600 to obtain the DSA chemical prepatches. Finally, the mixture containing block copolymer 1 (PS 43%, FT 35nm) was coated and annealed at 250°C for 5 or 30 minutes.

[0131] The critical dimension (CD) of the formed BCP line was determined for post-development inspection (ADI), pre-etching inspection, and post-etching inspection (AEI). The following figures show the dose (mJ / cm²) for Examples 1, 2, and 3, which contain polar methacrylate monomer, compared to those observed using Comparative Example 1, which does not contain polar methacrylate monomer. 2 This shows how CD changes with ). In each case, CD is slightly larger in Example 3 compared to the other materials.

[0132] Figure 5 compares the lithography performance at P90nm. Example 3 yields a higher ADI / CD than other novel polymers.

[0133] Figure 6 compares lithography performance at P90nm, and in this case as well, Example 3 yields a higher post-etching inspection (AEI) CD than the other Examples 1, 2, or Comparative Example 1.

[0134] Figure 7 shows the DSA process window of the novel pinned MAT pinning layers derived from Examples 1, 2, and 3, compared to the MAT pinning layer derived from Comparative Example 1. The DSA dislocation ratio was evaluated after N2O2 etching for PMMA removal. The process window was found to be in a similar region for each material, except for the formulation based on Example 3, which showed a slight shift. This means that despite the increased polarity and hydrophobicity of the pinning material, these polymers remained non-neutral, and their pinning strength was sufficient to maintain without affecting the DSA process window.

[0135] DSA limit dimension (CD) variation: Figure 8 shows the average CD and 3σ of DSA lines formed using Comparative Example 1 and Examples 1, 2, and 3. This indicates that the DSA line widths in the guided (pinned) and unguided (unpinned) regions were also compared. Line CD values ​​were determined by averaging 10 lines from each of the 30 images. The images below show the line CD and 3σ from these images. No significant differences in CD are observed. Figure 9 shows examples of guided and unguided DSA lines formed and used in the above CD evaluation. This application relates to the invention described in the claims, but the disclosure of this application also includes: 1. A random copolymer in which the repeating units consist of repeating units of structures (I), (II), and (III), wherein R 1 and R 2 is independently a C1-C4 alkyl group, and x and y are independently R 1 and R 2 The number is an independent integer ranging from 0 to 3, and R 3 It is a C1-C4 alkyl, and R 4 m, n, and o are selected from C2-C10 primary alkyl groups, or from a group consisting of substituted or unsubstituted biphenyl moieties, substituted or unsubstituted phenyl moieties, and substituted or unsubstituted benzyl moieties, and m, n, and o are the number of repeating units of structures (I), (II), and (III), respectively, where the mol% of repeating units of structure (I) is in the range of approximately 60 mol% to approximately 95 mol%, the mol% of repeating units of structure (II) is in the range of approximately 5 mol% to approximately 25 mol%, and the repeating units of structure (III) are The mol% of each repeating unit is in the range of approximately 2 mol% to approximately 18 mol%, the sum of the mol% of these repeating units is less than 100 mol% if other different repeating units are present, or equal to 100 mol% if only repeating units of structures (I), (II), and (III) are present, and furthermore, the random copolymer has polydispersity in the range of approximately 1.25 to approximately 1.80, and has Mw in the range of approximately 30,000 to approximately 45,000 Daltons, and the random copolymer does not contain reactive end groups including a benzyl alcohol-containing moiety. [ka] 2. The random copolymer according to 1., wherein the repeating units essentially consist of repeating units of structures (I), (II), and (III). 3. The random copolymer according to 1. or 2. above, wherein the repeating units consist of repeating units of structures (I), (II), and (III), and the total mol% of repeating units (I), (II), and (III) is equal to 100 mol%. 4. A random copolymer according to any one of 1. to 3. above, wherein the repeating units of structure (III) are in the range of approximately 2.5 mol% to approximately 16 mol%. 5. A random copolymer according to any one of 1. to 4. above, wherein the repeating units of structure (III) are in the range of approximately 3 mol% to approximately 15 mol%. 6. A random copolymer according to any one of 1. to 5. above, wherein the repeating units of structure (II) are in the range of approximately 6 mol% to approximately 23 mol%. 7. A random copolymer according to any one of 1. to 6. above, wherein the repeating units of structure (II) are in the range of approximately 7 mol% to approximately 20 mol%. 8. A random copolymer according to any one of 1. to 7. above, wherein the repeating units of structure (I) are in the range of approximately 62 mol% to approximately 93 mol%. 9. A random copolymer according to any one of 1. to 8. above, wherein the repeating units of structure (I) are in the range of approximately 60 mol% to approximately 90 mol%. 10. A random copolymer according to any one of 1. to 9. above, wherein the repeating units of structure (I) are in the range of about 60 mol% to about 90 mol%, the repeating units of structure (II) are in the range of about 7 mol% to about 20 mol%, and the repeating units of structure (III) are in the range of about 3 mol% to about 15 mol%. 11. A random copolymer according to any one of items 1 to 10 above, wherein x is 0. 12. A random copolymer according to any one of items 1 to 11 above, wherein y is 0. 13. A random copolymer according to any one of items 1 to 12 above, wherein x and y are 0. 14. R 3 CH 3 The random copolymer described in any one of items 1 to 13 above. 15. R 4 A random copolymer according to any one of 1 to 14 above, wherein the first is a C2-C10 primary alkyl group. 16. R 4 A random copolymer according to any one of 1 to 15 above, wherein one of the members is a C2-C9 primary alkyl group. 17. R 4 A random copolymer according to any one of 1 to 16 above, wherein the parent molecule is a C2-C8 primary alkyl group. 18. R 4 A random copolymer according to any one of 1 to 17 above, wherein the alkyl group is a C2-C7 primary alkyl group. 19. R 4 A random copolymer according to any one of 1 to 18 above, wherein the C3-C7 primary alkyl group is a C3-C7 primary alkyl group. 20. R 4 A random copolymer according to any one of 1 to 19 above, wherein the parent molecule is a C3-C6 primary alkyl group. 21. R 4 A random copolymer according to any one of 1 to 20 above, wherein is a C4-C6 primary alkyl group. 22. R 4 A random copolymer according to any one of 1 to 21 above, wherein the first is a C4-C5 primary alkyl group. 23. R 4 A random copolymer according to any one of 1. to 22. above, wherein n-butyl is present. 24. R 4 A random copolymer according to any one of 1 to 18 above, wherein the first is a C2-C6 primary alkyl group. 25. R 4 A random copolymer according to any one of 1 to 18 and 24, wherein the C2-C5 primary alkyl group is a C2-C5 primary alkyl group. 26. R 4 A random copolymer according to any one of 1 to 18, 24, and 25, wherein the C2-C4 primary alkyl group is a C2-C4 primary alkyl group. 27. R 4 A random copolymer according to any one of 1 to 18 and 24 to 26, wherein the C2 to C3 primary alkyl group is a C2 to C3 primary alkyl group. 28. R 4 A random copolymer according to any one of 1. to 18. and 24. to 27., wherein n-propyl is present. 29. R 4 A random copolymer according to any one of items 1 to 18 and 24 to 27, wherein the derivative is ethyl. 30. R 4 A random copolymer according to any one of 1 to 14 above, wherein the benzyl moiety is the benzyl moiety. 31. R 4 A random copolymer according to any one of 1 to 14 and 21, wherein the derivative is benzyl. 32. R 4 A random copolymer according to any one of 1 to 14 above, wherein the phenyl portion is substituted. 33. R 4 A random copolymer according to any one of 1. to 14. and 23. above, wherein is phenyl. 34. R 4 A random copolymer according to any one of 1 to 14 above, wherein the compound is a substituted biphenyl. 35. R 4 A random copolymer according to any one of 1. to 14. and 25. above, wherein the biphenyl moiety is not substituted. 36. R 4 A random copolymer according to any one of 1. to 14., 25., and 26., wherein is [1,1'-biphenyl-4-yl]. 37. A random copolymer according to any one of 1. to 14., wherein the repeating unit has structures (Ia), (IIa), and (IIIa).

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Claims

1. A random copolymer in which the repeating unit comprises repeating units of structures (I), (II), and (III), wherein R １ and R ２ is independently a C1-C4 alkyl group, and x and y are independently R １ and R ２ The number is an independent integer ranging from 0 to 3, and R ３ is C1-C4 alkyl, and R ４ m, n, and o are selected from C2 to C10 primary alkyl groups, or from a portion containing an arene selected from the group consisting of substituted or unsubstituted biphenyl moieties, substituted or unsubstituted phenyl moieties, and substituted or unsubstituted benzyl moieties, and m, n, and o are the number of repeating units of structures (I), (II), and (III), respectively, where the mol% of repeating units of structure (I) is in the range of 60 mol% to 93 mol%, the mol% of repeating units of structure (II) is in the range of 5 mol% to 25 mol%, and the repeating units of structure (III) The mol% of the repeating units is in the range of 2 mol% to 18 mol%, the sum of the mol% of these repeating units is less than 100 mol% if other different repeating units are present, or equal to 100 mol% if only repeating units of structures (I), (II), and (III) are present, and furthermore, the random copolymer has polydispersity in the range of 1.25 to 1.80 and has Mw in the range of 30,000 to 45,000 Daltons, and the random copolymer does not contain reactive end groups including a benzyl alcohol-containing moiety. 【Chemistry 1】

2. The random copolymer according to claim 1, wherein the repeating units essentially consist of repeating units of structures (I), (II), and (III).

3. The random copolymer according to claim 1 or 2, wherein the repeating units consist of repeating units of structures (I), (II), and (III), where the total mol% of repeating units (I), (II), and (III) is equal to 100 mol%.

4. The random copolymer according to claim 1 or 2, wherein the repeating units of structure (III) are in the range of 2 mol% to 16 mol%.

5. The random copolymer according to claim 1 or 2, wherein the repeating units of structure (II) are in the range of 5 mol% to 23 mol%.

6. The random copolymer according to claim 1 or 2, wherein the repeating units of structure (I) are in the range of 62 mol% to 93 mol%.

7. The random copolymer according to claim 1 or 2, wherein the repeating units of structure (I) are in the range of 60 mol% to 90 mol%, the repeating units of structure (II) are in the range of 7 mol% to 20 mol%, and the repeating units of structure (III) are in the range of 3 mol% to 15 mol%.

8. The random copolymer according to claim 1 or 2, wherein x is 0.

9. The random copolymer according to claim 1 or 2, wherein y is 0.

10. The random copolymer according to claim 1 or 2, wherein x and y are 0.

11. R ３ ga CH ３ The random copolymer according to claim 1 or 2.

12. R ４ The random copolymer according to claim 1 or 2, wherein R is a C2-C10 primary alkyl group.

13. R ４ The random copolymer according to claim 1 or 2, wherein is a C3-C7 primary alkyl group.

14. R ４ The random copolymer according to claim 1 or 2, wherein n-butyl is present.

15. R ４ The random copolymer according to claim 1 or 2, wherein is a C2-C6 primary alkyl group.

16. R ４ The random copolymer according to claim 1 or 2, wherein is n-propyl.

17. R ４ The random copolymer according to claim 1 or 2, wherein is ethyl.

18. R ４ The random copolymer according to claim 1 or 2, wherein the benzyl moiety is the benzyl moiety.

19. R ４ The random copolymer according to claim 1 or 2, wherein is benzyl.

20. R ４ The random copolymer according to claim 1 or 2, wherein the phenyl moiety is substituted.

21. R ４ The random copolymer according to claim 1 or 2, wherein is phenyl.

22. R ４ The random copolymer according to claim 1 or 2, wherein the compound is a substituted biphenyl.

23. R ４ The random copolymer according to claim 1 or 2, wherein the biphenyl moiety is not substituted.

24. R ４ The random copolymer according to claim 1 or 2, wherein is [1,1'-biphenyl-4-yl].

25. The random copolymer according to claim 1 or 2, wherein the repeating units have structures (Ia), (IIa), and (IIIa). 【Chemistry 2】

26. The random copolymer according to claim 1 or 2, wherein the repeating unit has structures (Ia), (IIa), and (IIIa-1). 【Transformation 3】

27. The random copolymer according to claim 1 or 2, wherein the repeating units have structures (Ia), (IIa), and (IIIb). 【Chemistry 4】

28. The random copolymer according to claim 1 or 2, wherein the repeating units have structures (Ia), (IIa), and (IIIc). 【Transformation 5】

29. The random copolymer according to claim 1 or 2, wherein the repeating units have structures (Ia), (IIa), and (IIId). 【Transformation 6】

30. A composition comprising the random copolymer described in claim 1 and an organic spin-casting solvent.

31. A method for forming a crosslinked copolymer layer on a substrate, the following steps: a) A step of forming a coating of the composition of claim 30 on a substrate; b) The step of heating the coating at a temperature in the range of 90°C to 180°C to remove the solvent; c) Heating the coating at a temperature in the range of 200°C to 350°C to form a crosslinked copolymer coating layer; The method, including the method described above.

32. A chemoepitaxy-induced self-assembly method for block copolymer layers used to form an image, the following steps: a-1) A step of coating the substrate with a graftable neutral layer polymer precursor to form a coat layer 1; b-1) A step of heating the coating layer 1 at a temperature between 90°C and 180°C to remove the solvent; c-1) A step in which the coating layer 1 is heated at a temperature of 200°C to 350°C after step b-1) to bring about grafting; d-1) After step c-1), the coating layer 1 is treated with an organic solvent to remove the ungrafted neutral layer polymer, leaving an insoluble grafted neutral layer on the substrate; e-1) A step of coating the grafted neutral layer with a negative-type photoresist layer; f-1) A negative pattern is formed in the photoresist layer, thereby forming a grafted neutral layer with areas covered by the photoresist and areas that are not covered, wherein the pattern in the photoresist includes both small nanometer-sized repeating patterns and larger areas where the photoresist was removed during the formation of the negative pattern, which does not include the repeating nanometer-sized patterns; g-1) Etching and removing the neutral layer regions that were not covered in step f-1), thereby leaving the exposed substrate in these regions; h-1) After step g-1), the photoresist is peeled off from the substrate, leaving a patterned substrate, wherein the area of ​​the substrate that was not covered with photoresist in step f-1) does not contain a grafted neutral layer, and the area covered with photoresist in step f-1) retains a grafted neutral layer; i-1) The patterned substrate is coated with the composition according to claim 30 to form a coat layer 2; j-1) A step of heating the coating layer 2 at a temperature of 90°C to 180°C to remove the solvent; k-1) A step of heating the coating layer 2 at a temperature in the range of 200°C to 350°C to leave an insoluble crosslinked pinned MAT layer on the substrate in the region where the grafted neutral layer is absent, thereby generating a substrate having both a pinned MAT layer region and a neutral layer region; l-1) A step of applying a coating of a block copolymer comprising an etchable styrene-based block and a highly etchable aliphatic block onto the substrate comprising a patterned neutral layer and a pinned MAT layer to produce a substrate comprising both a patterned neutral layer and a patterned pinned MAT layer; m-1) Anneal the block copolymer layer until induced self-assembly occurs in the small nanometer-sized repeating pattern of the substrate, provided that vertical orientation of the block polymer domains does not occur in the larger regions containing the crosslinked pinned MAT layer; o-1) Etching the block copolymer to remove highly etchable blocks of the copolymer and form a repeating nanometer-sized pattern in the region where induced self-assembly of the block copolymer occurred on the substrate in step m-1); The method, including the method described above.

33. A chemoepitaxy-induced self-assembly method for block copolymer layers used to form an image, the following steps: a-2) A step of forming a coating of a neutral layer polymer precursor, wherein the neutral layer polymer precursor is crosslinkable or crosslinkable and graftable onto a substrate; b-2) A step of heating the crosslinkable coating of the neutral layer polymer precursor, or the crosslinkable and graftable coating of the neutral layer polymer precursor, at a temperature of 90°C to 180°C to remove the solvent; c-2) A step of heating a coating of the crosslinkable neutral layer polymer precursor, or a coating of the crosslinkable and graftable neutral layer polymer precursor, at a temperature of 200°C to 330°C to form a crosslinked neutral layer, or a crosslinked and grafted neutral layer; d-2) A step of coating the crosslinked neutral layer or the crosslinked and grafted neutral layer with a photoresist layer; e-2) A negative pattern is formed in the photoresist layer to form regions where the crosslinked neutral layer or crosslinked and grafted neutral layer is covered by the photoresist and regions where it is not covered, wherein the pattern in the photoresist consists of both small nanometer repeating patterns and larger regions where the photoresist is removed during the image formation process and does not contain repeating nanometer-sized patterns; f-2) Etching with plasma to remove the neutral layer region not covered in step e-2), thereby removing the crosslinked neutral layer or the crosslinked and grafted neutral layer, leaving the exposed substrate in the region not covered in step e-2); g-2) After step f-2), the photoresist is peeled off from the substrate, leaving the patterned substrate, wherein the area of ​​the substrate left uncovered by the photoresist in step e-2) does not contain a crosslinked neutral layer or a crosslinked and grafted neutral layer, and the area covered by the photoresist in step f2) retains a crosslinked neutral layer or a crosslinked and grafted neutral layer; h-2) A step of coating the patterned substrate with the composition described in claim 30 to form a coat layer 3; i-2) A step of heating the coating layer 3 at a temperature of 90°C to 180°C to remove the solvent; j-2) The step of heating the coating layer 3 at a temperature in the range of 200°C to 350°C to leave an insoluble crosslinked pinned MAT layer on the substrate in the region where there is no grafted neutral layer, thereby generating a substrate that includes both the pinned MAT layer region and the neutral layer region; k-2) A step of applying a coating of a block copolymer comprising an etchable styrene-based block and a highly etchable aliphatic block onto the substrate comprising a patterned neutral layer and a pinned MAT layer; l-2) Annealing the block copolymer layer until induced self-assembly occurs in small nanometer-sized repeating patterns of the substrate, provided that in larger regions including the crosslinked pinned MAT layer, vertical orientation of the block copolymer domains does not occur; m-2) Etching the block copolymer to remove highly etchable blocks of the copolymer and form a repeating nanometer-sized pattern in the region where induced self-assembly of the block copolymer occurred in step l-2); The method, including the method described above.

34. A chemoepitaxy-induced self-assembly method for block copolymer layers used to form an image, the following steps: a-3) A step of forming a film by forming a coating of the composition according to claim 30 on a substrate; b-3) The step of baking the film at a temperature of 200°C to 350°C for 1 to 10 minutes to form an insoluble crosslinked pinned MAT layer. c-3) A step of applying a positive or negative photoresist layer coating onto the crosslinked pinned MAT layer, d-3) A step of forming a negative or positive image in a negative or positive photoresist layer, thereby forming regions of the crosslinked pinned MAT layer that are covered with photoresist and regions that are not covered; e-3) Etching using plasma to remove the crosslinked pinned MAT layer in the areas not covered in step d-3), leaving the exposed substrate, and leaving the crosslinked pinned MAT layer in the areas covered in step d-3), thereby forming a patterned crosslinked pinned MAT layer. f-3) A step of coating the patterned crosslinked pinned MAT layer with a neutral brush layer coating; g-3) The neutral brush layer coating is cured, and the ungrafted neutral layer is washed and removed with a solvent to form a neutral brush induction layer in the area of ​​the substrate not covered by the patterned crosslinked pinned MAT layer, thereby forming a chemoepitaxy induction layer on the substrate; h-3) A step of coating the chemoepitaxy induction layer with a block copolymer solution to form a block copolymer coating. i-3) Annealing the coating of the block copolymer to form an induced self-assembly film of the block copolymer on the chemoepitaxy induction layer; j-3) Etching the block copolymer to remove highly etchable blocks of the copolymer in the region where induced self-assembly of the block copolymer occurred on the substrate in step h-3), thereby forming a repeating nanometer-sized pattern; The method, including the method described above.

35. Use of the copolymer according to claim 1 or the composition according to claim 30 for coating a substrate.

36. In a chemoepitaxy process, use of the copolymer according to claim 1 or the composition according to claim 30 for coating a substrate.

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