Novel compositions and methods for the self-assembly of block copolymers

Abstract

To provide a novel styrenic polymer and a novel composition, wherein a grafted film is formed on a substrate, and the grafted film may be used in a directed self-assembly process.SOLUTION: A styrenic polymer has polydispersity from 1 to 1.3, and each polymer chain of the styrenic polymer is capped with one end group of a structure 1), wherein, L is a linking group selected from a group consisting of a direct valence bond, oxy (-O-), carbonyloxy, (-(C=O)-O-), carbonate (-O-(C=O)-O-); L2 is a C-1 to C-20 substituted or unsubstituted alkylene spacer, an arylene spacer or a direct valence bond, R is hydrogen, a halide, a C-1 to C-20 alkyl moiety, or a C-1 to C-20 alkyloxy moiety, m is an integer from 1 to 3; and a wavy line represents the direct valence bond attaching the end group 1) to the end of the polymer chain of the styrenic polymer.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to novel polymers, novel compositions, and novel methods of using the novel compositions for aligning microdomains of directed self-assembly block copolymers (BCPs), which compositions and methods are useful in the manufacture of electronic devices. [Background technology]

[0002] Directed self-assembly of block copolymers is a useful method for generating ever smaller patterned features for the fabrication of microelectronic devices, which can achieve nanoscale feature critical dimensions (CD). Directed self-assembly methods are desirable for extending the resolution capabilities of microlithography techniques. Conventional lithography methods may use ultraviolet (UV) light to expose through a mask to a photoresist layer coated on a substrate or layered substrate. Positive or negative photoresists are useful, and they may also contain refractory elements such as silicon to allow dry development using conventional integrated circuit (IC) plasma processing. In positive photoresists, UV radiation passing through a mask causes a photochemical reaction in the photoresist that renders the exposed areas removable with a developer solution or by conventional IC plasma processing. Conversely, in negative photoresists, UV radiation passing through a mask renders the exposed areas less removable with a developer solution or by conventional IC plasma processing. Integrated circuit features such as gates, vias or interconnects are then etched into the substrate or layered substrate, and the remaining photoresist is removed. Using conventional lithographic exposure processes, there are limitations to the feature size of integrated circuit features. Further reduction in pattern size is difficult to achieve using radiation exposure due to limitations related to aberrations, focus, proximity effects, minimum achievable exposure wavelength, and maximum achievable numerical aperture. Due to the need for large scale integration, device circuit dimensions and features have been continually reduced. In the past, the final resolution of features has depended on the wavelength of light used to expose the photoresist, which has its own limitations. Directed assembly techniques such as graphoepitaxy and chemoepitaxy using block copolymer imaging are highly desirable techniques used to improve resolution while reducing CD variation. These techniques can be used to augment conventional UV lithography techniques or to enable even higher resolution and CD control in approaches using EUV, e-beam, deep UV, or immersion lithography.The directed self-assembly block copolymers contain blocks of etch-resistant and easily etched copolymer units, which when coated, aligned and etched on a substrate, provide highly dense patterned regions. In the graphoepitaxy directed self-assembly method, the block copolymers self-assemble around a substrate that has been pre-patterned using conventional lithography (ultraviolet, deep UV, e-beam, extreme ultraviolet (EUV) exposure sources) to form repeating topographical features such as line / space (L / S) or contact hole (CH) patterns. In one example of an L / S directed self-assembly array, the block copolymers form self-aligned lamellar regions that can form parallel line-space patterns of different pitches in the trenches between the pre-patterned lines, enhancing pattern resolution by dividing the spaces in the trenches between the topographical lines into finer patterns. For example, a diblock copolymer that can microphase separate and includes a carbon-rich block (e.g., styrene or some other element such as Si, Ge, Ti) that is resistant to plasma etching and a block that is highly plasma etchable or removable can provide high resolution pattern definition. An example of a highly etchable block can include a monomer that is oxygen-rich and does not include a refractory element, and can also form a highly etchable block, such as methyl methacrylate. The plasma etching gas used in the etching process that defines the self-assembled pattern is typically a gas used in the process used to manufacture integrated circuits (ICs). In this way, very fine patterns can be generated in typical IC substrates compared to those that can be defined by conventional lithography techniques, thus achieving pattern multiplication.Similarly, features such as contact holes can be produced in greater density by using graphoepitaxy in which a suitable block copolymer aligns itself by directed self-assembly around an array of contact holes or posts defined by conventional lithography, thus forming a greater density array of regions of etchable and etch-resistant domains that, when etched, give a greater density array of contact holes. Graphoepitaxy thus has the potential to provide both pattern modification and pattern multiplication.

[0003] In chemical epitaxy or pinned chemical epitaxy (also known as chemoepitaxy), the self-assembly of block copolymers is formed around a surface that has regions of different chemical affinity but little or no topography to guide the self-assembly process. For example, the surface of a substrate can be patterned using conventional lithography (UV, deep UV, e-beam, EUV) to generate surfaces of different chemical affinity as line and space (L / S) patterns in which exposed regions, where the surface chemistry has been modified by radiation, alternate with unexposed regions that show no chemical change. These regions do not have topographical differences, but show surface chemical differences or pinning that guide the self-assembly of block copolymer segments. Specifically, the guided self-assembly of block copolymers with block segments containing etch-resistant repeat units (e.g., styrene repeat units) and fast-etching repeat units (e.g., methyl methacrylate repeat units) would allow precise placement of etch-resistant and fast-etching block segments on a pattern. This technique allows for precise placement of these block copolymers and subsequent pattern transfer into the substrate after plasma or wet etching processing. Chemical epitaxy has the advantage that it can be fine-tuned by changing chemical differences to allow for modification of the pattern, helping to improve line edge roughness and CD control. Other types of patterns, such as repeating contact hole (CH) arrays, can also be pattern modified using chemoepitaxy.

[0004] A neutral layer is a layer on a substrate or a surface of a treated substrate that has no affinity for any of the block segments of the block copolymer used for directed self-assembly. Neutral phases are useful in graphoepitaxy methods of directed self-assembly of block copolymers because they allow for proper placement or orientation of the block polymer segments for directed self-assembly resulting in proper placement of the etch-resistant and highly etchable block polymer segments relative to the substrate. For example, in a surface containing line-and-space features defined by conventional radiation lithography, the neutral layer allows for the orientation of the block segments such that they are oriented perpendicular to the surface of the substrate, which is an ideal orientation for both pattern modification and pattern multiplication depending on the length of the block segments in the block copolymer relative to the length between the lines defined by conventional lithography. If the substrate interacts too strongly with one of the block segments, the segment will lie flat on its surface, maximizing the contact area between the segment and the substrate; such a surface will disrupt the desired vertical alignment that can be used to achieve either pattern modification or pattern multiplication based on features generated by conventional lithography. Modifying or pinning selected small regions of the substrate to cause them to interact strongly with one block of the block copolymer, while leaving the remainder of the substrate coated with a pinning layer, can be useful to align the domains of the block copolymer in a desired direction, and this is the basis for pinned chemo- or graphoepitaxy used for pattern multiplication.

[0005] One problem with current methods of chemoepitaxy-induced layers using pinning layers is the ability to form uniform, dense films over large areas using conventional brush-type precursors on substrates such as Si or SiO2. Formation of such dense films of induced layers would be advantageous to more effectively form vertical morphology of block copolymer domains during self-assembly of block copolymers as overlayers that contain styrenic and aliphatic blocks. A non-limiting example of such a block copolymer is one that contains a block of methyl methacrylate and a block of styrene. We disclose herein novel graftable styrenic polymers that contain benzyl alcohol end group moieties and have low polydispersity of 1 to about 1.3. These novel materials can form surprisingly dense and uniform grafted layers when coated and baked from solvent-containing formulations. These dense grafted layers provide surprisingly effective pinning layers where vertical orientation of domains occurs during chemoepitaxy-induced self-assembly in the case of block copolymers that contain styrenic and aliphatic blocks. When used in combination with graftable or crosslinkable or crosslinkable and graftable neutral layer precursors, these new pinning layer precursors surprisingly allow access to chemoepitaxy-induced self-assembly schemes where small nanometer-sized patterns comprising neutral and pinning layers can undergo chemoepitaxy-induced self-assembly, while at the same time allowing the formation of large unpatterned areas of the substrate that are only coated with the pinning layer, which does not allow perpendicular orientation of the block polymer domains in these areas that would otherwise cause undesired defect formation during pattern transfer into the substrate during etching. [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] US20160122579A1 [Patent Document 7] U.S. Application Serial No. 14 / 885,328 [Non-patent literature]

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

[0008] In two of its aspects, the present invention relates to novel styrenic polymers and to novel compositions comprising the same and a solvent, wherein the styrenic polymer has a polydispersity of 1 to 1.3, and further wherein each polymer chain of the styrenic polymer is capped with one end group of structure 1);

[0009] [ka]

[0010] Further, wherein L1 is a linking group selected from the group consisting of a direct valence bond, oxy (-O-), carbonyloxy, (-(C=O)-O-), carbonate (-O-(C=O)-O-); L2 is a C1-C20 substituted or unsubstituted alkylene spacer, arylene spacer, or direct valence bond, R is selected from hydrogen, halide, C1-C20 alkyl moiety, or C1-C20 alkyloxy moiety, and m is an integer from 1 to 3; and

[0011] [ka] The end group 1) represents a direct valence bond that connects the polymer chain end of a styrene-based polymer. In another aspect, the invention relates to the use of this composition for forming a grafted film on a substrate, and in yet another aspect, the grafted film can be used in a directed self-assembly process. [Brief description of the drawings]

[0012] [Figure 1] AFM images of polystyrene brush-treated Si and SiO2 surfaces. 1a) Comparative Example 1 grafted onto Si substrate; 1b) Synthesis Example 2 grafted onto Si substrate; 1c) Comparative Synthesis Example 2 grafted onto SiO2 substrate; 1d) Synthesis Example 2 grafted onto SiO2 substrate. [Diagram 2] Self-assembled morphology of PS-b-PMMA (Lo=30 nm) film on polystyrene brush-treated substrate; 2A: “Comparative Synthesis Example 2”, 2B: “Synthesis Example 2” DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Both the general description above and the detailed description below are exemplary and should not be construed as limiting the invention as claimed. In this application, the use of the singular includes the plural, and unless specifically stated otherwise, the singular means "at least one," and the use of "or" means "and / or." Furthermore, the use of the term "comprises," as well as other verb forms such as "comprises," is not limiting. Also, the use of terms such as "element" or "component" includes elements and components that contain one unit, as well as elements or components that contain more than one unit, unless specifically stated otherwise. As used herein, the conjunction "and" is intended to be inclusive, and the conjunction "or" is not intended to be exclusive unless otherwise indicated. For example, the phrase "or instead of" is intended to be exclusive. As used herein, the conjunction "and / or" refers to any combination of the described elements, including the use of a single element.

[0014] The section headings used herein are for organizational purposes only and should not be construed as limiting the technical subject matter described. All references or portions of references cited herein, including but not limited to patents, patent applications, papers, books, and treatises, are incorporated herein in their entirety for all purposes. In the event that the definition of a term in one or more of the references and similar materials incorporated herein conflicts with that herein, the definition in the present application shall control.

[0015] As used herein, alkyl refers to a hydrocarbon group which can be linear, branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, and the like) or cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, and the like).

[0016] Alkyloxy refers to an alkyl group as defined above attached through an oxy (-O-) moiety (eg, methoxy, ethoxy, propoxy, butoxy, 1,2-isopropoxy, cyclopentyloxy, cyclohexyloxy, and the like).

[0017] Fluoroalkyl refers to a linear, cyclic or branched saturated alkyl group as defined above in which hydrogen has been partially or fully replaced by fluorine (e.g., trifluoromethyl, perfluoroethyl, 2,2,2-trifluoroethyl, perfluoroisopropyl, perfluorocyclohexyl, and the like).

[0018] Fluoroalkyloxy refers to a fluoroalkyl group as defined above attached through an oxy (-O-) moiety (eg, trifluoromethyloxy, perfluoroethyloxy, 2,2,2-trifluoroethoxy, perfluorocyclohexyloxy, and the like).

[0019] When referring herein to alkyl, alkyloxy, fluoroalkyl, fluoroalkyloxy moieties having a range of possible carbon atoms starting from C1, such as, as non-limiting examples, "C1-C10 alkyl" or "C1-C10 fluoroalkyl," this range includes linear alkyl, alkyloxy, fluoroalkyl, and fluoroalkyloxy starting from C1, but specifies only branched alkyl, branched alkyloxy, cycloalkyl, cycloalkyloxy, branched fluoroalkyl, and cyclic fluoroalkyl starting from C3.

[0020] Here, the term alkylene refers to a hydrocarbon group that can be linear, branched or cyclic and has two points of attachment (e.g., methylene, ethylene, 1,2-isopropylene, 1,4-cyclohexylene, and the like). Again, when specifying a possible carbon range, such as C1-C20 as a non-limiting example, the range includes linear alkylene starting at C1, but also specifies branched alkylene or branched cycloalkylene starting at C3. The term alkylene also includes unsubstituted alkylene (aka linear, branched or cyclic alkylene in which only hydrogen is present), and substituted alkylene (aka linear, branched or cyclic alkylene containing substituents other than hydrogen), where one or more hydrogens are replaced by a substituent selected from an aryl group, a halide, a C1-C20 alkyl, or a C1-C20 alkyloxy.

[0021] Here, the term aryl refers to an aromatic hydrocarbon moiety having one point of attachment, which may be a single benzene moiety (e.g., phenyl), a polycyclic aromatic moiety having one point of attachment, such as moieties derived from naphthalene, anthracene, pyrene, and the like, or multiple linked benzene rings having one point of attachment (e.g., 1,4-biphenyl). The term aryl also encompasses the above moieties that are unsubstituted aryl (i.e., only hydrogen as a substituent) or substituted aryl, where the substituents are selected from halide, C1-C20 alkyl, or C1-C20 alkyloxy.

[0022] As used herein, the term arylene refers to an aromatic hydrocarbon moiety having two points of attachment, which may be a single benzene moiety (e.g., 1,4-phenylene, 1,3-phenylene, and 1,2-phenylene), a polycyclic aromatic moiety having two points of attachment, such as those derived from naphthalene, anthracene, pyrene, and the like, or multiple linked benzene rings having two points of attachment (e.g., biphenylene).

[0023] Lo is the bulk repeat period of the block copolymer as defined in Erik W. Edwards et al., Macromolecules 2007, 40, p. 90-96 (Non-Patent Document 1).

[0024] When two linking moieties are adjacent to one another and both are designated as monovalent bonds, this designation represents a single linking moiety that is a monovalent bond (e.g., when linking moieties L1 and L2 are both designated as monovalent bonds, this represents a single linking moiety that is a monovalent bond).

[0025] A first embodiment is a styrenic polymer having a polydispersity of 1 to about 1.3 and each polymer chain of the styrenic polymer is capped with one end group of structure 1);

[0026] [ka]

[0027] wherein L1 is a linking group selected from the group consisting of a direct valence bond, oxy (-O-), carbonyloxy, (-(C=O)-O-), carbonate (-O-(C=O)-O-); L2 is a C1-C20 substituted or unsubstituted alkylene spacer, arylene spacer, or direct valence bond, R is hydrogen, halide, C1-C20 alkyl moiety, or C1-C20 alkyloxy moiety, and m is 1 to 3; and

[0028] [ka] The end group 1) represents the direct valence bond that attaches the polymer chain end of the styrenic polymer.

[0029] In another embodiment of the above embodiment of the styrenic polymer having an end group having structure 1), either one of the L1 or L2 moieties is not selected from a direct valence bond.

[0030] In another embodiment of the above embodiment of the styrenic polymer having an end group having structure 1), m is 1 or 2.

[0031] In another embodiment of the above embodiment of the styrenic polymer having an end group having structure 1), m is 1.

[0032] In another of the above embodiments of the styrenic polymer having an end group having structure 1), m is 2.

[0033] In another of the above embodiments of the styrenic polymer having an end group having structure 1), m is 3.

[0034] In another embodiment of any one of the above embodiments of the styrenic polymer, the end group has the structure 1a).

[0035] [ka]

[0036] In another embodiment of any one of the above embodiments of the styrenic polymer, the end group has the structure 1b).

[0037] [ka]

[0038] In another embodiment of any one of the above embodiments where the styrenic polymer has an end group having structure 1), 1a), or 1b), L1 is a direct valence bond.

[0039] In another embodiment of any one of the above embodiments of the styrenic polymer having an end group having structure 1), 1a), or 1b), L1 is oxy (-O-).

[0040] In another embodiment of any one of the above embodiments of the styrenic polymer having an end group having structure 1), 1a), or 1b), L1 is carbonyloxy (-(C=O)-O-).

[0041] In another embodiment of any one of the above embodiments of the styrenic polymer having an end group having structure 1), 1a), or 1b), L1 is carbonate (-(C=O)-O-).

[0042] In another embodiment of any one of the above embodiments of the styrenic polymer having an end group having structure 1), 1a), or 1b), L2 is a C1-C20 substituted or unsubstituted alkylene spacer.

[0043] In another embodiment of any one of the above embodiments of the styrenic polymer having an end group having structure 1), 1a), or 1b), L2 is a C1-C20 unsubstituted alkylene spacer.

[0044] In another embodiment of any one of the above embodiments of the styrenic polymer having an end group having structure 1), 1a), or 1b), L2 is a C1-C20 substituted alkylene spacer.

[0045] In another embodiment of any one of the above embodiments of the styrenic polymer having an end group having structure 1), 1a), or 1b), L2 is an alkylene spacer.

[0046] In another embodiment of any one of the above embodiments of the styrenic polymer having an end group having structure 1), 1a), or 1b), L2 is a direct valence bond.

[0047] In another embodiment of any one of the above embodiments of the styrenic polymer having an end group having structure 1), 1a), or 1b), R is hydrogen.

[0048] In another embodiment of any one of the above embodiments of the styrenic polymer having an end group having structure 1), 1a), or 1b), R is a halide.

[0049] In another embodiment of any one of the above embodiments of the styrenic polymer having an end group having structure 1), 1a), or 1b), L2 is a C1-C20 alkylene spacer, L1 is oxy (-O-), and R is hydrogen.

[0050] In another embodiment of any one of the above embodiments of the styrenic polymer having an end group having structure 1), 1a) or 1b), L2 is a C2 alkylene spacer.

[0051] In another embodiment of any one of the above embodiments of the styrenic polymer having an end group having structure 1), 1a) or 1b), L2 is a C2 alkylene spacer, L1 is oxy (-O-), and R is hydrogen.

[0052] In another embodiment of any one of the above embodiments of the styrenic polymer having an end group having structure 1), 1a), or 1b), where R is a halide, the halide may be selected from the group consisting of F, Cl, Br, or I. In another embodiment of this embodiment, the halide is F, in another embodiment the halide is Cl, in another embodiment the halide is Br, and in yet another embodiment the halide is I.

[0053] In another aspect of any one of the above embodiments of the styrenic polymer having an end group having structure 1), 1a), or 1b), R is a C1-C20 alkyl moiety. In another aspect of this embodiment, R is a C1-C15 alkyl moiety, R is a C1-C10 alkyl moiety, R is a C1-C5 alkyl moiety, R is a C1-C4 alkyl moiety, R is a C1-C3 alkyl moiety, R is a C1-C2 alkyl moiety, or R is a C1 alkyl moiety.

[0054] In another aspect of any one of the above embodiments of the styrenic polymer having an end group having structure 1), 1a), or 1b), R is a C1-C20 alkyloxy moiety. In another aspect of this embodiment, R is a C1-C15 alkyloxy moiety, R is a C1-C10 alkyloxy moiety, R is a C1-C5 alkyloxy moiety, R is a C1-C4 alkyloxy moiety, R is a C1-C3 alkyloxy moiety, R is a C1-C2 alkyloxy moiety, or R is a C1 alkyloxy moiety.

[0055] In another embodiment of any one of the above embodiments of the styrenic polymer having an end group having structure 1), 1a) or 1b), it has the more specific structure 1c).

[0056] [ka]

[0057] In any other embodiment of the styrenic polymer described above, wherein the end group has the structure 1c), L1 is a direct valence bond.

[0058] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has the structure 1c), L1 is oxy (-O-).

[0059] In another embodiment of any one of the above embodiments of the styrenic polymer in which the end group has the structure 1c), L1 is carbonyloxy (-(C=O)-O-).

[0060] In another embodiment of any one of the above embodiments of the styrenic polymer in which the end group has the structure 1c), L1 is carbonate (-O-(C=O)-O-).

[0061] In another embodiment of any one of the above embodiments of the styrenic polymer in which the end group has the structure 1c), L1 is carbonate (-O-(C=O)-O-).

[0062] In another embodiment of the styrenic polymer according to any one of the above, wherein the end group has the structure 1c), L2 is a C1-C20 substituted or unsubstituted alkylene spacer.

[0063] In another embodiment of any one of the above embodiments of the styrenic polymer in which the end group has structure 1c), L2 is a C1-C20 unsubstituted alkylene spacer.

[0064] In another embodiment of any one of the above embodiments of the styrenic polymer in which the end group has structure 1c), L2 is a C1-C20 substituted alkylene spacer.

[0065] In any other embodiment of the styrenic polymer described above, in which the end group has the structure 1c), L2 is an arylene spacer.

[0066] In any other embodiment of the styrenic polymer described above, wherein the end group has the structure 1c), L2 is a direct valence bond.

[0067] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has the structure 1c), R is hydrogen.

[0068] In another embodiment of any one of the above embodiments of the styrenic polymer, where the end group has the structure 1c), R is a halide.

[0069] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has structure 1c), R is a C1-C20 alkyl moiety.

[0070] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has structure 1c), R is a C1-C20 alkyloxy moiety.

[0071] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has the structure 1c), L2 is a C1-C20 alkylene spacer, L1 is oxy (—O—), and R is hydrogen.

[0072] In any other embodiment of the styrenic polymer described above, in which the end group has the structure 1c), L2 is a C2 alkylene spacer.

[0073] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has the structure 1c), L1 is oxy (-O-).

[0074] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has the structure 1c), R is hydrogen.

[0075] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has the structure 1c), L2 is a C2 alkylene spacer, L1 is oxy (-O-), and R is hydrogen.

[0076] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has the structure 1c), R is hydrogen.

[0077] In another embodiment of any one of the above embodiments of the styrenic polymer where the end group has structure 1c) and R is a halide, the halide may be selected from the group consisting of F, Cl, Br or I. In another aspect of this embodiment, the halide is F, in another embodiment the halide is Cl, in another embodiment the halide is Br, and in yet another embodiment the halide is I.

[0078] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the terminal group has structure 1c), R is a C1-C20 alkyl moiety. In another aspect of this embodiment, R is a C1-C15 alkyl moiety, R is a C1-C10 alkyl moiety, R is a C1-C5 alkyl moiety, R is a C1-C4 alkyl moiety, R is a C1-C3 alkyl moiety, R is a C1-C2 alkyl moiety, or R is a C1 alkyl moiety.

[0079] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the terminal group has structure 1c), R is a C1-C20 alkyloxy moiety. In another aspect of this embodiment, R is a C1-C15 alkyloxy moiety, R is a C1-C10 alkyloxy moiety, R is a C1-C5 alkyloxy moiety, R is a C1-C4 alkyloxy moiety, R is a C1-C3 alkyloxy moiety, R is a C1-C2 alkyloxy moiety, or R is a C1 alkyloxy moiety.

[0080] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has the structure 1c), L2 is a C1-C20 alkylene spacer, L1 is oxy (—O—), and R is hydrogen.

[0081] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has the structure 1c), L2 is a C2 alkylene spacer. In another aspect of this embodiment, R is hydrogen.

[0082] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has the structure 1c), R is hydrogen.

[0083] In another embodiment of the styrenic polymer according to any one of the above, in which the end group has the structure 1, 1a), 1b) or 1c), L2 is a C1 to C20 alkylene spacer substituted with an aryl group.

[0084] In another embodiment of any one of the above embodiments of the styrenic polymer, where the end group has structure 1, 1a), 1b), or 1c), L1 is a direct valence bond and L2 is a C1-C20 alkylene spacer substituted with an aryl group. In yet another aspect of this embodiment, the end group has structure 2), where L3 is a C1-C19 alkylene group, R' and R'' are independently selected from hydrogen, halide, C1-C20 alkyl moieties, or C1-C20 alkyloxy moieties, and m' is an integer from 1 to 3, and

[0085] [ka] represents a direct valence bond attaching the end group 2) to the end of the polymer chain of the styrenic polymer.

[0086] [ka]

[0087] In another embodiment of the styrenic polymer according to any one of the above embodiments, in which the end group has the structure 2), L3 is a C1-C5 alkylene moiety.

[0088] In another embodiment of the styrenic polymer according to any one of the above embodiments, in which the end group has the structure 2), L3 is a C1-C2 alkylene moiety.

[0089] In any other embodiment of the styrenic polymer described above, wherein the end group has structure 2), L3 is a C1 alkylene moiety.

[0090] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has structure 2), m' is 1.

[0091] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has structure 2), m' is 2.

[0092] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has structure 2), m' is 3.

[0093] In another embodiment of any one of the above embodiments of the styrenic polymer in which the end group has structure 2), m' is 1 or 2.

[0094] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has structure 2), R' is hydrogen.

[0095] In another embodiment of any one of the above embodiments of the styrenic polymer, where the end group has structure 2), R' is a halide.

[0096] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has structure 2), R' is a C1-C20 alkyl moiety.

[0097] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has structure 2), R' is a C1-C20 alkyloxy moiety.

[0098] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has structure 2), R'' is hydrogen.

[0099] In another embodiment of any one of the above embodiments of the styrenic polymer, where the end group has structure 2), R'' is a halide.

[0100] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has structure 2), R'' is a C1-C20 alkyl moiety.

[0101] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has structure 2), R'' is a C1-C20 alkyloxy moiety.

[0102] In any other embodiment of the styrenic polymer described above, wherein the end group has structure 2), R' and R'' are both selected from the same substituent selected from hydrogen, halide, a C1-C20 alkyl moiety, or a C1-C20 alkyloxy moiety.

[0103] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end groups have structure 2), R' and R'' are hydrogen.

[0104] In another embodiment of any one of the above embodiments of the styrenic polymer, where the end group has structure 2), which end group has the more specific structure 2a) below, and L3 is a C1-C19 alkylene group, R' and R'' are independently selected from hydrogen, halide, a C1-C20 alkyl moiety, or a C1-C20 alkyloxy moiety; and m' is an integer from 1 to 3; and

[0105] [ka] represents a direct valence bond connecting the end group 2a) to the end of the polymer chain of the styrenic polymer:

[0106] [ka]

[0107] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has structure 2a), L3 is a C1-C5 alkylene moiety.

[0108] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has structure 2a), L3 is a C1-C2 alkylene moiety.

[0109] In any other embodiment of the above styrenic polymer, wherein the end group has structure 2a), L3 is a C1 alkylene moiety.

[0110] In another embodiment of any one of the above embodiments of the styrenic polymer, where the end group has the structure 2a), R' is hydrogen.

[0111] In another embodiment of any one of the above embodiments of the styrenic polymer, where the end group has structure 2a), R' is a halide.

[0112] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has structure 2a), R' is a C1-C20 alkyl moiety.

[0113] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has structure 2a), R' is a C1-C20 alkyloxy moiety.

[0114] In another embodiment of any one of the above embodiments of the styrenic polymer, where the end group has the structure 2a), R'' is hydrogen.

[0115] In another embodiment of any one of the above embodiments of the styrenic polymer, where the end group has structure 2a), R'' is a halide.

[0116] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has structure 2a), R'' is a C1-C20 alkyl moiety.

[0117] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has structure 2a), R'' is a C1-C20 alkyloxy moiety.

[0118] In another embodiment of any one of the above embodiments of the styrenic polymer, where the end group has structure 2a), R' and R'' are both selected from the same substituent selected from hydrogen, halide, a C1-C20 alkyl moiety, or a C1-C20 alkyloxy moiety.

[0119] In another embodiment of any one of the above embodiments of the styrenic polymer, where the end groups have the structure 2a), R' and R'' are hydrogen.

[0120] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has structure 2), the end group has the more specific structure 2b) below, where L3 is a C1-C19 alkylene; and

[0121] [ka] represents a direct valence bond attaching the end group 2b) to the end of the polymer chain of the styrenic polymer:

[0122] [ka]

[0123] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has structure 2b), L3 is a C1-C5 alkylene moiety.

[0124] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end group has structure 2b), L3 is a C1-C2 alkylene moiety.

[0125] In any other embodiment of the above styrenic polymer, wherein the end group has the structure 2b), L3 is a C1 alkylene moiety.

[0126] In another embodiment of any one of the above embodiments of the styrenic polymer, in which the end groups have the structure 1), 1a), 1b), 1c), 2), 2a), or 2b), the styrenic polymer has a polydispersity of 1 to about 1.1. In another aspect of this embodiment, the polymer has a polydispersity of 1 to about 1.09, 1 to about 1.08, 1 to about 1.07, 1 to about 1.06, 1 to about 1.05, 1 to about 1.04, 1 to about 1.03, 1 to about 1.02, or 1 to about 1.01.

[0127] In another embodiment of the styrenic polymer, in which the end groups have the structures 1), 1a), 1b), 1c), 2), 2a), or 2b), the styrenic polymer has a Mw of about 1,000 g / mol to about 50,000 g / mol. In other embodiments of this aspect of the invention, the styrenic polymer may have a Mw of about 1000 g / mol to about 40000 g / mol, about 1000 to about 30000, about 1000 to about 20000, about 1000 to about 10000, about 1000 to about 9000, about 1000 to about 8000, about 1000 to about 7000, about 1000 to about 6000, about 2000 to about 6000, about 3000 to about 6000, about 4000 to about 6000, about 5000 to about 6000, about 5100 to about 5500, or about 5100 to about 5400.

[0128] In another embodiment of the invention, the styrenic polymer has a polydispersity of 1 to about 1.3 and has structure 3):

[0129] [ka]

[0130] wherein R1 is a C1-C20 alkyl; R2, R3, R4, and R5 are independently selected from hydrogen or a C1-C20 alkyl moiety; R6, R 6a , R 6b , R 6c and R 6d is independently selected from the group consisting of hydrogen, C1-C20 alkyl, C1-C20 alkyloxy, C1-C10 fluoroalkyl, C1-C10 fluoroalkyloxy, trialkylsilyl, (trialkylsilyl)alkylene, and (trialkylsilyl)alkyleneoxy; R is selected from the group consisting of hydrogen, halide, a C1-C20 alkyl moiety, and a C1-C20 alkyloxy moiety; n is the number of repeat units in the polymer chain and is a positive integer other than 0; and m is 1 to 3.

[0131] In another embodiment of any one of the above embodiments, wherein the styrenic polymer has structure 3, m is 1.

[0132] In another embodiment of any one of the above embodiments, wherein the styrenic polymer has structure 3, m is 2.

[0133] In another embodiment of any one of the above embodiments, wherein the styrenic polymer has structure 3, m is 3.

[0134] In another embodiment of any one of the above embodiments, wherein the styrenic polymer has structure 3, R2, R3, R4, and R5 are all hydrogen.

[0135] In another embodiment of any one of the above embodiments, wherein the styrenic polymer has structure 3, R6, R 6a , R 6b , R 6c and R 6d are all hydrogen.

[0136] In another embodiment of any one of the above embodiments of the styrenic polymer, where the styrenic polymer has structure 3, and more specifically structure 3a), the styrenic polymer has a polydispersity of 1 to about 1.3.

[0137] [ka]

[0138] In another embodiment of any one of the above embodiments, wherein the styrenic polymer has structure 3a), R2, R3, R4 and R5 are all hydrogen.

[0139] In another embodiment of any one of the above embodiments, in which the styrenic polymer has structure 3a), R6, R 6a , R 6b , R 6c and R 6d are all hydrogen.

[0140] In another embodiment of any one of the above embodiments, where the styrenic polymer has structure 3a), the styrenic polymer has the more specific structure 3b).

[0141] [ka]

[0142] In another embodiment of any one of the above embodiments, wherein the styrenic polymer has structure 3b), R2, R3, R4 and R5 are all hydrogen.

[0143] In another embodiment of any one of the above embodiments, wherein the styrenic polymer has structure 3b), R6, R 6a , R 6b , R 6c and R 6d are all hydrogen.

[0144] In another embodiment of any one of the above embodiments, wherein the styrenic polymer has structure 3b), R1 is a C1-C6 alkyl, R2, R3, R4, and R5 are independently selected from the group consisting of hydrogen and C1-C4 alkyl moieties, and R6, R 6a , R 6b , R 6c and R 6d is independently selected from the group consisting of hydrogen and C1-C4 alkyl, and R is hydrogen.

[0145] In another embodiment of any one of the above embodiments, wherein the styrenic polymer has structure 3a) or 3b), R1 is C1-C6 alkyl, R2 and R3 are hydrogen, and R4 and R5 are independently selected from the group consisting of hydrogen and C1-C4 alkyl moieties; R6, R 6a , R 6b , R 6c and R 6d is independently selected from the group consisting of hydrogen and C1-C4 alkyl, and R is hydrogen.

[0146] In another embodiment of any one of the above embodiments, wherein the styrenic polymer has structure 3), 3a) or 3b), the styrenic polymer is one in which R2 is hydrogen.

[0147] In another embodiment of any one of the above embodiments, wherein the styrenic polymer has structure 3), 3a) or 3b), the styrenic polymer is one in which R2 is a C1-C4 alkyl moiety.

[0148] In another embodiment of any one of the above embodiments, in which the styrenic polymer has structure 3), 3a), or 3b), R3 is hydrogen.

[0149] In another embodiment of any one of the above embodiments, wherein the styrenic polymer has structure 3), 3a) or 3b), R3 is a C1-C4 alkyl moiety.

[0150] In another embodiment of any one of the above embodiments, in which the styrenic polymer has structure 3), 3a), or 3b), R4 is hydrogen.

[0151] In another embodiment of any one of the above embodiments, wherein the styrenic polymer has structure 3), 3a) or 3b), R4 is a C1-C4 alkyl moiety.

[0152] In another embodiment of any one of the above embodiments, in which the styrenic polymer has structure 3), 3a) or 3b), R5 is hydrogen.

[0153] In another embodiment of any one of the above embodiments, wherein the styrenic polymer has structure 3), 3a) or 3b), R5 is a C1-C4 alkyl moiety.

[0154] In another embodiment of any one of the above embodiments, wherein the styrenic polymer has structure 3), 3a) or 3b), R, R 6a , R 6b , R 6c and R 6d is hydrogen.

[0155] In another embodiment of any one of the above embodiments, in which the styrenic polymer has 3), 3a) or 3b), R1 is C1-C6 alkyl, R2, R3, R4 and R5 are hydrogen, and R6, R 6a , R 6b , R 6c and R 6dis independently selected from the group consisting of hydrogen and C1-C4 alkyl, and R is hydrogen.

[0156] In another embodiment of any one of the above embodiments, in which the styrenic polymer has 3), 3a) or 3b), R1 is C1-C6 alkyl, R2, R3, R4 and R5 are hydrogen, and R6, R 6a , R 6b , R 6c and R 6d is hydrogen and R is hydrogen.

[0157] In another embodiment of any one of the above embodiments, where the styrenic polymer has structure 3), 3a), or 3b), the styrenic polymer is one where R is a halide, which may be selected from the group consisting of F, Cl, Br, or I. In another aspect of this embodiment, the halide is F, in another aspect the halide is Cl, in another aspect the halide is Br, and in yet another aspect the halide is I.

[0158] In another embodiment of any one of the above embodiments, where the styrenic polymer has structure 3), 3a) or 3b), the styrenic polymer is one in which R is an alkyl moiety and R is a C1-C20 alkyl moiety. In another aspect of this embodiment, R is a C1-C15 alkyl moiety, R is a C1-C10 alkyl moiety, R is a C1-C5 alkyl moiety, R is a C1-C4 alkyl moiety, R is a C1-C3 alkyl moiety, R is a C1-C2 alkyl moiety, or R is a C1 alkyl moiety.

[0159] In another embodiment of any one of the above embodiments, wherein the styrenic polymer has structure 3), 3a), or 3b), R is an alkyloxy moiety and R is a C1-C20 alkyloxy moiety. In another aspect of this embodiment, R is a C1-C15 alkyloxy moiety, R is a C1-C10 alkyloxy moiety, R is a C1-C5 alkyloxy moiety, R is a C1-C4 alkyloxy moiety, R is a C1-C3 alkyloxy moiety, R is a C1-C2 alkyloxy moiety, or R is a C1 alkyloxy moiety.

[0160] In another embodiment of the invention, the styrenic polymer has a polydispersity of 1 to about 1.3 and has structure 4), where R1 is a C1-C20 alkyl, R'2, R'3 are independently selected from hydrogen or a C1-C20 alkyl moiety, R6, R 6a , R 6b , R 6c and R 6d are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C1-C20 alkyloxy, C1-C10 fluoroalkyl, C1-C10 fluoroalkyloxy, trialkylsilyl, (trialkylsilyl)alkylene, and (trialkylsilyl)alkyleneoxy; R' is selected from the group consisting of hydrogen, halide, a C1-C20 alkyl moiety, and a C1-C20 alkyloxy moiety; n is the number of repeat units in the polymer chain and is a positive integer other than 0; and m' is an integer from 1 to 3.

[0161] [ka]

[0162] In any one of the above embodiments, wherein the styrenic polymer has structure 4), R'2 and R'3 are independently selected from C1-C10 alkylene moieties.

[0163] In another embodiment of the styrenic polymer having structure 4), the styrenic polymer is one where m' is 1 or 2.

[0164] In another embodiment of any one of the above embodiments, wherein the styrenic polymer has structure 4), R' and R'' are hydrogen.

[0165] In another embodiment of any one of the above embodiments, the styrenic polymer has structure 4), R6, R 6a , R 6b , R 6c and R 6d is independently selected from the group consisting of hydrogen.

[0166] In another embodiment of any one of the above embodiments, where the styrene-based polymer has structure 4), the styrene-based polymer has the more specific structure 4a), where R1 is a C1-C20 alkyl, R'2, R'3 are independently selected from hydrogen or a C1-C20 alkyl moiety, and R6, R 6a , R 6b , R 6c and R 6d are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C1-C20 alkyloxy, C1-C10 fluoroalkyl, C1-C10 fluoroalkyloxy, trialkylsilyl, (trialkylsilyl)alkylene, and (trialkylsilyl)alkyleneoxy; R' is selected from the group consisting of hydrogen, halide, a C1-C20 alkyl moiety, and a C1-C20 alkyloxy moiety; and n is the number of repeat units in the polymer chain and is a positive integer other than 0.

[0167] [ka]

[0168] In any one of the above embodiments, wherein the styrenic polymer has structure 4a), R'2 and R'3 are independently selected from C1-C10 alkylene moieties.

[0169] In another embodiment of the styrenic polymer having structure 4a), the styrenic polymer is one in which R' and R'' are hydrogen.

[0170] In another embodiment of any one of the above embodiments, in which the styrenic polymer has structure 4a), R6, R 6a , R 6b , R 6c and R 6d is independently selected from the group consisting of hydrogen.

[0171] In another embodiment of any one of the above embodiments, where the styrenic polymer has structure 4) or 4a), the styrenic polymer has the more specific structure 4b).

[0172] wherein R1 is a C1-C20 alkyl, R'2, R'3 are independently selected from hydrogen or a C1-C20 alkyl moiety, and R6, R 6a , R 6b , R 6c and R 6d are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C1-C20 alkyloxy, C1-C10 fluoroalkyl, C1-C10 fluoroalkyloxy, trialkylsilyl, (trialkylsilyl)alkylene, and (trialkylsilyl)alkyleneoxy; R' is selected from the group consisting of hydrogen, halide, a C1-C20 alkyl moiety, and a C1-C20 alkyloxy moiety; and n is the number of repeat units in the polymer chain and is a positive integer other than 0.

[0173] [ka]

[0174] In any other embodiment of the above embodiments, wherein the styrenic polymer has structure 4), 4a), or 4b), R'2 and R'3 are independently selected from C1 to C10 alkylene moieties.

[0175] In another embodiment of any one of the above embodiments, where the styrenic polymer has structure 4), 4a) or 4b), R' and R'' are hydrogen.

[0176] In another embodiment of any one of the above embodiments, where the styrenic polymer has structure 4), 4a) or 4b), R' and R'' are hydrogen.

[0177] In another embodiment of any one of the above embodiments, in which the styrenic polymer has structure 4), 4a) or 4b), R, R 6a , R 6b , R 6c and R 6d is hydrogen.

[0178] In another embodiment of any one of the above embodiments, in which the styrenic polymer has structure 4), 4a) or 4b), R1 is a C1-C6 alkyl, R'2, R'3 are independently selected from the group consisting of hydrogen and C1-C4 alkyl moieties, and R6, R 6a , R 6b , R 6c and R 6d are independently selected from the group consisting of hydrogen and C1-C4 alkyl, and R' and R'' are hydrogen.

[0179] In another embodiment of any one of the above embodiments, in which the styrenic polymer has structure 4), 4a) or 4b), R1 is C1-C6 alkyl, R'2 and R'3 are hydrogen, and R6, R 6a , R 6b , R 6c and R 6d are independently selected from the group consisting of hydrogen and C1-C4 alkyl, and R' and R'' are hydrogen.

[0180] In another embodiment of any one of the above embodiments, in which the styrenic polymer has structure 4), 4a) or 4b), R1 is C1-C6 alkyl, R'2 and R'3 are hydrogen, and R6 and R 6a , R 6b , R 6c and R 6d is hydrogen, and R' and R'' are hydrogen.

[0181] In another embodiment of any one of the above embodiments, where the styrenic polymer has structure 4), 4a) or 4b), R' and R'' are hydrogen.

[0182] In another embodiment of any one of the above embodiments, where the styrenic polymer has structure 4), 4a) or 4b), R′ and R″ are halides.

[0183] In another embodiment of any one of the above embodiments, where the styrenic polymer has structure 4), 4a) or 4b), R' and R'' are C1-C20 alkyl moieties.

[0184] In another embodiment of any one of the above embodiments, where the styrenic polymer has structure 4), 4a) or 4b), R' and R'' are C1-C20 alkyloxy moieties.

[0185] In another embodiment of any one of the above embodiments, in which the styrenic polymer has structure 4), 4a) or 4b), R, R 6a , R 6b , R 6c and R 6d is hydrogen.

[0186] In another embodiment of any one of the above embodiments, in which the styrenic polymer has structure 4), 4a) or 4b), R'2 is hydrogen.

[0187] In any one of the above embodiments, wherein the styrenic polymer has structure 4), 4a) or 4b), R'2 is a C1-C20 alkyl moiety.

[0188] In another embodiment of any one of the above embodiments, in which the styrenic polymer has structure 4), 4a) or 4b), R'3 is hydrogen.

[0189] In any one of the above embodiments, wherein the styrenic polymer has structure 4), 4a) or 4b), R'3 is a C1-C20 alkyl moiety.

[0190] In another embodiment of any one of the above embodiments, wherein the polymer has structure 3), 3a), 3b), 4), 4a), or 4b), the polystyrene has a polydispersity of 1 to about 1.1. In another aspect of this embodiment, the polymer has a polydispersity of 1 to about 1.09, 1 to about 1.08, 1 to about 1.07, 1 to about 1.06, 1 to about 1.05, 1 to about 1.04, 1 to about 1.03, 1 to about 1.02, or 1 to about 1.01.

[0191] In another embodiment of any one of the above embodiments, wherein the polymer has structure 3), 3a), 3b), 4), 4a), or 4b), the styrenic polymer has a Mw of about 1000 g / mol to about 50000 g / mol. In another embodiment of this aspect of the invention, the styrenic polymer may have a Mw of about 1000 g / mol to about 40000 g / mol, about 1000 to about 30000, about 1000 to about 20000, about 1000 to about 10000, about 1000 to about 9000, about 1000 to about 8000, about 1000 to about 7000, about 1000 to about 6000, about 2000 to about 6000, about 3000 to about 6000, about 4000 to about 6000, about 5000 to about 6000, about 5100 to about 5500, or about 5100 to about 5400.

[0192] Another aspect of the present invention is a composition comprising a styrenic polymer and a solvent, wherein the styrenic polymer is selected from any one of the above embodiments of the styrenic polymer.

[0193] In another embodiment of the present invention, the styrenic polymer may be a mixture of two or more different styrenic polymers selected from any of the above embodiments of the styrenic polymer.

[0194] In another aspect of the novel composition, the composition may include as components further additives such as surfactants, leveling agents, stabilizers, thermal acid generators, photoacid generators, and the like.

[0195] In the above embodiment of the novel composition, the solvent is one that dissolves the novel styrenic polymer and any other additional components. The solvent may be a single solvent or a mixture of solvents. Suitable solvents are organic solvents, for example glycol ether derivatives, such as ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, propylene glycol n-propyl ether or diethylene glycol dimethyl ether; glycol ether ester derivatives, such as ethyl cellosolve acetate, methyl cellosolve acetate or propylene glycol monomethyl ether acetate (PGMEA); carboxylates, such as ethyl acetate, n-butyl acetate and amyl acetate; carboxylates of dibasic acids, such as diethyl oxylate and diethyl malonate; dicarboxylates of glycols, such as ethylene glycol diacetate and propylene glycol diacetate; and hydroxycarboxylates, such as methyl lactate, ethyl lactate (EL), ethyl glycolate and ethyl 3-hydroxypropionate; ketone esters, such as methyl pyruvate or ethyl pyruvate; Mention may be made of alkyloxycarboxylic acid esters, such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate or methyl ethoxypropionate; ketone derivatives, such as methyl ethyl ketone, acetylacetone, cyclopentanone, cyclohexanone or 2-heptanone; ketone ether derivatives, such as diacetone alcohol methyl ether; ketone alcohol derivatives, such as acetol or diacetone alcohol; ketals or acetals, such as 1,3 dioxalane and diethoxypropane; lactones, such as butyrolactone; amide derivatives, such as dimethylacetamide or dimethylformamide, anisole and mixtures thereof.

[0196] In addition to the solvent, the novel composition may contain a surfactant as an additive to facilitate coating.

[0197] The novel composition may also optionally include an acid generator, such as a thermal acid generator and / or a photoacid generator. Although such additives are not required for assistance, they may release acid to assist the benzyl alcohol end group portion of the novel styrene-based polymer to graft on the substrate to form a pinning layer. This may help achieve a higher level of grafting on the substrate surface, and also allows for a lower bake temperature required for grafting to occur after coating.

[0198] Suitable thermal acid generators include onium salts, halogen-containing compounds, perfluorobenzenesulfonate esters, perfluoroalkanesulfonate esters, etc. Non-limiting exemplary thermal acid generators for the above formulations include tri-C1-C8-alkylammonium p-toluenesulfonate, C1-C8-alkylammonium dedecylbenzenesulfonate, tri-C1-C8-alkylammonium perfluorobutane-1-sulfonate, tri-C1-C8-alkylammonium trifluoromethane-sulfonate, N-hydroxyphthalimidotrifluoromethane-sulfonate, bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, bis(4-t-butylphenyl)iodonium perfluoro-1 ... -butanesulfonate, bis(4-t-butylphenyl)iodonium perfluoro-1-octanesulfonate, bis(phenyl)iodonium hexafluoroantimonate, N-hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butanesulfonate, 2-nitrobenzyl trifluoromethanesulfonate, 4-nitrobenzyl trifluoromethanesulfonate, 2-nitrobenzyl perfluorobutanesulfonate, 4-nitrobenzyl perfluorobutanesulfonate, or a combination comprising at least one of the foregoing. Suitable photoacid generators include, for example, aromatic and aliphatic sulfonium and iodonium salts.

[0199] Another aspect of the present invention is a novel method for grafting a pinning layer onto a substrate, comprising the steps of: a) coating a substrate with any of the above compositions comprising any of the novel styrenic polymers of embodiment 1 or 2 to form a coated layer; b) heating the coated layer of polymer at a temperature of about 120° C. to about 190° C. to remove the solvent and cause grafting; c) treating the heated coated layer with an organic solvent to remove ungrafted polymer leaving an insoluble graft pinning layer on the substrate.

[0200] In another aspect of the novel method of grafting a pinning layer onto a substrate, in the novel composition step b) of removing the solvent and grafting the copolymer onto the substrate, this step may be carried out at a temperature ranging from about 140° C. to about 170° C., or from 150° C. to about 170° C. The time for removing the solvent and grafting the novel styrenic polymer onto the substrate is about 1 to 10 minutes, or about 1 to 5 minutes.

[0201] In another aspect of the novel method of grafting a pinning layer, a typical initial film thickness, prior to removal of ungrafted material in step c), after heating ranges from about 10 nm to about 200 nm, or from about 20 nm to about 100 nm, or from about 20 nm to about 80 nm, or from about 30 nm to about 60 nm, or from about 40 nm to about 60 nm.

[0202] When a thermal acid generator is present as an additive, the temperature required for solvent removal and grafting in step b) may be from about 90° C. to about 170° C., or from about 100° C. to about 170° C. Again, the time for removing the solvent and grafting the novel styrenic polymer onto the substrate may be from about 1 to 10 minutes, or in another embodiment from about 2 to 5 minutes.

[0203] If a photoacid generator is present, the acid is released during an optional blanket irradiation step with UV, deep UV or VUV radiation after a bake to remove only the solvent in the range of about 90 to about 150 °C. High acidity photoacids (i.e., pK a Following the irradiation step for photoacid generators releasing an acid radical (A) of 100 to 150° C., the grafting can be carried out without a subsequent graft bake step, or can be followed by a mild graft bake step at about 90 to about 150° C. In other cases, a relatively low acidity photoacid (i.e., pH a For photoacid generators to release ≧−2), bake temperatures ranging from about 90° C. to about 200° C. may be used. Generally, the heating time to remove the solvent and graft the copolymer to the substrate is 1 to 10 minutes, or in another embodiment 1 to 5 minutes.

[0204] Another aspect of the present invention is a novel first method for chemoepitaxy-induced self-assembly of block copolymer layers used to form images, comprising the steps of: a1) coating a substrate with a graftable neutral layer polymer precursor to form a coated layer 1; b1) heating the coated layer 1 to a temperature of 90°C to 180°C to remove the solvent; c1) heating the coating after step b1) to a temperature of 200°C-300°C to cause grafting; d1) treating the coating after step c1) with an organic solvent to remove ungrafted neutral layer polymer, thus leaving an insoluble grafted neutral layer on the substrate; e1) coating a photoresist layer on said grafted neutral layer; f1) forming a negative tone pattern in said photoresist layer, whereby said grafted neutral layer forms areas covered with resist and areas not covered with resist, where the pattern in the resist includes both small nanometer sized repeating patterns and large areas of resist removed during the imaging process that do not contain the repeating nanometer sized patterns; g1) etching to remove the neutral layer areas not covered in step f1) leaving bare substrate in these areas; h1) stripping the resist from the substrate after step g1) to leave a patterned substrate, where areas of the substrate left uncovered with resist in step f1) do not include the grafted neutral layer and areas covered with resist in step f1) retain the grafted neutral layer; i1) coating the patterned substrate with the composition of claim 26 or 27 to form a coated layer 2; j1) heating the coated layer 2 at a temperature of 120°C to 190°C; k1) treating the coated layer 2 after heating step j1) with an organic solvent to remove ungrafted polymer, thereby leaving insoluble grafted pinning layer material on the substrate in areas not including the grafted neutral layer to form a substrate having both pinned layer and neutral layer regions; l1) applying a coating of a block copolymer comprising an etch resistant styrenic block and a highly etchable aliphatic block onto a substrate comprising a patterned neutral layer and a pinned layer to form a substrate comprising both a patterned neutral layer and a patterned pinned layer; m1) annealing the block copolymer layer until self-organization occurs in small nanometer-sized repeating patterns on the substrate, whereby perpendicular orientation of the block polymer domains does not occur in the large regions containing the graft pinning layer.

[0205] In another aspect of the above novel first method of chemoepitaxy in step j1), the temperature for grafting can be varied as described above for the method of forming a grafted crosslinked coating of the novel copolymer of the present invention. Also, the bake time of this step can be varied as described above. In another embodiment of this aspect of the present invention, step m1) is followed by step n1) to form an image in the substrate by using self-assembled block copolymer domains to provide a selective barrier to etching into the substrate. This selective etching can be provided by different reactivity of the assembled block domains to chemical etchants or to plasma etching steps, each of which is used to etch the substrate. An example is when one block is a plasma etch resistant block and the other is highly etchable in plasma. The selective etching into the substrate by the self-assembled block copolymer can be used to provide an image in the substrate. This image can then be used in the manufacture of microelectronic devices by defining structures in a particular layer used in the method for manufacturing memory or logic devices. Negative or positive resists can be used in steps e1) and f1). In the case of positive resists, their tone is reversed by developing with an organic solvent instead of a TMAH based developer to obtain a negative image instead of a positive, and the radiation used to form the photoresist pattern formed in step f1) may be selected from e-beam, broadband, UV, 193 nm immersion lithography, 13.5 nm, 193 nm, 248 nm, 365 nm and 436 nm radiation.

[0206] Another aspect of the present invention is a novel second method for chemoepitaxy-induced self-assembly of block copolymer layers used to form images, comprising the steps of: a2) forming a coating of a neutral layer polymer precursor, which is crosslinkable or crosslinkable and graftable onto a substrate; b2) heating the crosslinkable neutral polymer layer precursor coating or the crosslinkable and graftable precursor coating at a temperature of about 90° C. to about 180° C. to remove the solvent; c2) heating the crosslinkable neutral layer polymer layer precursor coating, or the crosslinkable and graftable precursor coating, at a temperature of about 200° C. to about 300° C. to form a crosslinked neutral layer, or a crosslinked and grafted neutral layer; d2) providing a coating of a photoresist layer on said crosslinked neutral layer or on said crosslinked and grafted neutral layer; e2) forming a negative tone pattern in said photoresist layer, whereby said crosslinked neutral layer or crosslinked and grafted neutral layer forms areas covered and uncovered by resist, wherein said pattern in resist includes both small nanometer repeating patterns and large areas of resist removed during the imaging process that do not contain repeating nanometer sized patterns; f2) etching away the crosslinked neutral layer or the crosslinked and grafted neutral layer in the neutral layer areas not covered in step e2) using plasma to leave a bare substrate in the areas not covered in step e2); g2) stripping the resist from the substrate after step f2) to leave a patterned substrate, where the substrate in areas left uncovered by resist in step e2) does not contain the crosslinked neutral layer or the crosslinked and grafted neutral layer, and the areas covered by resist in step f2) retain the crosslinked neutral layer or the crosslinked and grafted neutral layer; h2) coating the patterned substrate with the composition of claim 26 or 27 to form a coated layer; i2) heating the coated layer at a temperature of 120°C to 190°C; j2) treating the coated layer after heating step i1) with an organic solvent to remove ungrafted polymer, thereby leaving insoluble crosslinked or crosslinked and grafted pinning layer material on the substrate in areas that do not include a crosslinked neutral layer or areas that do not include a crosslinked and grafted neutral layer, to form a substrate that includes both a patterned neutral layer and a patterned pinning layer; k2) applying a coating of a block copolymer comprising an etch resistant styrenic block and a highly etchable aliphatic block onto the substrate comprising the patterned neutral layer and the pinned layer; l2) annealing the block copolymer layer until directed self-organization occurs in small nanometer-sized repeating patterns on the substrate, whereby perpendicular orientation of the block polymer domains does not occur in the large areas containing the graft pinned layer.

[0207] In another aspect of the above novel second method of chemoepitaxy in step j2), the temperature for grafting can be varied as described above for the method of forming a grafted crosslinked coating of the novel copolymer of the present invention. Also, the bake time of this step can be varied as described above. In another embodiment of this aspect of the present invention, step l2) is followed by step m2) to form an image in the substrate by using self-assembled block copolymer domains to provide a selective barrier to etching into the substrate. This selective etching can be provided by different reactivity of the assembled block domains to chemical etchants or to plasma etching steps, each of which is used to etch the substrate. An example is when one block is a plasma etch resistant block and the other is highly etchable in plasma. The selective etching into the substrate by the self-assembled block copolymer can be used to provide an image in the substrate. This image can then be used in the manufacture of microelectronic devices by defining structures in a particular layer used in the method for manufacturing memory or logic devices. Negative or positive resists can be used in steps d2) and e2). In the case of positive photoresists, their tone is reversed by developing with an organic solvent instead of a TMAH-based developer to obtain a negative image instead of a positive, and the radiation used to form the photoresist pattern formed in step f2) may be selected from electron beam, broadband, 193 nm immersion lithography, 13.5 nm, 193 nm, 248 nm, 365 nm and 436 nm radiation.

[0208] In general, but without being bound by theory, if the substrate has a more favorable interfacial energy for one domain of the lamella-forming diblock copolymer than for the other, the interaction between the substrate and the favorable domain will cause the lamella to be oriented parallel to the substrate in the thin film instead of perpendicular orientation. This parallel geometry in the thin film has three typical structures, such as asymmetric structure, symmetric structure, and hole-island structure, depending on the BCP film thickness and the interfacial energy between the BCP domain and the surrounding environment (e.g., air or N2). On a substrate grafted with polystyrene (PS), coated with BCP and annealed in N2 atmosphere, both the PS domain and the PMMA domain have the same interfacial energy. As a result, both the PS domain and the PMMA domain can be arranged in a parallel orientation to the substrate surface.

[0209] Specifically, in the large areas where the neutral layer has been removed in the above-described method where the layer of the novel polystyrenic polymer can be grafted onto a bare substrate, the grafted layer forms a surprisingly strong, dense and uniform pinning layer, which can be used to avoid the formation of defects in these large areas that would occur in the case of a diblock-type lamella-forming block copolymer with a styrenic block (or other etch-resistant polymer block with a similar polarity to the novel grafted polystyrenic layer formed from the novel polymer) and an aliphatic block (or other etchable polymer block with a different polarity from the styrenic block). The formation of such a surprisingly strong pinning layer creates a surface that is highly favorable for consistent parallel lamellar orientation of the block copolymer consistently over the entire large surface with the grafted pinning layer. These parallel lamellar orientations result in a block copolymer coating that, along with its orientation uniformity, provides a general etch rate over the entire surface during pattern etching. This uniformity of etching of the block copolymer coating over large areas prevents the formation of defective areas with inconsistent etch rates. This will occur when the block copolymer coating forms self-organized island or hole structure shapes during self-assembly. Such shapes will occur on a substrate for a given coating of a lamella-forming diblock copolymer with a given Lo that would otherwise form either an asymmetric or symmetric structure with parallel lamellar-type orientation of the block copolymer domains on a good pinning area. Therefore, in summary, the grafted pinning layer formed from the novel styrenic polymer forms a surprisingly strong and uniform pinning layer that results in the consistent formation of parallel lamella formation over a large area that does not contain nanometer-sized repeating patterns such as lines and spaces or trenches.

[0210] In the above grafting process and in chemo-epitaxy method 1 or 2, the solvent required to remove the ungrafted novel styrenic polymer may be any of the solvents previously described as suitable for dissolving these materials to form the novel compositions described herein.

[0211] Similarly, in the above chemoepitaxy methods 1 or 2, suitable solvents for removing the ungrafted neutral layer precursor, the uncrosslinked neutral layer precursor, or the ungrafted and uncrosslinked neutral layer precursor are those described as suitable in the references previously cited herein used to describe suitable neutral layer materials.

[0212] In the above chemoepitaxy method 1 or 2, the block copolymer for use in combination with the novel styrenic composition capable of forming a pinning layer can be any block copolymer capable of forming domains through self-organization. Blocks of the same type that tend to self-associate form microdomains. Typically, the block copolymers used for this purpose are polymers in which repeat units derived from monomers are arranged into blocks that are compositionally, structurally, or both different and capable of phase separation and domain formation. These blocks have different properties such that one block can be removed and the other block can remain intact on the surface and can thus be used to provide a pattern on the surface. Therefore, the block can be selectively removed by plasma etching, solvent etching, developer etching with aqueous alkaline solution, etc. In block copolymers based on organic monomers, one block can be made of polyolefinic monomers, including polydienes, poly(alkylene oxides), such as poly(ethylene oxide), poly(propylene oxide), poly(butylene oxide) and mixtures thereof; the other block can be made of various monomers, including poly((meth)acrylates), polystyrenes, polyesters, polyorganosiloxanes, polyorganogermanes and / or mixtures thereof. Each of these blocks in the polymer chain can contain one or more repeat units derived from a monomer. Depending on the pattern required and the type of method used, different types of block copolymers can be used. For example, they can consist of diblock, triblock, terpolymers or multiblock copolymers. The blocks of these block copolymers can themselves consist of homopolymers or copolymers.Different types of block copolymers can also be used for self-assembly, such as resinous block copolymers, hyperbranched block copolymers, graft block copolymers, organic diblock copolymers, organic multiblock copolymers, linear block copolymers, star block copolymers, amphiphilic inorganic block copolymers, amphiphilic organic block copolymers, or a mixture of at least different types of block copolymers.

[0213] The blocks of the organic block copolymer may contain repeat units derived from monomers such as C2-C30 olefins, (meth)acrylate monomers derived from C1-C30 alcohols, inorganic containing monomers such as monomers based on Si, Ge, Ti, Fe, Al. The C2-C30 olefin-based monomers may constitute the high etch resistant block alone or may form such a block in combination with one other olefinic monomer. Specific examples of this type of olefinic monomer are 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.

[0214] An illustrative example of a block copolymer containing one type of highly etch resistant repeat unit would be a polystyrene block containing only repeat units derived from styrene and another type of highly etchable polymethyl methacrylate block containing only repeat units derived from methyl methacrylate, which together form the block copolymer poly(styrene-b-methyl methacrylate), where b refers to the block.

[0215] Specific non-limiting examples of block copolymers useful for graphoepitaxy, chemoepitaxy or pinned chemoepitaxy used for directed self-assembly on patterned substrates containing patterned regions of a neutral layer and patterned regions of a novel polystyrene-based pinned layer are poly(styrene-b-vinylpyridine), poly(styrene-b-butadiene), poly(styrene-b-isoprene), poly(styrene-b-methyl methacrylate), poly(styrene-b-alkenyl aromatics), poly(isoprene-b-ethylene oxide), poly(styrene-b-(ethylene- Poly(ethylene oxide-b-caprolactone), poly(butadiene-b-ethylene oxide), poly(styrene-b-butyl(meth)acrylate), poly(methyl methacrylate-b-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 comprising at least one of the block copolymers described above. All of these polymeric materials have in common the presence of at least one block rich in repeating units that are resistant to etching techniques typically used in the manufacture of IC devices, and at least one block that is rapidly etched under these same conditions. This allows the directed self-assembled polymer to perform pattern transfer to a substrate, resulting in either pattern modification or pattern multiplication.

[0216] Typically, block copolymers used for directed self-assembly, such as in graphoepitaxy, chemoepitaxy, or pinned chemoepitaxy, have a weight average molecular weight (M) in the range of about 3,000 to about 500,000 g / mol. w ), and a number average molecular weight (M n ), and a polydispersity (M) of 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 ) M w and M n Both molecular weights can be determined, for example, by gel permeation chromatography using universal calibration methods, calibrated against polystyrene standards, to ensure that the polymer blocks have sufficient mobility to self-assemble when applied to a given surface, either spontaneously, or through a purely thermal treatment, or through a thermal process assisted by imbibing solvent vapors into the polymer framework to enhance the flow of segments so that self-assembly occurs.

[0217] Solvents suitable for dissolving block copolymers to form films may vary with the solubility requirements 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, n-amyl ketone (MAK), gamma-butyrolactone (GBL), toluene, and the like. In one embodiment, particularly useful casting solvents include propylene glycol monomethyl ether acetate (PGMEA), gamma-butyrolactone (GBL), or a combination of these solvents.

[0218] The block copolymer composition can include additional components and / or additives selected from the group consisting of inorganic-containing polymers; additives including small molecules, inorganic-containing molecules, surfactants, photoacid generators, thermal acid generators, quenchers, hardeners, crosslinkers, chain extenders, and the like; and combinations comprising at least one of the foregoing, wherein one or more of the additional components and / or additives assemble with the block copolymer to form a block copolymer assembly.

[0219] The block copolymer composition is applied onto a patterned substrate containing a patterned region of a neutral layer, and the patterned region of the novel polystyrenic pinning layer is defined on the surface by conventional lithography as described above, where the neutral layer surface is formed by a material as described above, and the pinning layer is formed by the novel styrenic polymer described herein. Upon application and solvent removal, the block copolymer undergoes self-assembly on the neutral layer, guided by the specific pattern formed by conventional lithographic processing, through the patterned chemical differences of the substrate surface created by conventional lithographic processing. Depending on the relative pitch of the pattern and the microphase separation distance after standard IC processing for pattern transfer, pattern modification while maintaining the same resolution can be achieved, and / or pattern multiplication can also be achieved if multiphase boundaries are formed between the features defined by conventional lithography.

[0220] Application of the block copolymer by spinning techniques (including spin drying) may be sufficient to form a self-derivatized block copolymer texture. Other methods of self-derivatized domain formation may occur during application, baking, annealing, or a combination of one or more of these operations. Thus, the above methods produce oriented block copolymer assemblies, which have microphase-separated domains that include cylindrical microdomains oriented perpendicular to the neutral surface or lamellar domains oriented perpendicular to the neutral surface. Typically, the microphase-separated domains are lamellar domains oriented perpendicular to the neutral surface, which provides a parallel line / space pattern to the block copolymer texture. It is desirable that the domains oriented in this way are thermally stable under subsequent processing conditions. Therefore, after coating a layer of a block copolymer assembly containing a useful diblock copolymer, such as poly(styrene-b-methyl methacrylate), and optionally baking and / or annealing, the domains of the block copolymer form on and remain perpendicular to the neutral surface, thus providing highly resistant and highly etchable areas on the substrate surface, which can be further pattern-transferred into the substrate layer. The directed self-assembled block copolymer pattern is transferred into the underlying substrate using known techniques. In one example, wet etching or plasma etching can be used, optionally in combination with UV exposure. The wet etching can be with acetic acid. Standard plasma etching processes can be used, such as plasmas containing oxygen; additionally, argon, carbon monoxide, carbon dioxide, CF4, CHF3 can also be present in the plasma.

[0221] In the present invention, the initial negative tone photoresist pattern used to form the directed self-assembly pattern can be defined by a negative tone development process using either a negative or positive tone photoresist, and can be imaged using conventional lithography techniques, such as e-beam, ion beam, x-ray, EUV (13.5 nm), broadband, or UV (450 nm to 10 nm) exposure, immersion lithography, and the like. In one embodiment, the present invention is particularly useful for 193 nm imagewise exposure using either dry lithography or immersion lithography. For 193 nm lithography, commercially available positive tone 193 nm photoresists can be used, including, but not limited to, AZ AX2110P (available from EMD Performance Materials Corp., Somerville, NJ), photoresists from Shin-Etsu Chemical Corp., JSR Micro from Japan Synthetic Rubber, and other photoresists available from FjiFilm, TOK. These photoresists, after exposure and post-exposure bake, can be developed with aqueous alkaline developers containing tetramethylammonium hydroxide to give positive tone patterns, or with organic solvents such as n-amyl ketone (MAK), n-butyl acetate, anisole, etc. to give negative tone patterns. Alternatively, commercially available negative tone photoresists may be used for 193 nm exposure. One particular feature of the present invention is that, surprisingly, the neutrality of the neutral layer with respect to the block copolymer is maintained, despite the high level of crosslinking of the neutral layer. A high level of crosslinking is required when process steps such as overcoating with photoresist, baking the photoresist, exposing the photoresist, developing the photoresist pattern with the developer used as described above for each type of photoresist, and stripping conditions are performed; however, the novel neutral film still maintains neutrality to allow proper orientation of the block copolymer domains between topographic lithographic features.Neutrality is necessary to control the orientation of the block copolymer during the alignment process, so that domains of the block copolymer form on the neutral surface and remain perpendicular to it, as shown in Figures 1a-1c, which show how the block copolymer orients itself into domains perpendicular to the substrate, and one of these domains is removed to form a pattern on the substrate.

[0222] Substrates useful with these chemoepitaxy and grafting processes according to the invention can be any required for IC device fabrication. In one example, the substrate is a wafer coated with a layer of high carbon content organic layer on top of which is coated with a coating of silicon or titanium containing ARC (highly etch resistant to oxygen plasma). This allows for pattern transfer from the patterned block copolymer into these coatings. Suitable substrates include, but are not limited to, silicon, silicon substrates coated with metal surfaces, silicon wafers coated with copper, copper, aluminum, polymeric resins, silicon dioxide, metals, doped silicon dioxide, silicon nitride, silicon carbide, tantalum, polysilicon, ceramics, aluminum / copper mixtures, glass, coated glass; gallium arsenide and other such III / V compounds. These substrates may be coated with anti-reflective coating(s). The substrates may include any number of layers made of the above materials.

[0223] For the present invention, various methods including pinned chemoepitaxy can be used to achieve directed self-assembly of the block copolymers described above using known neutral layers such as those described in US8,835,581, US9,181,449, US9,093,263, US8691925, US20140335324A1, US2016-0122579A1 or US application Ser. No. 14 / 885,328 together with the novel styrenic polymer composition. The contents of these documents are incorporated herein by reference. This pattern can then be further transferred into the substrate. In this way, various high resolution patterns can be pattern transferred into the substrate to achieve pattern modification, pattern multiplication or both.

[0224] In chemoepitaxy, the substrate surface provides a pinning surface pattern in the novel neutral layer that has a specific chemical affinity for one block of the block copolymer, and this affinity and the presence of the neutral layer direct the alignment of the block copolymer. A neutral layer that is resistant to lithographic processes and remains neutral after crosslinking can be used as described above. The pinning pattern in the novel chemoepitaxy methods 1 and 2 described above is formed from a composition that includes the novel styrenic polymer described herein.

[0225] It has also been unexpectedly found that the novel copolymer, when formulated in a composition consisting of the novel polymer and a solvent and coated on a substrate via the novel method, can provide and maintain a grafted layer with very good film uniformity and act as a pinning layer for the block copolymer during processing involving self-assembly. This has the advantage that during self-assembly of the block copolymer covering the top surface, as detailed above, it allows for consistent formation of parallel lamellae over a large area that does not contain nanometer-sized repeating patterns such as lines and spaces or trenches. On the other hand, it avoids the random formation of vertical lamellar orientation of polymer block domains in the block copolymer film covering this large area of ​​the substrate that does not contain a pattern. This random vertical orientation of the block copolymer film covering the top surface would result in a block copolymer with randomly distributed regions with dramatically different etch resistance that would cause defects during pattern transfer into the substrate. EXAMPLES

[0226] More specific aspects of the present invention and experimental results supporting such aspects are described below, but it should be noted that the following disclosure is for illustrative purposes only and is therefore not intended to limit the scope of the invention as defined in the claims in any manner.

[0227] Polymer molecular weights were determined using a Waters 2695 Alliance Module Gel Permeation Chromatograph (Waters Corporation, 34 Maple Street, Milford, Mass.) equipped with one Shodex KF-801 column, two KF-802 columns, one KF-804 column, and a dual UV detector (Model 2487) and a differential refractive index detector (Model 2414). The solvent used was tetrahydrofuran, flowed at 40° C. at a rate of 0.7 mL / min, and calibration was performed with standard polystyrene samples.

[0228] All chemicals were obtained from Millipore Sigma (Billerica Ma).

[0229] Lithography exposure was performed using an EX-mini from Hamamatsu Photonics (250 Wood Avenue, Middlesex, NJ08846). Etching tests were performed using a RIE-1700 from Thorson March (300 Nordson Dr. M / S 47 Amherst, OH 44001 USA). Spin-coating and development of films and patterns were performed using a LARC1012 from Litho Tech Japan Corporation (2-6-6-201 Namiki, Kawaguchi, Saitama 3320034 Japan) or a DuoTrack from SOKUDO (5F K.I. Shijo Building, 88, Shijo-dori, Muromachi Higashiiru, Kanyahoko-cho, Shimojo-ku, Kyoto 600-8009 Japan). Scanning electron micrographs were obtained using an AMAT (Applied Materials, Inc. 3050 Bowers Avenue, PO Box 58039 Stanta Clara, CA 95054-3299 USA) SEM. Cross-sectional SEM of the generated via arrays was examined using a Hitachi (Hitachi High Technologies America Inc. 10 North Martingale Road, Suite 500 Schaumburg, Illinois 60173-2295) S-5500. Contact angles were measured using a Kyowa (Kyowa Interface Science, 5-4-41 Nobidome, Niiza, Saitama 352-0011 Japan) Interface Science Drop Master DY-700.

[0230] Synthesis Example 1: Synthesis of polystyrene end-capped with CH2CH2OH A single-neck 1 L glass reactor was fitted with a septum adapter to facilitate the administration of N2 and depressurization of the reactor. The reactor was dried using a heat gun under dynamic vacuum and backfilled with N2. Approximately 600 mL of anhydrous cyclohexane was transferred into the reactor using a stainless steel cannula under N2. 110 mL (99.66 g) of styrene (degassed and stored under N2) was then added into the reactor using a N2-washed syringe. sec-BuLi (1.4 M) was added dropwise to destroy impurities in the monomer solution. This titration was carried out until a faint honey color persisted in the solution. Immediately, 14.5 mL of 0.020 moles of sec-BuLi (1.4 M) was added to the reaction using a syringe. The solution changed color to orange. The reaction was maintained at 45° C. in a water bath for 4 hours. The living polystyryllithium anion was end-capped with ethylene oxide (EO). A small amount of purified EO (2 mL) distilled over sec-BuLi was transferred into the reactor via cannula. The orange color of the living polystyryllithium disappeared immediately upon addition of EO. Special care should be taken while adding the low boiling monomer solution to the reactor maintained at 45°C. After the addition, the hot water bath was removed and the end-capping reaction was continued for 2 hours at 25°C. The reaction mixture was quenched with 0.5 mL of 1M HCl and an inlet N2 bubbling tube was inserted. Nitrogen was bubbled into the reaction to drive off remaining excess EO from the outlet cannula through a septum into a flask containing a NaOH solution in water for 15 minutes. The reaction mixture was diluted with 30 mL of THF and precipitated into excess ethanol or a solution of ethanol with 10% water. The polymer was washed with ethanol until the filtrate was neutral, and the polymer was dried in vacuum at 55° C. for 10 hours. The yield was 100%. Mw=5250 and Mn=5021 g / mol. Synthesis Example 2: Synthesis of polystyrene end-capped with CH2CH2OPhCH2OH Under nitrogen gas protection, 100 g of the polymer prepared in Example 1 dissolved in 95 g of methylene chloride was charged into a 3 L flask. To this was added 30 g of p-toluenesulfonyl chloride dissolved in 240 g of methylene chloride. While stirring the solution, 18.3 g of triethylamine was added in several portions. After stirring the reaction mixture for 24 hours at room temperature, the solution was slowly poured into methanol with vigorous stirring. The polymer was isolated by filtration. The polymer was purified by precipitation first into water and finally again into methanol. The purified polymer was dried in vacuum at 45° C. until constant weight was obtained, yielding 93 g of white polymer. Proton NMR showed that the OH end groups were successfully converted to OTs.

[0231] Under nitrogen protection, 5 g of 4-hydroxybenzyl alcohol was dissolved in 95 g of DMF, and 32 g of 1M potassium tert-butoxide in THF was added. After stirring at room temperature for about 30 minutes, 23 g of the previously prepared polymer dissolved in 80 g of DMF was slowly added. The reaction mixture was stirred at room temperature for 24 hours, and the solution was poured into 1 L of 1:1 (V / V) water / isopropanol with vigorous stirring. The resulting polymer was isolated by filtration. The polymer was purified by precipitating into water and finally again into isopropanol. The purified polymer was dried in a 50°C vacuum oven until constant weight, yielding 20 g of white polymer. HNMR NMR showed no OTs end groups [OTs groups have two distinct peaks: CH The results showed that the 3H in 3Ph (2.5 ppm, and the aromatic protons in CH3Ph (7.5 ppm)) were successfully converted to benzyl alcohol (H-1 NMR 2H (3.6 ppm), -CH2CH2OPhCH2OH; 2H (4.6 ppm), -CH2CH2OPhCH2OH). GPC molecular weights were found to be Mw=5408 g / mol, Mn=5153 g / mol, D=1.05.

[0232] Comparative Synthesis Example 1 (Azo Initiator Having a Benzyl Alcohol Group) (1) A solution was prepared by dissolving 5.0 g of 4,4'-azobis(4-cyanovaleric acid) in approximately 100 mL of methanol with stirring. To this solution, a solution consisting of an equimolar amount of tetramethylammonium hydroxide pentahydrate in methanol was slowly added with stirring, and stirring was continued for 30 minutes after addition was complete. The solution was then concentrated at room temperature using a rotary evaporator, and the residue was poured into diethyl ether, which produced a viscous oil when stirred. The oil was converted to a white solid by stirring in a mixture of diethyl ether and acetone. Drying at room temperature yielded 5.5 g of the ammonium salt of 4,4'-azobis(4-cyanovaleric acid). (2) A solution was prepared by dissolving 4 g of 4-(chloromethyl)benzyl alcohol in 30 ml of acetone. To this solution was added 5.7 g of sodium iodide dissolved in 25 g of acetone. The mixture was stirred at room temperature for 17 hours. The resulting thorium chloride was removed by filtration. The filtrate was then concentrated to a small volume using a rotary evaporator and poured into stirred deionized water. The resulting white solid was isolated, washed thoroughly with deionized water, and dried in a vacuum oven. Yield: 5 g of 4-(iodomethyl)benzyl alcohol. (3) A solution was prepared by dissolving 4.9 g of 4-(iodomethyl)benzyl alcohol obtained in step (2) in 11 g of dimethyl sulfoxide (DMSO). To this solution, 4.3 g of the ammonium salt prepared in step (1) dissolved in 100 g of DMSO was added. The reaction mixture was stirred at room temperature for 18 hours. Tetramethylammonium iodide was filtered off to obtain a filtrate. The filtrate was poured into deionized water with stirring. The resulting solid was filtered, washed thoroughly with water, and dried at room temperature to obtain 4 g of an azo initiator having two benzyl alcohol groups, i.e., (E)-bis(4-hydroxyphenyl)4,4'-(diazene-1,2-diyl)bis(4-cyanopentanoate)H-1 (yield 45%). H-1 NMR(HOCH2PhCH2OC(O)CH2CH2C(CH3)(CN)N)2:6H(1.7ppm), 8H(2.5ppm), 4H(4.6ppm), 4H(5.1ppm) and 8H(7.4ppm) Comparative synthesis example 2 (benzyl alcohol-terminated PS homopolymer) A solution was prepared in a 250 ml flask equipped with a magnetic bar and cold water condenser using 1.43 g of the azo initiator prepared in Synthesis Example 1 and 28.6 g of styrene dissolved in 54 g of 2-butanone. After purging with nitrogen for 30 minutes, the flask was immersed in an oil bath at 80° C. The polymerization reaction was carried out at this temperature for 18 hours. The resulting solution was then allowed to cool to room temperature and precipitated in methanol. The crude polymer was isolated by filtration and purified by dissolving it in 2-butanone and then reprecipitating it with methanol. Finally, the isolated polymer was dried in a vacuum oven at 50° C. until a constant weight (16.4 g) was reached (yield 57%). The polymer had an M of 15,175 g / mol. w and M of 9783 g / mol n It was confirmed that the compound had the following structure: Characteristic proton peaks (4.6, 5.1, and 7.3 ppm) assigned to benzyl alcohol end groups were clearly observed.

[0233] Synthesis Example 3: Synthesis of polystyrene end-capped with tert-butyldimethyl((3-(1-phenylvinyl)benzyl)oxy)silane (3-TBDMPVBOS) Approximately 55 mL of styrene (passed through the column and degassed) was taken into a calibrated ampoule equipped with two rotor flow stopcocks and a 19F connecting glass joint. After careful degassing under dynamic vacuum while keeping the styrene cold, the desired amount of styrene (55 mL) monomer was collected and the ampoule was closed under vacuum using the stopcock. In a glove box, the required amount of 3-TBDMPVBOS was weighed into a vial (1.2 molar excess relative to Sec-BuLi) and dissolved in approximately 5-10 mL of toluene and transferred into a calibrated ampoule equipped with a single rotor flow stopcock and a 19F joint. A dilute lithium 3-methyl-1,1-diphenylpentan-1-ide solution was prepared by reacting sec-butyllithium with 1,1-diphenylethane (DPE) in toluene until a dark color was produced. The solution of 3-TBDMPVBOS was titrated rapidly with the dilute solution of lithium-3-methyl-1,1-diphenylpentan-1-ide until a pale orange / red color was persistent. After closing the stopcock, the ampoule was removed from the glove box. Both the styrene and DPE ampoules were attached to the flask using glass joints and yellow grease. The flask was vacuumed and dried using a heat gun. After 10 minutes, the flask was brought to room temperature and backfilled with argon. Under positive pressure, approximately 600 mL of anhydrous THF was transferred to the flask via cannula transfer. The temperature of the flask was reduced to -78°C using a dry ice / acetone bath. The THF solution was titrated with sec-BuLi (1.4M) until a persistent lemon yellow / yellow color was obtained. While the flask was at -78°C, the styrene ampoule was backfilled with argon and the pressure-equalizing stopcock was closed. After 5 min, the dry ice / acetone bath was removed and the flask was allowed to reach room temperature (RT). After 15-30 min, the yellow color of sec-BuLi faded (complete destruction of excess sec-BuLi) and a colorless solution was obtained. After a colorless solution was obtained, the temperature of the flask was reduced to -78°C and the required amount of sec-BuLi was added using an airtight glass syringe.After 2-3 min, styrene was added dropwise over 3-6 min while keeping the initiator solution under rapid stirring. The reaction was continued for an additional 30 min and quenched with 3 mL of degassed methanol. The flask was brought to RT and the polymer was recovered by precipitation in MeOH. The precipitated polymer was filtered and dried in vacuum at 80 °C to give 3-TBDMPVBOS end-capped polystyrene (PS) in quantitative yield.

[0234] Deprotection of the tert-butyldimethylsilyl (TBDMS) protecting group: A single-neck 500 mL round-bottom flask was taken with 3-TBDMPVBOS end-capped polystyrene (PS) as a dry polymer and dissolved in approximately 200 mL of anhydrous tetrahydrofuran. The flask was closed with a rubber septum and excess tetrabutylammonium fluoride (TBAF) (1:6) was added via cannula. The reaction was carried out at room temperature for >24 hours. After complete deprotection of the siloxy groups, the (3-(1-phenylvinyl)phenyl)methanol-capped polystyrene (PS-DPE-CHOH) was recovered by precipitation into a large excess of methanol (approximately 5k M n (PS-DPE-CH2OH with 1,2-dichlorophenylsilyl tends to be partially soluble in methanol, so care must be taken to avoid loss during precipitation). A deionized water / methanol mixture (1:1) was used to remove silanol and LiOH by-products. After filtration, the polymer was dried at 80 °C in a vacuum oven for 24 h, resulting in a white powder as PS-DPE-CH2OH in a yield of 42 g. In proton NMR, the disappearance of the characteristic proton peak (-0.9 ppm) assigned to the tert-butyldimethylsilyl protecting group was clearly observed.

[0235] Comparative example of Fig. 1 The polymer of "Synthesis Example 2" and the polymer of "Comparative Synthesis Example 2" were dissolved separately in PGMEA to prepare 2 wt% solutions. The solutions were individually filtered using nylon filters (Entegris, Billerica, Ma). The two solutions were then separately coated on both Si and SiO2 wafers at 1500 rpm, and the wafers were then baked at 150°C for 5 minutes, respectively. After the bake, the wafers were washed with PGMEA for 1 minute to remove the ungrafted polymer from the wafers, which were then spun dry by spinning at "1,500 ppm", and then baked at 110°C for 1 minute. AFM images of the processed substrates were taken, and the scanned surface images are shown in Figure 1. The prepared grafted brush-type polymer from "Synthesis Example 2" showed uniform and dense films on both b) Si substrates and d) SiO2 substrates. In contrast, the wafer treated with the polymer of "Comparative Synthesis Example 2" had non-grafted regions (white holes), indicating that the grafted polymer brush film was not uniform on either a) the Si substrate or c) the SiO2 substrate.

[0236] Comparative Example of Figures 2A and 2B Si wafers were coated with Si anti-reflective coating (ARC) (SHB A940) obtained from Fujifilm (419 West Avenue Stamford, CT06902) at 1500 rpm and baked at 220° C. for 90 seconds, then the wafers were rinsed with TMAH. The ARC-coated wafers were then individually coated with a 2 wt % filtered solution of either the polymer of “Synthesis Example 2” or the polymer of “Comparative Example 2” in PGMEA to obtain a thickness of 51 nm. After coating, each of the wafers was baked at 160° C. for 5 minutes, then rinsed with PGMEA for 1 minute to remove ungrafted styrenic polymer, and after this bake, spun dry at 1500 rpm and baked at 110° C. for 1 minute to produce polystyrene-grafted wafers. Onto each of these polystyrene grafted wafers, a block copolymer (BCP) film was coated from a diblock copolymer of methyl methacrylate (MMA) and AZEMBLY EXP PME-190 (EMD Performance Materials, 70 Meister Ave, Branchburg, NJ 08876, USA) with Lo of 30 nm and polystyrene Vf of about 40-60%. The material was coated by varying the speed during coating to coat thicknesses in the range of (20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, and 50 nm). The BCP coated wafers were then annealed at 250 °C for 5 min under N2 to anneal the block copolymer film. NanoSEM (NanoSEM 3D, Applied Materials, Santa Clara, CA) top-down images were taken of the different coated and annealed wafers (Figure 2). In the annealed BCP films with film thicknesses of 30 nm and 45 nm, parallel features were observed on the wafers prepared from the polymer of "Synthetic Example 2" (FIG. 2B), but no such features were observed on any of the wafers prepared from the polymer of "Comparative Synthetic Example 2" (FIG. 2A).This indicated that the polymer of "Synthesis Example 2" provided strong and consistent surface energy by forming a uniform and dense polymer graft brush film, while the brush-type material from "Comparative Synthesis Example 2" did not have comparable graft polymer brush film quality. In general, but without being bound by theory, if the substrate has a more favorable interfacial energy for one domain of the diblock copolymer than for the other, the interaction between the substrate and the favorable domain will cause the lamellae to be oriented parallel to the substrate in the thin film instead of perpendicular orientation. This parallel shape of the thin film has three typical structures, such as asymmetric structure, symmetric structure, and hole-island structure, depending on the BCP film thickness and the interfacial energy between the BCP domain and the surrounding environment (e.g., air or N2). On a substrate grafted with polystyrene (PS), coated with BCP and annealed in N2 atmosphere, both the PS domain and the PMMA domain would be expected to have the same interfacial energy with the N2 surroundings. As a result, both the PS domain and the PMMA domain can be arranged on the top surface of the BCP film. Figures 2A and 2B compare how efficiently a BCP with Lo of 30 nm self-assembles on a substrate that is a grafted PS brush from a polystyrene material with a polydispersity of about 1.7 in 2A and a grafted PS brush from a polystyrene material with a polydispersity of 1.05 in 2B, respectively. Theoretically, for this BCP with Lo of 30 nm, there should be symmetric and asymmetric wetting structures at BCP film thicknesses of 30 nm and 45 nm, while holes and islands structures should predominate at other BCP film thicknesses. However, to support this theory, the interfacial energy between the substrate and the PS domains should be high enough. If not, both the PS and PMMA domains will be able to interact with the substrate that will not produce a perfectly parallel thin film structure at the corresponding film thickness. To achieve this theoretical result, the grafted PS brush region should have a dense and uniform film on the substrate to allow for strong and consistent interfacial interactions with the PS domains of the BCP.In Fig. 2A, as the film thickness increases, the SEM pictures consistently show hole and island structures regardless of the change in film thickness, whereas in Fig. 2B, the SEM pictures reveal the presence of perfectly parallel thin film structures. This result indicates that the PS brush material applied with narrow polydispersity in 2B provides a dense and strong PS grafted surface. On the other hand, in the Fig. 2A form, it is clear that the use of PS precursors with high polydispersity gives poor grafted PS films, since the theoretical parallel orientation is evidence of asymmetric and symmetric wetting structures. While this application is directed to the invention set forth in the claims, the disclosure of this application also includes: 1. A styrenic polymer, said styrenic polymer having a polydispersity of 1 to 1.3, and further wherein each polymer chain of said styrenic polymer is capped with one end group of structure 1). [ka] In the formula, L 1 is a linking group selected from the group consisting of a direct valence bond, oxy (-O-), carbonyloxy, (-(C=O)-O-), and carbonate (-O-(C=O)-O-); L 2 is selected from the group consisting of a C1-C20 substituted or unsubstituted alkylene spacer, an arylene spacer, and a direct valence bond, R is selected from the group consisting of hydrogen, halide, a C1-C20 alkyl moiety, and a C1-C20 alkyloxy moiety, and m is 1 to 3; and [ka] The end group 1) represents a direct valence bond attached to the terminal polymer chain of the styrenic polymer. 2. The styrene-based polymer according to 1 above, wherein m is 1 or 2. 3. 3. The styrenic polymer according to claim 1 or 2, wherein the end group has the structure 1a). [ka] 4. The styrene-based polymer according to any one of 1. to 3. above, wherein the terminal group has the structure 1b). [ka] 5. L 2 is a C1-C20 alkylene spacer, and L 1 The styrene-based polymer according to any one of 1. to 4. above, wherein is oxy (-O-). 6. L 2 is a C2 alkylene spacer, and L 1 The styrene-based polymer according to any one of 1. to 5. above, wherein is oxy (—O—). 7. 7. The styrene-based polymer according to any one of 1. to 6. above, wherein R is hydrogen. 8. 7. The styrene-based polymer according to any one of 1. to 6. above, wherein R is a halide. 9. The styrene-based polymer according to any one of the above 1. to 4., wherein R is a C1 to C20 alkyl moiety. 10. The styrene-based polymer according to any one of the above 1. to 4., wherein R is a C1 to C20 alkyloxy moiety. 11. The styrene-based polymer according to any one of 1. to 10. above, which has a polydispersity of 1 to 1.1. 12. 12. The styrene-based polymer according to any one of 1. to 11. above, having a Mw of 1000 g / mol to 50000 g / mol. 13. The styrenic polymer according to claim 1, having the structure 3).

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Claims

1. A styrenic polymer having a polydispersity of 1 to 1.3, the end groups having the following structure 1a): １ is oxy (—O—), and L ２ is a C1-C20 alkylene spacer unsubstituted or substituted by an aryl group, halide, C1-C20 alkyl, or C1-C20 alkyloxy, R is selected from the group consisting of hydrogen, halide, C1-C20 alkyl, and C1-C20 alkyloxy; and 【Chemistry 1】 The styrenic polymer wherein the end group 1a) represents a direct valence bond attaching the polymer chain end of the styrenic polymer. 【Chemistry 2】

2. 2. The styrenic polymer of claim 1 , wherein the end group has the following structure 1b): 【Chemistry 3】

3. 3. The styrenic polymer of claim 1, having the following structural formula 3c): ６ , R ６ａ , R ６ｂ , R ６ｃ and R ６ｄ is independently selected from the group consisting of hydrogen, C1-C20 alkyl, C1-C20 alkyloxy, C1-C10 fluoroalkyl, C1-C10 fluoroalkyloxy, trialkylsilyl, (trialkylsilyl)alkylene, and (trialkylsilyl)alkyleneoxy groups; R is selected from the group consisting of hydrogen, halide, a C1-C20 alkyl moiety, and a C1-C20 alkyloxy moiety; n is the number of repeat units in the polymer chain and is a positive integer other than 0; and R １ is a C1 to C20 alkyl. 【Chemistry 4】

4. R ６ , R ６ａ , R ６ｂ , R ６ｃ and R ６ｄ The styrenic polymer of claim 3 , wherein is hydrogen.

5. L ２ The styrenic polymer of claim 1 or 2, wherein is an unsubstituted C1 to C20 alkylene spacer.

6. A composition comprising the styrenic polymer according to any one of claims 1 to 5 and a solvent.

7. The composition of claim 6 further comprising a thermal acid generator.

8. 1. A method of grafting a pinning layer onto a substrate, comprising the steps of: a) coating a substrate with the composition of claim 6 or 7 to form a coated layer; b) heating the coated layer at a temperature of 140° C. to 170° C. to cause grafting; and c) treating the heated coated layer with an organic solvent to remove ungrafted polymer leaving an insoluble graft pinning layer on the substrate; A method comprising:

9. A method for chemo-epitaxy directed self-assembly of block copolymer layers used to form images, comprising the steps of: a1) coating a substrate with a graftable neutral layer polymer precursor to form a coated layer 1; b1) heating the coated layer 1 at a temperature between 90° C. and 180° C. to remove the solvent; c1) heating the coated layer 1 after step b1) at a temperature of 200° C. to 300° C. to cause grafting; d1) treating the coated Layer 1 after step c1) with an organic solvent to remove ungrafted neutral layer polymer, leaving an insoluble grafted neutral layer on the substrate; e1) coating a photoresist layer on the grafted neutral layer; f1) forming a negative pattern in said photoresist layer, whereby said grafted neutral layer forms areas covered with resist and areas not covered with resist, where the pattern in the resist includes both small nanometer sized repeating patterns and large areas of resist removed during the imaging process that do not contain repeating nanometer sized patterns; g1) etching to remove the neutral layer areas not covered by step f1) leaving bare substrate in these areas; h1) stripping the resist from the substrate after step g1) to leave a patterned substrate, where areas of the substrate left uncovered with resist in step f1) do not include the grafted neutral layer and areas covered with resist in step f1) retain the grafted neutral layer; i1) coating a patterned substrate with the composition of claim 6 or 7 to form a coated layer 2; j1) heating the coated layer 2 at a temperature between 120°C and 190°C; k1) treating the coated layer 2 after heating step j1) with an organic solvent to remove ungrafted polymer and leave insoluble grafted pinning layer material on the substrate in areas not including a grafted neutral layer to form a substrate having both pinned layer and neutral layer regions; 11) applying a coating of a block copolymer comprising an etch resistant styrenic block and a highly etchable aliphatic block onto a substrate comprising a patterned neutral layer and a pinned layer to form a substrate comprising both a patterned neutral layer and a patterned pinned layer; m1) annealing the block copolymer layer until directed self-assembly occurs in small nanometer-sized repeating patterns on the substrate, with the proviso that perpendicular orientation of the block polymer domains does not occur in the broad areas including the graft pinned layer; n1) etching the block copolymer to remove highly etchable blocks of the copolymer and form nanometer sized repeating patterns in the areas where directed self-assembly of the block copolymer occurred on the substrate in step m1); The method comprising:

10. A method for chemo-epitaxy directed self-assembly of block copolymer layers used to form images, comprising the steps of: a2) forming a coating of a crosslinkable or crosslinkable and graftable neutral layer polymer precursor on a substrate; b2) heating the crosslinkable neutral polymer layer precursor coating or the crosslinkable and graftable precursor coating at a temperature between 90° C. and 180° C. to remove the solvent; c2) heating the crosslinkable neutral layer polymer precursor coating, or the crosslinkable and graftable precursor coating, at a temperature of 200° C. to 300° C. to form a crosslinked neutral layer, or a crosslinked and grafted neutral layer; d2) providing a coating of a photoresist layer on said crosslinked neutral layer or on the crosslinked and grafted neutral layer; e2) forming a negative pattern in said photoresist layer, whereby said crosslinked neutral layer or crosslinked and grafted neutral layer forms areas covered and uncovered by resist, wherein said pattern in resist includes both small nanometer repeating patterns and large areas of resist removed during the imaging process that do not contain repeating nanometer sized patterns; f2) etching away the crosslinked neutral layer or the crosslinked and grafted neutral layer in the neutral layer areas not covered in step e2) using plasma to leave a bare substrate in the areas not covered in step e2); g2) stripping the resist from the substrate after step f2) to leave a patterned substrate, where the substrate in areas left uncovered by resist in step e2) does not contain the crosslinked neutral layer or the crosslinked and grafted neutral layer, and the areas covered by resist in step f2) retain the crosslinked neutral layer or the crosslinked and grafted neutral layer; h2) coating the patterned substrate with the composition of claim 6 or 7 to form a coated layer; i2) heating the coated layer at a temperature of 120°C to 190°C; j2) treating the coated layer after heating step i2) with an organic solvent to remove ungrafted polymer, thereby leaving insoluble crosslinked or crosslinked and grafted pinning layer material on the substrate in areas that do not include a crosslinked neutral layer or areas that do not include a crosslinked and grafted neutral layer, to form a substrate that includes both a patterned neutral layer and a patterned pinning layer; k2) applying a coating of a block copolymer comprising an etch resistant styrenic block and a highly etchable aliphatic block onto the substrate comprising the patterned neutral layer and the pinned layer; l2) annealing the block copolymer layer until directed self-organization occurs in small nanometer-sized repeating patterns on the substrate, with the proviso that perpendicular orientation of the block polymer domains does not occur in the broad areas including the graft pinned layer; m2) etching the block copolymer to remove the highly etchable blocks of the copolymer and form a repeating nanometer sized pattern in the areas where directed self-assembly of the block copolymer occurred on the substrate in step l2); The method comprising:

Images