Coating compositions and methods

Abstract

A coating composition including a block copolymer; a second polymer that is different from the block copolymer; and a solvent, wherein the block copolymer includes a first block formed from an oxirane monomer comprising a substituent group comprising 3 or more carbon atoms; and a second block that is different from the first block, and wherein the block copolymer is free of CF2 and CF3 groups that are bonded to a carbon atom.

Description

COATING COMPOSITIONS AND METHODSCROSS REFERENCE TO RELATED APPLICATIONSThe application claims priority to U.S. provisional application Nos. 63 / 665592, filed on June 28, 2024, and 63 / 623089, filed on January 19, 2024, the entire disclosures of which are incorporated herein by reference.FIELD

[0001] The subject matter relates generally to coating compositions. More specifically, the subject matter relates to coating compositions that include a polymer that may function as a surfactant, for example, as a surface leveling agent (SLA), and to coating methods using such compositions. The coating compositions find particular use in the formation of semiconductor devices, for example, in the formation of lithographic patterns as a lithographic material composition such as photoresist, antireflective coating, gap-fill, photoresist underlayer, photoresist topcoat, photoresist pattern overcoat, nanoimprint lithography, surfactant rinse, and developer compositions.BACKGROUND

[0002] The use of surface leveling agents (SLAs) in coating compositions, such as photoresist compositions, used in the manufacture of semiconductor devices is known (see, e.g., U.S. Patent Pub. No. US 2022 / 0204760 Al). Photoresist compositions are photosensitive materials used to transfer a pattern to one or more underlying layers, such as a metal, semiconductor, or dielectric layer disposed on a substrate. After spin-coating the photoresist composition on the substrate, the photoresist layer is pattern- wise exposed to activating radiation and developed to form a photoresist relief image. The resulting photoresist pattern allows for selective processing of the underlying substrate, for example, by etching or ion implantation.

[0003] SLAs are typically in oligomeric or polymeric form, having a lower surface energy as compared with other solid components of the coating composition. The SLA can thereby segregate from other components of the coating composition to the free surface (e.g., a surface that contacts air) of the layer during the coating process. The presence of SLAs in the coating composition can provide for good flow and leveling during coating, resulting in a planar, uniformly coated film.

[0004] Commonly used photoresist developers are aqueous bases or organic solvent / solvent mixtures, with aqueous tetramethyl ammonium hydroxide (TMAH) solutions being typical. Itis desired in the case of a positive-tone photoresist that the exposed regions of the layer are completely removed during development, or that the unexposed regions are completely removed in the case of a negative-tone resist, as resist residue in those regions can result in patterning defects, for example, one or more of scumming, bridging, and footing defects. SLAs, however, can be a major source of such defects in photoresist patterning owing to their low surface energy (greater hydrophobicity) and resulting poor solubility in the developer solution. For example, to impart desired surface energy properties to SLAs, the inclusion on the SLAs of silicon-containing or fluorine-containing moieties is known. The use of silicon- containing materials in typical photoresist compositions can, however, result in etching defects due to their typically high etch resistance during oxygen based etch transfer of the pattern. While the use of fluorinated SLAs is also known, investigation of alternatives to certain fluorinated compounds is becoming of increased interest by the semiconductor manufacturing industry and governmental regulatory bodies for replacement with more sustainable alternatives.

[0005] With increasingly stringent requirements for advanced semiconductor devices in the form of increased pattern resolutions and aspect ratios, there is a need in the art for new methods of forming semiconductor devices that address one or more problems associated with the state of the art.SUMMARY

[0006] An aspect provides a coating composition including a block copolymer; a second polymer that is different from the block copolymer; and a solvent, wherein the block copolymer includes a first block formed from an oxirane monomer comprising a substituent group comprising 3 or more carbon atoms; and a second block that is different from the first block, and wherein the block copolymer is free of CFT and CF3 groups that are bonded to a carbon atom.

[0007] Another aspect provides a method including (a) providing a substrate; and (b) coating a coating composition over the substrate, wherein the coating composition comprises a block copolymer and a solvent, wherein the block copolymer includes a first block formed from an oxirane monomer comprising a substituent group comprising 3 or more carbon atoms; and a second block that is different from the first block, and wherein the block copolymer is free of CF2 and CF3 groups that are bonded to a carbon atom.

[0008] Another aspect provides a pattern forming method including forming on a substrate a photoresist composition layer from the coating composition described herein, pattern-wiseexposing the photoresist composition layer to activating radiation; and developing the exposed photoresist composition layer to provide a resist relief image.

[0009] Another aspect provides a pattern forming method including coating the coating composition as described herein on a substrate to form an underlayer; forming a photoresist layer over the underlayer; pattern-wise exposing the photoresist layer to activating radiation; and developing the exposed photoresist layer to provide a resist relief image.

[0010] Another aspect provides a pattern forming method including forming a photoresist composition layer on a substrate; coating the coating composition as described herein on the photoresist composition layer to form an overlayer; pattern- wise exposing the overlayer to activating radiation; and developing the photoresist composition layer to provide a resist relief image.DETAILED DESCRIPTION

[0011] Reference will now be made in detail to exemplary embodiments, examples of which are illustrated in the present description. In this regard, the present exemplary embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein. Accordingly, the exemplary embodiments are merely described below to explain aspects of the present description. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items. Expressions such as "at least one of," when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list.

[0012] As used herein, the terms “a,” “an,” and “the” do not denote a limitation of quantity and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted hy context. “Or” means “and / or” unless clearly indicated otherwise. The modifier “about” used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (e.g., includes the degree of error associated with measurement of the particular quantity). All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. The suffix “(s)” is intended to include both the singular and the plural of the term that it modifies, thereby including at least one of that term. “Optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where the event occurs and instances where it does not. The terms “first,” “second,” and the like, herein do not denote an order, quantity, or importance, but rather are used to distinguish one element from another. When an element is referred to asbeing “on” another element, it may be directly in contact with the other element or intervening elements may be present therebetween. In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present. It is to be understood that the described components, elements, limitations, and / or features of aspects may be combined in any suitable manner in the various aspects.

[0013] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

[0014] As used herein, “actinic rays” or “radiation” means, for example, a bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, particle rays such as electron beams and ion beams, or the like. In addition, as used herein, “light” means actinic rays or radiation. The krypton fluoride laser (KrF laser) is a particular type of excimer laser, which is sometimes referred to as an exciplex laser. “Excimer” is short for “excited dimer,” while “exciplex” is short for “excited complex.” An excimer laser uses a mixture of a noble gas (argon, krypton, or xenon) and a halogen gas (fluorine or chlorine), which under suitable conditions of electrical stimulation and high pressure, emits coherent stimulated radiation (laser light) in the ultraviolet range. Furthermore, “exposure” in the present specification includes, unless otherwise specified, not only exposure by a mercury lamp, far ultraviolet rays represented by an excimer laser, X-rays, extreme ultraviolet rays (EUV light), or the like, but also writing by particle rays such as electron beams and ion beams.

[0015] As used herein, the term “hydrocarbon” refers to an organic compound or group having at least one carbon atom and at least one hydrogen atom; “alkyl” refers to a straight or branched chain saturated hydrocarbon group having the specified number of carbon atoms and having a valence of one; “alkylene” refers to an alkyl group having a valence of two; “hydroxyalkyl” refers to an alkyl group substituted with at least one hydroxyl group (-OH); “alkoxy” refers to “alkyl-O-”; “carboxyl" and "carboxylic acid group” refer to a group having the formula “-C(O)-OH”; “cycloalkyl” refers to a monovalent group having one or more saturated rings in which all ring members are carbon; “cycloalkylene” refers to a cycloalkyl group having a valence of two; “alkenyl” refers to a straight or branched chain, monovalent hydrocarbon group having at least one carbon-carbon double bond; “alkenoxy” refers to“alkenyl-O-“; “alkenylene” refers to an alkenyl group having a valence of two; “cycloalkenyl” refers to a non-aromatic cyclic divalent hydrocarbon group having at least three carbon atoms, with at least one carbon-carbon double bond; “alkynyl” refers to a monovalent hydrocarbon group having at least one carbon-carbon triple bond; the term “aromatic group” refers to a monocyclic or polycyclic aromatic ring system that satisfies Huckel’s Rule (4n+2 7t electrons) and includes carbon atoms in the ring; the term “heteroaromatic group” refers to an aromatic group that includes one or more heteroatoms (e.g., 1-4 heteroatoms) selected from N, O, and S instead of a carbon atom in the ring; “aryl” refers to a monovalent monocyclic or polycyclic aromatic ring system where every ring member is carbon, and may include a group with an aromatic ring fused to at least one cycloalkyl or heterocycloalkyl ring; “arylene” refers to an aryl group having a valence of two; “alkylaryl” refers to an aryl group that has been substituted with an alkyl group; “arylalkyl” refers to an alkyl group that has been substituted with an aryl group; “aryloxy” refers to “aryl- O-”; and “arylthio” refers to “aryl-S-”.

[0016] The prefix “hetero” means that the compound or group includes at least one member that is a heteroatom (e.g., 1, 2, 3, or 4 or more heteroatom(s)) instead of a carbon atom, wherein the heteroatom(s) is each independently N, O, S, Si, or P; “heteroatom-containing group” refers to a substituent group that includes at least one heteroatom; “heteroalkyl” refers to an alkyl group having at least one heteroatom instead of carbon; “heterocycloalkyl” refers to a cycloalkyl group having 1-4 heteroatoms as ring members instead of carbon; “heterocycloalkylene” refers to a heterocycloalkyl group having a valence of two;“heteroaryl” refers to an aromatic 4-8 membered monocyclic, 8-12 membered bicyclic, or 11- 14 membered tricyclic ring system having 1-4 heteroatoms (if monocyclic), 1-6 heteroatoms (if bicyclic), or 1-9 heteroatoms (if tricyclic) that are each independently selected from N, O, S, Si, or P (e.g., carbon atoms and 1-3, 1-6, or 1-9 heteroatoms of N, O, or S, if monocyclic, bicyclic, or tricyclic, respectively). Examples of heteroaryl groups include pyridyl, furyl (furyl or furanyl), imidazolyl, benzimidazolyl, pyrimidinyl, thiophenyl or thienyl, quinolinyl, indolyl, thiazolyl, and the like; and “heteroarylene” refers to a heteroaryl group having a valence of two.

[0017] The term “halogen” means a monovalent substituent that is fluorine (fluoro), chlorine (chloro), bromine (bromo), or iodine (iodo). The prefix "halo" means a group including one or more of a fluoro, chloro, bromo, or iodo substituent instead of a hydrogen atom. A combination of halo groups (e.g., bromo and fluoro), or only fluoro groups may be present.For example, the term "haloalkyl" refers to an alkyl group substituted with one or more halogens. As used herein, "substituted Ci-s haloalkyl" refers to a Ci-8 alkyl group substituted with at least one halogen, and is further substituted with one or more other substituent groups that are not halogens. It is to be understood that substitution of a group with a halogen atom is not to be considered a heteroatom-containing group, because a halogen atom does not replace a carbon atom.

[0018] Each of the foregoing substituent groups optionally may be substituted unless expressly provided otherwise. The term “optionally substituted” refers to being substituted or unsubstituted. “Substituted” means that at least one hydrogen atom of the chemical structure or group is replaced with another terminal substituent group that is typically monovalent, provided that the designated atom’s normal valence is not exceeded. When the substituent is oxo (i.e., O), then two geminal hydrogen atoms on the carbon atom are replaced with the terminal oxo group. It is further noted that the oxo group is bonded to carbon via a double bond to form a carbonyl (CAO), where the carbonyl group is represented herein as -C(O)-. Combinations of substituents or variables are permissible. Exemplary substituent groups that may be present on a “substituted” position include, but are not limited to, nitro (-NO2), cyano (-CN), hydroxyl (-OH), oxo (O), amino (-NH2), mono- or di-(Ci-6)alkylamino, alkanoyl (such as a C2-6 alkanoyl group such as acyl), formyl (-C(O)H), carboxylic acid or an alkali metal or ammonium salt thereof; esters (including acrylates, methacrylates, and lactones) such as C2-6 alkyl esters (-C(O)O-alkyl or -OC(O)-alkyl) and C7-13 aryl esters (-C(O)O-aryl or -OC(O)- aryl); amido (-C(0)NR2 wherein R is hydrogen or Ci-6 alkyl), carboxamido (-CH2C(O)NR2 wherein R is hydrogen or C1-6 alkyl), halogen, thiol (-SH), C1-6 alkylthio (-S-alkyl), thiocyano (-SCN), C1-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, C1-6 haloalkyl, C1-9 alkoxy, C1-6 haloalkoxy, C3- 12 cycloalkyl, C5-18 cycloalkenyl, C2-18 heterocycloalkenyl, C6-12 aryl having at least one aromatic ring (e.g., phenyl, biphenyl, naphthyl, or the like, each ring either substituted or unsubstituted aromatic), C7-19 arylalkyl having 1 to 3 separate or fused rings and from 6 to 18 ring carbon atoms, arylalkoxy having 1 to 3 separate or fused rings and from 6 to 18 ring carbon atoms, C7-12 alkylaryl, C3-12 heterocycloalkyl, C3-12 heteroaryl, C1-6 alkyl sulfonyl (- S(0)2-alkyl), C6-12 arylsulfonyl (-S(0)2-aryl), or tosyl (CH3C6H4SO2-).

[0019] As used herein, when a definition is not otherwise provided, a "divalent linking group" and a “linking group” refer to a group including one or more of -O-, -S-, -Te-, -Se-, - C(O)-, -C(O)O-, -Si(R )2-, -N(R’)-, -C(0)N(R )-, -S(O)-, -S(O)2-, -C(S)-, -C(Te)-, -C(Se)-, substituted or unsubstituted C1-30 alkylene, substituted or unsubstituted C3-30 cycloalkylene, substituted or unsubstituted C3-30 heterocycloalkylene, substituted or unsubstituted Ce-30arylene, substituted or unsubstituted C3-30 heteroarylene, or a combination thereof, wherein each R is independently hydrogen, substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C1-20 heteroalkyl, substituted or unsubstituted Ce-30 aryl, or substituted or unsubstituted C3-30 heteroaryl. Typically, the divalent linking group includes one or more of - O-, -S-, -C(O)-, -C(O)O-, -N(R’)-, -C(O)N(R )-, -S(O)-, -S(O)2-, substituted or unsubstituted Ci-30 alkylene, substituted or unsubstituted C3-30 cycloalkylene, substituted or unsubstituted C3-30 heterocycloalkylene, substituted or unsubstituted C6-30 arylene, substituted or unsubstituted C3-30 heteroarylene, or a combination thereof, wherein each R’ is hydrogen, substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C1-20 heteroalkyl, substituted or unsubstituted Ce-30 aryl, or substituted or unsubstituted C3-30 heteroaryl. More typically, the divalent linking group includes at least one of -O-, -C(O)-, -C(O)O-, -N(R )-, - C(O)N(R’)-, substituted or unsubstituted Ci-10 alkylene, substituted or unsubstituted C3-10 cycloalkylene , substituted or unsubstituted C3-10 heterocycloalkylene, substituted or unsubstituted Ce-io arylene, substituted or unsubstituted C3-10 heteroarylene, or a combination thereof, wherein R is hydrogen, substituted or unsubstituted C1-10 alkyl, substituted or unsubstituted C1-10 heteroalkyl, substituted or unsubstituted C6-10 aryl, or substituted or unsubstituted C3-10 heteroaryl.

[0020] As used herein, an "acid-labile group" refers to a group in which a bond is cleaved by the catalytic action of an acid, optionally and typically with thermal treatment, resulting in formation of a polar group, such as a carboxylic acid or alcohol group, being formed on the polymer, and optionally and typically with a moiety connected to the cleaved bond becoming disconnected from the polymer. Such acid is typically a photo-generated acid with bond cleavage occurring during post-exposure baking. Suitable acid-labile groups include, for example: tertiary alkyl ester groups, secondary or tertiary aryl ester groups, secondary or tertiary ester groups having a combination of alkyl and aryl groups, tertiary alkoxy groups, acetal groups, or ketal groups. Acid-labile groups are also referred to in the art as "acid- cleavable groups," "acid-cleavable protecting groups," "acid-labile protecting groups," "acidleaving groups," "acid-decomposable groups," and "acid-sensitive groups." Suitable acid- labile groups include, for example, tertiary alkyl ester groups, secondary or tertiary aryl ester groups, secondary or tertiary ester groups having a combination of alkyl and aryl groups, tertiary alkoxy groups, acetal groups (including ester acetal and non-ester acetal groups), or ketal groups (including ester ketal and non-ester ketal groups).

[0021] As used herein, a “base-labile group” refers to a group that can undergo cleavage reaction to provide polar groups such as hydroxyl, carboxylic acid, sulfonic acid, and the like,in the presence of a base, for example, an aqueous alkaline developer after exposure and postexposure baking steps. The base-labile group will not react significantly (e.g., will not undergo a bond-breaking reaction) prior to a development step of a photoresist layer that comprises the first polymer. Thus, for instance, a base-labile group will be substantially inert during pre-exposure soft-bake, exposure, and post-exposure bake steps. By “substantially inert” it is meant that ^5%, preferably ^1%, of the base-labile groups (or moieties) will decompose, cleave, or react during the pre-exposure soft-bake, exposure, and post-exposure bake steps. The base-labile group is reactive under typical photoresist development conditions using, for example, an aqueous alkaline photoresist developer such as a 0.26 normal (N) aqueous solution of tetramethylammonium hydroxide (TMAH). For example, a 0.26 N aqueous solution of TMAH may be used to develop the resist pattern using a single puddle development or dynamic development process, e.g., where the 0.26 N TMAH developer is dispensed onto an imaged photoresist layer for a suitable time such as 10 to 120 seconds. Exemplary base-labile groups include activated esters and amides.

[0022] The coating compositions provided herein include a block copolymer; a second polymer that is different from the block copolymer; and a solvent. The block copolymer includes a first block formed from an oxirane monomer comprising a substituent group comprising 3 or more carbon atoms, and a second block that is different from the first block. The block copolymer is free of CF2 and CF3 groups that are bonded to a carbon atom.

[0023] The block copolymer can function as a surface leveling agent in the coating composition. The surface leveling agent may be used as a wetting agent for improving flow control. The surface leveling and wetting capability properties can result in beneficial optical properties, for example, high gloss to provide extremely smooth coatings with low surface roughness, for example, on the angstrom level. The block copolymer can be blended with a wide variety of solutions, waxes, polishes, coatings, blends, or the like. In an embodiment, the surface leveling agent may be used in floor polish formulations, painting, powder coating compositions, or the like. The coating compositions find particular benefit in semiconductor manufacturing such as for lithography applications. Coating compositions including the block copolymer, for example, can exhibit improved depth-of- focus (DOF) properties and a surface with minimal or no defects, for example, those caused by pinholes and light diffraction between layers, which can result in improved pattern imaging.

[0024] The polyoxirane-containing backbone can provide the block copolymer with hydrophilic properties for miscibility with water and aqueous base developers, while the carbon-containing substituent(s) can provide hydrophobic properties allowing for the blockcopolymer to migrate to the layer / air surface of the coated layer of the coating composition. In some embodiments, the block copolymer can be sufficiently hydrophilic to be miscible with water or an aqueous base developer. In some embodiments, the block copolymer can display a level of hydrophobicity such that it is not miscible with water and aqueous developers, but renders it miscible with an organic solvent developer.

[0025] The block copolymer is preferably free of silicon- and fluorine-containing moieties. The absence of such silicon- and fluorine-containing moieties in the block copolymer can help to minimize defect formation, for example, coating defects such as spot, striation, fisheye, and dewet defects, patterning defects, and dry (plasma) and etch defects. The absence of certain fluorinated groups such as CF2 and CF3 groups that are bonded to a carbon atom in the block copolymer may further be desired from the standpoint of providing sustainable alternative chemistries.

[0026] In some embodiments, the first block of the block copolymer may include a repeating unit of Formula (1):

[0027] In Formula (1), R1to R4are each independently hydrogen, deuterium, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C3-30 cycloalkenyl, substituted or unsubstituted C2-30 alkynyl, substituted or unsubstituted C3-30 cycloalkynyl, substituted or unsubstituted Ce-30 aryl, substituted or unsubstituted C4-30 heteroaryl, optionally comprising one or more of -O-, -S-, -Si(Rc)2-, -N(RC)-, -S(O)-, -S(O)2-, -C(O)-, -C(O)O-, -C(O)S-, -OC(O)O-, -N(RC)C(O)-, or -C(O)N(RC)-; and Rcis hydrogen, deuterium, or substituted or unsubstituted Ci-Ce alkyl. Any two or more of R1, R2. R3, and R4together may optionally form a ring, and at least one of R1, R2R3, and R4has 3 or more carbon atoms, for example, from 3 to 12 carbon atoms, preferably from 3 to 8 carbon atoms, and more preferably from 3 to 5 carbon atoms. The aforementioned alkyl, alkenyl, and alkynyl groups may be a straight chain or branched, and may optionally contain other atoms such as O, S, N, P, or other functional linkages, which include, for example, an ether, an ester, an amide, an imide, a urethane or a urea. The alkyl, alkenyl, and alkynyl groups may optionally contain an end functional group such as for example, a hydroxyl, a thiol, a cyano, an amine, or a sulfonate. In the herein-mentioned optional substitutions, such substitutions can include deuterium withpartial or full deuteration.

[0028] In addition to the ether linkages that are part of the first block of the block copolymer backbone, there may be additional functional linkages present in pendent groups (side chains) that are covalently bonded to the copolymer backbone. In an embodiment, these side chains may include only carbon-carbon linkages. In another embodiment, these side chains may include carbon-carbon linkages in addition to other functional linkages or functional groups, including but not limited to one or more of ether, ester, amide, sulfonate, hydroxy, thiol, cyano, amine, thiol, aldehyde, carboxyl, alkyl halide, ketone, allyl, allenyl, norbornyl, ethynyl, acrylate, methacrylate, itaconate, maleimide, maleic anhydride, carbonate, carbamate, or the like. In other words, the side chain may contain heteroatoms such as nitrogen, sulfur, oxygen, or the like. The side chain can be linear, branched, or may have one or more ring structures as linkages.

[0029] One or both of R1and R2is typically chosen from C3-10 alkyl, optionally with one or more -O- groups, and R3and R4are typically independently chosen from -H or deuterium. One or more of R1, R2R3, and R4can include an acid-labile group, a base-labile group, a base-soluble group, or a base switchable group. Suitable base-soluble groups include, for example, hydroxyl, carboxyl, phenols, imides, or -NHS(O)2Y1groups, where Y1is substituted or unsubstituted C1-10 alkyl.

[0030] The first block of the block copolymer is derived from an oxirane monomer including a substituent group including three or more carbon atoms. For example, the first block of the block copolymer may be prepared from an oxirane monomer of Formula (la):wherein: R1, R2, R3, and R4are as defined herein with respect to Formula (1).

[0031] Non- limiting examples of the first block of the block copolymer include the following:

[0032] The first block of the block copolymer is typically present in the block copolymer in an amount of from 20 to 100 mol%, more typically from 50 to 100 mol%, and still more typically from 60 to 100 mol%, based on the total repeating units in the block copolymer.

[0033] The block copolymer further includes a second block that is different from the first block of the block copolymer. The block copolymer can, for example, include additional blocks of repeat units formed from one or more structurally different oxirane monomers than the first block and / or from one or more non-oxirane monomers. Suitable additional oxirane monomers include those described above with reference to the first block of the block copolymer, or a different oxirane monomer. Suitable additional repeat units include, for example, those formed from heterocyclic monomers capable of ring-opening copolymerization with the above-described oxirane monomers. Suitable such heterocyclic monomers include, for example, cyclic ethers, cyclic thioethers, cyclic esters such as lactones, lactides, cyclic carbonates, cyclic phosphates, cyclic phosphonates, cyclic phosphinates, cyclic sulfonates, cyclic sulfinates, and cyclic thioesters, cyclic acid anhydrides, amino acid N-carboxyanhydrides, or the like, or a combination thereof.

[0034] In some embodiments, the second block may include one or more repeating units of Formulae (2) to (5):

[0035] In Formula (2), L1is a single bond or a divalent linking group. For example, L1may be a divalent linking group including at least one carbon atom, at least one heteroatom, or a combination thereof. For example, L1may include 1 to 10 carbon atoms and at least one heteroatom. In one or more embodiments, L1may be -OCH2-, -OCH2CH2O- or -N(RC)-, wherein Rcis hydrogen, deuterium, or substituted or unsubstituted C1-6 alkyl. For example, L1may be -O-, -C(O)-, -C(O)O-, -N(RC)-, -C(O)N(RC)-, substituted or unsubstituted C1-10 alkylene, substituted or unsubstituted C3-30 cycloalkylene, substituted or unsubstituted C3-30 heterocycloalkylene, substituted or unsubstituted Ce-30 arylene, substituted or unsubstituted C2-30 heteroarylene, or a combination thereof, wherein Rcis hydrogen, deuterium, or substituted or unsubstituted C1-6 alkyl. In some embodiments, L1may be, for example, substituted or unsubstituted Ce-30 arylene or substituted or unsubstituted C3-30 cycloalkylene.

[0036] In Formula (2), R5is substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted Ci-30 heterocycloalkyl, substituted or unsubstituted Ce-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C2-30 heteroaryl, substituted or unsubstituted C3-30 heteroarylalkyl, or substituted or unsubstituted C3-30 alkylheteroaryl. In some embodiments, R5may be a monocyclic, polycyclic, or fused polycyclic C4-20 lactone- containing group.

[0037] In some embodiments, R5may be a substituted C5-30 aromatic group that optionally includes one or more aromatic ring heteroatoms chosen from N, O, S, or a combination thereof, wherein the aromatic group may be monocyclic, non-fused polycyclic, or fused polycyclic, and wherein the aromatic group is substituted with 1 to 6, typically 1 to 3 hydroxyl and / or methyl groups.

[0038] In some embodiments, R5may include a polar group. Exemplary polar groups include a sultone group, a sulfonamide group, a hydroxyalkyl group, a hydroxycycloalkyl group, or acombination thereof. For example, R5may be substituted or unsubstituted C1-30 or C1-20 alkyl, typically C1-12 alkyl; substituted or unsubstituted C3-30 or C3-20 cycloalkyl; or substituted or unsubstituted poly(Ci-3 alkylene oxide). The substituted C1-30 or C1-20 alkyl, the substituted C3-30 or C3-20 cycloalkyl, and the substituted poly(Ci-3 alkylene oxide) are substituted with one or more of a sulfonamide group (e.g., -NHSO2CF3), a hydroxy group (-OH), or a fluoroalcohol group (e.g., -QCFs OH).

[0039] In Formula (3), R6and R7are each independently hydrogen, deuterium, substituted or unsubstituted Ci-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C1-30 heterocycloalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C3-30 cycloalkenyl, substituted or unsubstituted C2-30 alkynyl, substituted or unsubstituted C3-30 cycloalkynyl, substituted or unsubstituted Ce-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C4-30 heteroaryl, substituted or unsubstituted C3-30 heteroarylalkyl, or substituted or unsubstituted C3-30 alkylheteroaryl, optionally comprising one or more of -O-, - S-, -Si(Rc)2-, -N(RC)-, -S(O)-, -S(O)2-, -C(O)-, -C(O)O-, -C(O)S-, -OC(O)O-, -N(RC)C(O)-, or -C(O)N(RC)-; and Rcis hydrogen, deuterium, or substituted or unsubstituted C1-C6 alkyl. R6and R7together may optionally form a ring. In some embodiments, one or more of R6or R7may include an acid-labile group, a base-labile group, or a base-soluble group.

[0040] In Formulae (4) and (5), X is O, S, or NRC; Y1and Y2are each independently a single bond, -C(O)-, -S(O)-, -S(O)2-, or -P(O)ORC; Z is a single bond, -O-, -S-, -NRC-, C2-5 alkenylene, C2-5 alkynylene, Ce 12 arylene, or Ct, -12 heteroarylene; each R8and R9independently represents hydrogen, deuterium, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C3-30 cycloalkenyl, substituted or unsubstituted C2-30 alkynyl, substituted or unsubstituted C3-30 cycloalkynyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C4-30 heteroaryl, optionally including one or more of -O-, -S-, - Si(Rc)2-, -N(RC)-, -S(O)-, -S(O)2-, -C(O)-, -C(O)O-, -C(O)S-, -OC(O)O-, -N(RC)C(O)-, or - C(O)N(RC)-, any two or more of R8and R9together may optionally form a ring; Rcis hydrogen, deuterium, or substituted or unsubstituted C1-C6 alkyl; a is an integer from 0 to 9; b is an integer from 0 to 9; a+b is an integer from 1 to 18, typically from 1 to 10, and more typically from 1 to 6. The aforementioned alkyl, alkenyl, and alkynyl groups may be a straight chain or branched, and may optionally contain other atoms such as O, S, N, P, or other functional linkages, which include, for example, an ether, an ester, an amide, an imide, a urethane or a urea. The alkyl, alkenyl, and alkynyl groups may optionally contain an endfunctional group such as for example, a hydroxyl, a thiol, a cyano, an amine, or a sulfonate.

[0041] In still other embodiments, the second block may include one or more repeating units of Formulae (6) to (10):

[0042] In Formula (6), R10is substituted or unsubstituted Ci-6 alkylene, C2-6 alkenylene, C2-6 alkynylene, C6-12 arylene, or C6-12 heteroarylene, optionally comprising one or more of -O-, - S-, -SO-, -SO2-, -NRC-, -C(O)-, or -C(O)O- as part of its structure, wherein Rcis hydrogen, deuterium, or substituted or unsubstituted Ci-Ce alkyl.

[0043] In Formulae (7) to (10), R11to R20are each independently hydrogen, deuterium, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C3-30 cycloalkenyl, substituted or unsubstituted C2-30 alkynyl, substituted or unsubstituted C3-30 cycloalkynyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C4-30 heteroaryl, optionally including one or more of -O-, -S-, -Si(Rc)2-, -N(RC)-, -S(O)-, -S(O)2-, -C(O)-, -C(O)O-, - C(O)S-, -OC(O)O-, -N(RC)C(O)-, or -C(O)N(RC)-; Rcis hydrogen, deuterium, or substituted or unsubstituted Ci-Ce alkyl; any two or more of R11and R12, R13and R14, R15and R16, R17and R18, or R19and R20together may optionally form a ring. In some embodiments, one or more of R11to R20may include an acid-labile group, a base-labile group, or a base-soluble group.

[0044] In Formula (7) to (9), m, n, and p are each independently an integer from 1 to 9, typically 1 to 6. In some embodiments, in Formula (7), m may be an integer from 2 to 9, typically 2 to 6.

[0045] Exemplary and non- limiting repeating units of the second block include the following:

[0046] The second block of the block copolymer is typically present in the block copolymer in an amount of from 20 to 100 mol%, more typically from 50 to 100 mol%, and still more typically from 60 to 100 mol%, based on the total repeating units in the block copolymer.

[0047] In some embodiments, the block copolymer may further include a third block, wherein the third block is different from the first block and the second block, and wherein the third block comprises one or more repeating units of Formulae (2) to (5) and / or (6) to (10). In some embodiments, the block copolymer may further include a fourth block, a fifth block, etc., where each block may comprise one or more repeating units of Formulae (2) to (5) and / or (6) to (10). Such additional repeating units, if present in the block copolymer, may be used in an amount of up to 60 mol%, typically from 3 to 50 mol%, based on total repeating units of the block copolymer.

[0048] In some embodiments, the block copolymer may be free of repeat units formed from substituted or unsubstituted oxetane monomers.

[0049] In some embodiments, the second and / or third block of the block copolymer may be derived from an enol ether compound, such as a vinyl ether compound. Exemplary vinyl ether compounds include those of Formula (11):wherein each R21independently represents hydrogen, Ci-4 alkyl, optionally including as part of its structure one or more groups chosen from -O-, -S-, -N(RC)-, -C(O)-, -C(O)O-, or - C(O)N(RC)-, wherein Rcrepresents hydrogen or substituted or unsubstituted Ci-io alkyl, and any two R21groups together optionally forming a ring; and R22represents a Ci-io linear alkyl, C3-10 branched alkyl, C3-10 cyclic alkyl, C5-12 aryl, or a combination thereof, each of which may be substituted or unsubstituted, and optionally including as part of its structure one or more groups chosen from -O-, -S-, -N(RC)-, -C(O)-, -C(O)O-, or -C(O)N(RC)-, wherein Rcrepresents hydrogen, deuterium, or substituted or unsubstituted C1-10 alkyl.

[0050] Suitable enol ether compounds include, for example, the following:

[0051] If present, the blocks formed from the enol ether compound are typically present in the block copolymer in an amount of from 2 to 90 mol%, more typically from 5 to 70 mol%, and still more typically from 25 to 50 mol%, based on the total blocks of the block copolymer. Suitable enol ether monomers are commercially available and / or can readily be made by persons skilled in the art.

[0052] In some embodiments, the block copolymer may further include one or more spacers in the backbone between blocks of polymerized units. Suitable spacers include, for example, one or more spacers formed from a polyol such as a diol, triol, tetraol, or a sugar alcohol. The spacer typically comprises groups of Formula (12) or may itself be of Formula (12):wherein b is an integer from 2 to 4; and each R23is independently chosen from hydrogen, deuterium, substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C3-20 cycloalkyl, substituted or unsubstituted Ce-30 aryl, substituted or unsubstituted C4-30 heteroaryl, optionally including one or more of -O-, -S-, -N-, -S(O)-, -S(O)2-, -C(O)-, -C(O)O-, -OC(O)O-, -NRCC(O)-, -or -C(O)NRC-, wherein Rcis hydrogen, deuterium, or substituted or unsubstituted Ci-Ce alkyl. The aforementioned alkyl substituents may be astraight chain or branched, and may optionally contain other atoms such as O, S, N, P, or other functional linkages, which include an ether, an ester, an amide, an imide, a urethane, or a urea.

[0053] Exemplary spacers include, for example, the following:wherein a, b, c, d, and n are each independently an integer from 1 to 10.

[0054] If present, the units formed from the spacer(s) are typically present in the block copolymer in an amount of from 0.1 to 20 mol%, more typically from 1 to 20 mol%, and still more typically from 2 to 20 mol%, based on the total blocks of the block copolymer. Suitable polyols such as a diol, triol, tetraol, and sugar alcohols are commercially available and / or can readily be made by persons skilled in the art.

[0055] In some aspects, the block copolymer may further optionally include one or more additional repeating units. The additional repeating units may be, for example, one or more additional units for purposes of adjusting properties of the block copolymer. Exemplary additional repeating units may include those derived from one or more of (meth)acrylate, vinyl aromatic, vinyl ether, vinyl ketone, and / or vinyl ester monomers. The one or moreadditional repeating units, if present in the block copolymer, may be used in an amount of up to 60 mol%, typically from 3 to 50 mol%, based on total repeating units in the block copolymer.

[0056] The block copolymer may contain one or more functional end groups. The functional end group can be, for example, one or more of -ORC, -N(RC)2, -COOH, -SO3, Ce-3o aryl, or C4- 30 heteroaryl, wherein Rcis independently chosen from hydrogen, deuterium, substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C3-20 cycloalkyl, substituted or unsubstituted Ce 30 aryl, or substituted or unsubstituted C4-30 heteroaryl.

[0057] Non-limiting examples of the block copolymer include the following:

[0058] The block copolymer typically has a weight average molecular weight (Mw) of 500 to 50,000 Daltons (Da), more typically from 4,000 to 30,000 Da, or from 10,000 to 30,000 Da. The polydispersity index (PDI) of the block copolymer, which is the ratio of Mw to number average molecular weight (Mn) is typically 1.1 to 10, specifically 1.1 to 2. Molecular weight values are determined by gel permeation chromatography (GPC) using polystyrene standards. In some embodiments, the block copolymer has Mw of greater than or equal to 4,000 Da, as determined by GPC using polystyrene standards.

[0059] In some embodiments, the block copolymer has Mw of greater than or equal to 4,000 Da, as determined by GPC using polystyrene standards; the block copolymer satisfies Equation 1 ; or a combination thereof.Mw x [1 - (2 x WP2)] > 1,500 Equation 1 wherein, in Equation 1, Mw is the weight average molecular weight of the block copolymer, and WP2 is a weight percent of the of the second block in the block copolymer, based on a total weight of blocks in the block copolymer. In some embodiments, WP2 may be a weight percent of the of the second block in the block copolymer, based on a total weight of the first blocks and the second blocks in the block copolymer.

[0060] In some embodiments, the block copolymer has Mw of greater than or equal to 4,000 Da, as determined by GPC using polystyrene standards; the block copolymer satisfies Equation 2; or a combination thereof.Mw x [1 - (2 x MP2)] > 1 ,500 Equation 2

[0061] wherein, in Equation 1, Mw is the weight average molecular weight of the block copolymer, and MP2 is a mole percent of the of the second block in the block copolymer, based on a total weight of blocks in the block copolymer. In some embodiments, WP2 may be a weight percent of the of the second block in the block copolymer, based on a total weight of the first blocks and the second blocks in the block copolymer.

[0062] The block copolymer may be present in the coating composition in an amount from 0.001 to 50 wt%, more typically 0.001 to 10 wt%, still more typically 0.001 to 2 wt%, based on total solids of the coating composition.

[0063] The block copolymers described herein can be prepared by various methods. For example, the block copolymers can be made by polymerization of one or more oxirane monomers as described above, together with one or more comonomers and optional spacers as described above. The block copolymers can be prepared using any suitable method in the art, for example, free-radical polymerization, anionic polymerization, cationic polymerization, or the like. One or more monomers corresponding to precursors for the repeating units and / or blocks of the block copolymer may, for example, be combined or fed separately, using a suitable solvent and initiator, and polymerized in a reactor. Polymerization may be performed under suitable conditions, such as by heating at an effective temperature, irradiation with actinic radiation at an effective wavelength, or a combination thereof. The block copolymer may be subjected to additional processes such as one or more of filtration, ion exchange, additional washing or extraction, or treatment with solids, for example, celite, silica, or activated charcoal, before being used.

[0064] The coating compositions can include a plurality of the above-described polymers having structurally different repeat units. In a further aspect, a plurality of the abovedescribed polymers having different molecular weights (e.g., Mw) can be used. The plurality of polymers can, for example, include the same repeat units as each other but differ in molecular weight.

[0065] The coating composition further includes a second polymer that is different from the block copolymer. The second polymer may include one or more polymerized (e.g., repeating) units, such as those described herein. Exemplary second polymer may be polyacrylates, polyvinylethers, polyesters, polynorbomenes, polyacetals, polyethylene glycols, polyamides, polyacrylamides, polyphenols, novolacs, styrenic polymers, polyvinyl alcohols, or a combination thereof.

[0066] The second polymer may include one or more repeating units that includes a functional group. For example, the second polymer may include a repeating unit that includes an acid labile group, an acidic group, a basic group, a hydroxyaryl group, a fluoroalcohol group, a sulfonamide group, a lactone group, or a combination thereof. In some embodiments, the second polymer may include a repeating unit that includes an acid labile group, a hydroxyaryl group, a fluoroalcohol group, a sulfonamide group, a lactone group, or a combination thereof. In some embodiments, the second polymer includes a repeating unit including an acid-labile group.

[0067] The second polymer typically has a Mwfrom 1,000 to 500,000 Dalton, specifically from 2,000 to 30,000 Dalton, more specifically from 3,000 to 20,000 Dalton, still more specifically from 3,000 to 10,000 Dalton. The PDI of the polymer, which is the ratio of Mwto Mnis typically from 1.1 to 10, and specifically from 1.1 to 2. Molecular weights are determined by GPC using polystyrene standards.

[0068] The second polymer may be prepared using any suitable methods in the art. For example, one or more monomers corresponding to the polymerized units described herein may be combined, or fed separately, and / or sequentially using suitable solvent(s) and initiator, and polymerized in a reactor. For example, the second polymer may be obtained by polymerization of the respective monomers under any suitable conditions, such as by heating at an effective temperature, irradiation with actinic radiation at an effective wavelength, or a combination thereof.

[0069] The second polymer may be present in the coating composition in an amount from 0.001 to 50 wt%, more typically 0.001 to 10 wt%, still more typically 0.001 to 2 wt%, based on total solids of the coating composition.

[0070] The coating compositions further include a solvent for dissolving the block copolymer, the second polymer, and any additional solid components of the composition and facilitating its coating on the substrate. The solvent can, for example, be an organic -based solvent or an aqueous-based solvent such as water, with an organic-based solvent being typical. Preferably, the solvent is an organic solvent conventionally used in the manufacture of electronic devices. Suitable solvents include, for example: aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane, 1 ,2-dichloroethane and 1 -chlorohexane; alcohols such as methanol, ethanol, 1-propanol, iso-propanol, tert-butanol, 2-methyl-2-butanol, 4- methyl-2-pentanol, and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone) (DAA); propylene glycol monomethyl ether (PGME); ethers such as diethyl ether, tetrahydrofuran, 1 ,4-dioxane and anisole; ketones such as acetone, methyl ethyl ketone, methyl iso-butyl ketone, 2-heptanone and cyclohexanone (CHO); esters such as ethyl acetate, n-butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), hydroxyisobutyrate methyl ester (HBM) and ethyl acetoacetate; lactones such as gammabutyrolactone (GBL) and epsilon-caprolactone; lactams such as N-methyl pyrrolidone; nitriles such as acetonitrile and propionitrile; cyclic or non-cyclic carbonate esters such as propylene carbonate, dimethyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, and propylene carbonate; polar aprotic solvents such as dimethyl sulfoxide and dimethyl formamide; water; and combinations thereof. Of these, preferred solvents are PGME, PGMEA, EL, GBL, HBM, CHO, DAA and combinations thereof. A solvent being “organic-based” means the cumulative content of organic solvents (less impurities) in the solvent is 50 wt% or more, typically 90 wt% or more, 95 wt% or more, 98 wt% or more, or 100 wt%, based on total weight of the solvents. The total solvent content (i.e., cumulative solvent content for all solvents) in the coating compositions is typically from 40 to 99 wt%, for example, from 70 to 99 wt%, or from 85 to 99 wt%, based on the total weight of the coating composition. The solids content of the coating composition is the non-solvent component(s) of the composition. The desired solvent content (i.e., cumulative solvent content for all solvents) will depend, for example, on the particular type of coating being applied, the desired thickness of the coated layer (if a coating is being formed as opposed to a rinsing application), and the coating conditions.

[0071] The coating compositions include the block copolymer, the second polymer that is different from the block copolymer, and a solvent, and may include one or more additional components depending on the application. For example, the coating compositions can furtherinclude a crosslinking agent, a thermal acid generator, a photoacid generator, or a combination thereof.

[0072] The photoresist composition may further include a photoacid generator (PAG). The PAG may be in ionic or non-ionic form. The PAG may be in polymeric or non-polymeric form. In polymeric form, the PAG may be present as a moiety in a repeating unit of a polymer that is derived from a polymerizable PAG monomer. In some embodiments, the block copolymer and / or the second polymer may further include a repeating unit that includes a PAG functionality (e.g., as a salt group of a repeating unit). Suitable PAG compounds may be of the formula G+A , wherein G+is a photoactive cation and A’ is an anion that can generate a photoacid. The PAG cation is preferably chosen from onium cations, preferably iodonium or sulfonium cations. Particularly suitable anions include those whose conjugated acids have a pKa from -15 to 10. The PAG anion is typically an organic anion having a sulfonate group or a non-sulfonate-type group, such as sulfonamidate, sulfonimidate, methide, or borate.

[0073] Commonly used onium salts may include, for example, triphenylsulf onium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; di-t-butyphenyliodonium perfluorobutanesulfonate, and di-t-butyphenyliodonium camphorsulfonate. Other useful PAG compounds are known in the art of chemically amplified photoresists and include, for example: non-ionic sulfonyl compounds, for example, 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p- toluenesulfonate, and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonic acid esters, for example,1.2.3-tris(methanesulfonyloxy)benzene, l,2,3-tris(trifluoromethanesulfonyloxy)benzene, and1.2.3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives, for example, bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane; glyoxime derivatives, for example, bis-O-(p-toluenesulfonyl)-a-dimethylglyoxime, and bis-O-(n- butanesulfonyl)-a-dimethylglyoxime; sulfonic acid ester derivatives of an N-hydroxy imide compound, for example, N-hydroxysuccinimide methanesulfonic acid ester, N- hydroxysuccinimide trifluoromethanesulfonic acid ester; and halogen-containing triazine compounds, for example, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-l,3,5-triazine, and 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-l,3,5-triazine. Suitable photoacid generators are further described in U.S. Patent Nos. 8,431,325 and 4,189,323.

[0074] Typically, when the composition includes a non-polymeric PAG, the PAG is present in the composition in an amount from 0.1 to 55 wt%, more typically from 1 to 25 wt%, basedon total solids of the composition. When present in polymeric form, the PAG is typically included in a polymer in an amount from 1 to 25 mol%, more typically from 1 to 20 mol%, or from 2 to 10 mol%, based on total polymerized units in the polymer.

[0075] In some aspects, the anion and / or cation of the PAG does not include and is free of -F, -CF3, or -CF2- groups. It should be understood that “free of -F, -CF3, or -CF2- groups” means that the anion and / or cation of the PAG excludes groups such as -CH2CF3 and -CH2CF2CH3. In still other aspects, the anion and / or the cation of the PAG is free of fluorine (i.e., does not contain a fluorine atom and is not substituted by a fluorine-containing group). In some aspects, the photoacid generator is free of fluorine (i.e., both the photoactive cation and the anion are free of fluorine).

[0076] A TAG compound is any compound that liberates acid upon exposure to heat. Exemplary thermal acid generators include, without limitation, amine blocked strong acids, such as amine blocked sulfonic acids such as amine blocked dodecylbenzenesulfonic acid. It will also be appreciated by those skilled in the art that certain photoacid generators are able to liberate acid upon heating and may function as thermal acid generators.

[0077] Suitable TAG compounds may include, for example, nitrobenzyl tosylates, such as 2- nitrobenzyl tosylate, 2,4-dinitrobenzyl tosylate, 2,6-dinitrobenzyl tosylate, 4-nitrobenzyl tosylate; benzenesulfonates such as 2-trifluoromethyl-6-nitrobenzyl 4- chlorobenzenesulfonate, 2-trifluoromethyl-6-nitrobenzyl 4-nitro benzenesulfonate; phenolic sulfonate esters such as phenyl, 4-methoxybenzenesulfonate; alkyl ammonium salts of organic acids, such as tri ethylammonium salt of 10-camphorsulfonic acid, trifluoromethylbenzenesulfonic acid, perfluorobutane sulfonic acid; and particular onium salts. A variety of aromatic (anthracene, naphthalene, or benzene derivatives) sulfonic acid amine salts can be employed as the TAG, including those disclosed in U.S. Pat. Nos.3,474,054, 4,200,729, 4,251,665 and 5,187,019. Examples of TAGs include those sold by King Industries, Norwalk, Conn. USA under NACURE, CDX and K-PURE names, for example, NACURE 5225, CDX-2168E, K-PURE 2678 and KPURE 2700. One or more of such TAGs can be used.

[0078] When present, the TAG is typically present in the compositions in an amount from 0.01 to 20 wt%, typically from 1 to 5 wt%, based on total solids of the coating composition.

[0079] Exemplary crosslinking agents may include novolac resins, melamine compounds, guanamine compounds, isocyanate-containing compounds, benzocyclobutenes, benzoxazines, and the like, and typically any of the foregoing having 2 or more, more typically 3 or more substituents selected from methylol, Ci-10 alkoxymethyl, and C2-10acyloxymethyl. Additional crosslinking agents are well-known in the art and are commercially available from a variety of sources. When present, the amount of the crosslinking agents useful in the present compositions may be, for example, from 0.01 to 30 wt%, and preferably from 0.01 to 20 wt%, based on total solids of the coating composition.

[0080] The coating composition may further include one or more additional, optional additives. For example, optional additives may include actinic and contrast dyes, antistriation agents, plasticizers, speed enhancers, sensitizers, a dissolution inhibitor, a dissolution promoter, one or more organic acids, one or more organic bases, photo- decomposable quenchers (PDQ) (and, also known as photo-decomposable bases), basic quenchers, thermal acid generators, surfactants, and the like, or combinations thereof. If present, the optional additives are typically present in the coating compositions in an amount from 0.01 to 10 wt%, based on total solids of the coating composition.

[0081] Organic acids include, but are not limited to, dicarboxylic acids, wherein the dicarboxylic acids include, but is not limited to, oxalic acid, succinic acid, adipic acid, maleic acid, malic acid, glutaric acid, tartaric acid, salts thereof, or mixtures thereof.

[0082] Preferred dissolution inhibitors are polymeric and / or comprise fluorine substitution. Exemplary dissolution inhibitor compounds include those that contain a photoacid-labile group, e.g. a photoacid-labile ester or acetal moiety. Lower molecular weight materials also are generally preferred, e.g. polymers or oligomers having an Mw of less than 5,000 Da.

[0083] PDQs generate a weak acid upon irradiation. The acid generated from a photo- decomposable quencher is not strong enough to react rapidly with acid-labile groups that are present in the resist matrix. Exemplary photo-decomposable quenchers include, for example, photo-decomposable cations, and preferably those also useful for preparing strong acid generator compounds, paired with an anion of a weak acid (pKa > 1) such as, for example, an anion of a C1-20 carboxylic acid or C1-20 sulfonic acid. Exemplary carboxylic acids include formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexanecarboxylic acid, benzoic acid, salicylic acid, and the like. Exemplary sulfonic acids include p-toluene sulfonic acid, camphor sulfonic acid and the like. In a preferred embodiment, the photo- decomposable quencher is a photo-decomposable organic zwitterion compound such as diphenyliodonium-2-carboxylate.

[0084] Exemplary basic quenchers include, for example, linear aliphatic amines such as tributylamine, trioctylamine, triisopropanolamine, tetrakis(2- hydroxypropyl)ethylenediamine:n-tert-butyldiethanolamine, tris(2-acetoxy-ethyl) amine, 2,2',2",2"'-(ethane-l,2-diylbis(azanetriyl))tetraethanol, 2-(dibutylamino)ethanol, and 2, 2', 2"-nitrilotriethanol; cyclic aliphatic amines such as l-(tert-butoxycarbonyl)-4- hydroxypiperidine, tert-butyl 1-pyrrolidinecarboxylate, tert-butyl 2-ethyl-lH-imidazole-l- carboxylate, di-tert-butyl piperazine- 1 ,4-dicarboxylate, and N-(2-acetoxy-ethyl)morpholine; aromatic amines such as pyridine, di-tert-butyl pyridine, and pyridinium; linear and cyclic amides and derivatives thereof such as N,N-bis(2-hydroxyethyl)pivalamide, N,N- diethylacetamide, N1,N1,N3,N3-tetrabutylmalonamide, l-methylazepan-2-one, 1-allylazepan- 2-one, and tert-butyl l,3-dihydroxy-2-(hydroxymethyl)propan-2-ylcarbamate; ammonium salts such as quaternary ammonium salts of sulfonates, sulfamates, carboxylates, and phosphonates; imines such as primary and secondary aldimines and ketimines; diazines such as optionally substituted pyrazine, piperazine, and phenazine; diazoles such as optionally substituted pyrazole, thiadiazole, and imidazole; and optionally substituted pyrrolidones such as 2-pyrrolidone and cyclohexyl pyrrolidine.

[0085] The coating composition can be used in a variety of coating compositions that can be applied by coating in the manufacture of semiconductor devices. Such applications include, for example, various lithography, wet chemical etching, and wafer rinsing compositions. Suitable lithography compositions include, for example, photoresist compositions, photoresist underlayer compositions such as bottom antireflective coating (BARC), spin-on-carbon (SOC), hardmask compositions, gap-fill compositions, immersion and non-immersion topcoat compositions, photoresist pattern overcoat compositions such as chemical trimming overcoat compositions, developer compositions, gap-fill compositions, surfactant rinse compositions, and imprint lithography compositions. Such compositions and their components are known to those skilled in the art. Coating compositions described herein may be applied by various known coating techniques, for example, spin-coating, dip-coating, brush-coating, meniscus-coating, roller-coating, slot-coating, flow-coating, or spray-coating, with spin-coating being preferred.

[0086] The coating compositions can be prepared following known procedures. For example, the coating compositions can be prepared by dissolving the block copolymer, the second polymer, and other solid components of the composition in the solvent. The compositions or one or more of the components of the compositions can optionally be subjected to one or more purification processes, for example, solvent exchange, filtration, and / or ion exchange processes.

[0087] Methods of forming semiconductor devices using the above-described coating compositions are described below. A substrate comprising a semiconductor material is provided and a coating composition as described herein is applied to the substrate by spin-T1coating. Suitable substrates on which the above-described coating compositions can be coated can be chosen from those typically used in the manufacture of semiconductor devices, for example, from semiconductor wafers such as those used in the manufacture of integrated circuits, optical sensors, integrated optical circuits, and LEDs. The substrates may have a flat surface, or more typically may include patterned features with topography. The substrates typically include one or more layers, structures, or features which may optionally include active or operable portions of devices being formed. The substrates are typically composed of one or more of silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, gold, and lithographic materials layers such as hardmask (e.g., metal or SOC), antireflective coating, and patterned or unpattemed photoresist layers. Such substrates may be any suitable size. Typical wafer substrate diameters are 200 to 300 millimeters (mm), although wafers having smaller and larger diameters may be suitably employed.

[0088] Typically, the substrate will include one or more lithographic material layers such as a hardmask layer, for example, SOC, amorphous carbon, or metal hardmask layer, a CVD layer such as a silicon nitride (SiN), a silicon oxide (SiO), or silicon oxynitride (SiON) layer, an organic or inorganic underlayer, or combinations thereof, on an upper surface of the substrate prior to coating the photoresist composition. Such layers, together with an overcoated photoresist layer, form a lithographic material stack or article.

[0089] Optionally, a layer of an adhesion promoter may be applied to the substrate surface prior to coating the photoresist composition. If an adhesion promoter is desired, any suitable adhesion promoter for polymer films may be used, such as silanes, typically organosilanes such as trimethoxyvinylsilane, triethoxyvinylsilane, hexamethyldisilazane, or an aminosilane coupler such as gamma-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those sold under the AP 3000, AP 8000, and AP 9000S designations, available from DuPont Electronics & Industrial (Marlborough, Massachusetts).

[0090] The photoresist composition is coated on the substrate by spin-coating. The spincoating is typically performed with a coating track by which the photoresist is dispensed on a spinning wafer. During dispensing, the wafer is typically spun at a speed of up to 4,000 rotations per minute (rpm), for example, from 200 to 3,000 rpm, for example, 1,000 to 2,500 rpm, for a period of from 15 to 120 seconds to obtain a layer of the photoresist composition on the substrate. It will be appreciated by those skilled in the art that the thickness of the coated layer may be adjusted by changing the spin speed and / or the solids content of the composition. A photoresist layer formed from the coating compositions described herein canhave a thickness that can vary greatly depending on the particular application and wavelength of light used during the exposure. The photoresist layer thickness may, for example, have a dried layer thickness of from 10 nm to 20 microns.

[0091] The photoresist composition is typically next soft-baked to minimize the solvent content in the layer, thereby forming a tack-free coating and improving adhesion of the layer to the substrate. The soft bake is performed, for example, on a hotplate or in an oven, with a hotplate being typical. The soft bake temperature and time will depend, for example, on the particular photoresist composition and thickness. The soft bake temperature is typically from 80 to 170°C, for example, from 110 to 150°C. The soft bake time is typically from 10 seconds to 20 minutes, for example, from 1 minute to 10 minutes, or from 1 minute to 5 minutes. The heating time can be readily determined by one of ordinary skill in the art based on the components of the composition.

[0092] The photoresist layer is next pattern-wise exposed to activating radiation to create a difference in solubility between exposed and unexposed regions. Reference herein to exposing a photoresist composition to radiation that is activating for the composition indicates that the radiation is capable of forming a latent image in the photoresist composition. The exposure is typically conducted through a patterned photomask that has optically transparent and optically opaque regions corresponding to regions of the resist layer to be exposed and unexposed, respectively. Such exposure may, alternatively, be conducted without a photomask in a direct writing method, typically used for e-beam lithography. The activating radiation is typically sub-400 nm, sub-300 nm or sub-200 nm, with 248 nm (KrF laser), 193 nm (ArF laser), 13.5 nm (EUV) wavelength, or e-beam lithography being preferred. The exposure energy is typically from 1 to 200 millijoules per square centimeter (mJ / cm2), preferably 10 to 100 mJ / cm2and more preferably 20 to 50 mJ / cm2, dependent upon the exposure tool and components of the photoresist composition.

[0093] Following exposure of the photoresist layer, a postexposure bake (FEB) of the exposed photoresist layer is performed. The PEB can be conducted, for example, on a hotplate or in an oven, with a hotplate being typical. Conditions for the PEB will depend, for example, on the particular photoresist composition and layer thickness. The PEB is typically conducted at a temperature of from 80 to 150°C, and a time of from 30 to 120 seconds. A latent image defined by the polarity-switched (exposed regions) and unswitched regions (unexposed regions) is formed in the photoresist.

[0094] The exposed photoresist layer is then developed with a suitable developer to selectively remove those regions of the layer that are soluble in the developer while theremaining insoluble regions form the resulting photoresist pattern relief image. In the case of a positive-tone development (PTD) process, the exposed regions of the photoresist layer are removed during development and unexposed regions remain. Conversely, in a negative-tone development (NTD) process, the exposed regions of the photoresist layer remain, and unexposed regions are removed during development. Application of the developer may be accomplished by any suitable method, with spin coating being typical. The development time is for a period effective to remove the developer- soluble regions of the photoresist, with a time of from 5 to 60 seconds being typical. Development is typically conducted at room temperature.

[0095] Suitable developers for a PTD process include aqueous base developers, for example, quaternary ammonium hydroxide solutions such as TMAH, preferably 0.26 normal (N) TMAH, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the like. Suitable developers for an NTD process are organic solvent-based, meaning the cumulative content of organic solvents in the developer is 50 wt% or more, typically 95 wt% or more, 95 wt% or more, 98 wt% or more, or 100 wt%, based on total weight of the developer. Suitable organic solvents for the NTD developer include, for example, those chosen from ketones, esters, ethers, hydrocarbons, alcohols, and mixtures thereof. The NTD developer is typically chosen from n-butyl acetate, 2-heptanone, or isopropanol. Additionally, there may be further steps during the exposure and / or developing stage (e.g., a prior rinsing, an after PEB rinse, and / or an after development rinse).

[0096] The resulting photoresist relief image can take various forms, for example, one or more of hole patterns such as for forming contact hole, via hole, or bump patterns, line-space patterns, or trench patterns. The resist relief image can be used, for example, as an etch mask, thereby allowing the patterns to be transferred to one or more sequentially underlying layers by known etching techniques, typically by dry etching such as reactive ion etching. The photoresist pattern may, for example, be used for pattern transfer to an underlying hardmask layer which, in turn, is used as an etch mask for pattern transfer to one or more layers below the hardmask layer. If the photoresist pattern is not consumed during pattern transfer, it may be removed from the substrate by known techniques, for example, oxygen plasma ashing or a wet strip process. The photoresist compositions may, when used in one or more such patterning processes, be used to fabricate semiconductor devices such as memory devices, processor chips (CPUs), graphics chips, optoelectronic chips, LEDs, OLEDs, as well as other electronic devices.

[0097] In the above-described process, any one or more of the lithography compositions described, for example, the photoresist composition, photoresist underlayer composition such as bottom antireflective coating (BARC), SOC, and hardmask compositions, or the developer composition may be the coating composition that is described herein that includes the block copolymer, the second polymer that is different from the block copolymer, and the solvent. For example, overcoating layers on top of the photoresist layer, like top coat, chemical trim overcoat, and / or top antireflective coating, could be further applied to form the lithographic material stack. The coating compositions described herein may be used in any or more of the bottom, resist, and / or overcoat layers in the stack.

[0098] In accordance with a further aspect, the coating composition that is the block copolymer, the second polymer that is different from the block copolymer, and the solvent is a photoresist topcoat composition. Topcoat compositions can be used in immersion or nonimmersion lithography processes. In immersion lithography, the topcoat composition is spin- coated above a photoresist layer prior to exposure of the photoresist layer for minimizing or preventing migration of components of the photoresist layer into an immersion fluid employed in an immersion lithography process. They can also provide a hydrophobic surface that enables fast scanning speed without defect formation. Topcoat compositions typically include a surface-active polymer that is self- segregating from other polymers of the composition during the coating process. The block copolymer can serve the function of the topcoat composition surface active polymer. As used herein, the term “immersion fluid” means a fluid, typically water, interposed between a lens of an exposure tool and a photoresist coated substrate to conduct immersion lithography. The photoresist layer with overcoated topcoat layer is then exposed through a patterned photomask to radiation activating for the photoactive component of the photoresist. The exposure is typically conducted with an immersion scanner but can alternatively be conducted with a dry (nonimmersion) exposure tool.

[0099] In accordance with a further aspect, the coating composition that is the block copolymer, the second polymer that is different from the block copolymer, and the solvent is a photoresist pattern overcoat composition that is applied to the substrate over the formed photoresist pattern relief image. Suitable pattern overcoat compositions include, for example, chemical trimming overcoat and pattern growth compositions, which allow for the formation of finer photoresist patterns than attainable by direct imaging alone. Photoresist pattern trimming processes involve contacting a formed photoresist pattern that includes a polymer having acid-labile groups with a trimming composition containing a solvent, an acid or athermal acid generator, and other optional components. A layer of the photoresist pattern trimming composition may be formed over the photoresist pattern by spin-coating. The solids content of the coating solution can be adjusted to provide a desired film thickness. A typical thickness for the pattern trimming composition layer is from 200 to 1500 A. The substrate is next baked to remove solvent in the trimming composition layer. The bake also allows the acid of the trimming composition to diffuse into the surface of the underlying resist pattern to cause a polarity-changing reaction in the resist pattern surface region. The bake can be conducted with a hotplate or oven, with a hotplate being typical. Suitable bake temperatures are greater than 50°C, for example, greater than 70°C, greater than 90°C, greater than 120°C or greater than 150°C, with a temperature from 70 tol60°C and a time from 30 to 90 seconds being typical. The photoresist pattern is next contacted with a rinsing agent, typically a developing solution, to remove the residual trimming composition layer and the surface region of the photoresist pattern. The rinsing agent is typically an aqueous alkaline developer, for example, a quaternary ammonium hydroxide solution, for example, a tetra-alkyl ammonium hydroxide solution such as 0.26 Normality (N) (2.38 wt%) TMAH. The rinsing agent can further be or include water. The resist pattern after trimming treatment has a dimension (L2) that is smaller as compared with the feature size prior to trimming treatment.

[0100] The following non-limiting examples are illustrative of the subject matter.EXAMPLESCoating Compositions

[0101] Dioxane, toluene, and oxirane monomers Ml and M2 were distilled and dried with molecular sieves before use. Pluronic L35, Pluronic L64, Pluronic P104, Pluronic L10, Pluronic 17R4, Pluronic P123, and Pluronic P105 were obtained from BASF. PPO-2000 (polypropylene oxide) and PEO-2000 (polyethylene oxide) were obtained from Fisher Scientific. Other materials were used as received from commercial sources unless mentioned otherwise.Ml M2Example 1

[0102] Pluronic L35 was dried under vacuum at 110°C for two hours in a flask. Then, 16.0 grams (g) of Pluronic L35 was transferred to a reactor and mixed with 5 milliliters (mL)of potassium tert-butoxide (KtBuO) (1.0M in THF), and the resulting mixture was reacted for 5 minutes. The volatiles were removed at 125°C for 30 minutes. Monomer Ml (epoxyhexane) and 20 mL of dioxane were then added into the reactor, and the reaction mixture was heated at 95°C for 48 hours. The mixture was then quenched with ~0. 1 mL 10M HC1 (in H2O) and Na2SO4 was added to remove water. The resulting solution was diluted with methyl t-butyl ether and filtered with a 0.2-micron PTFE filter. The mixture was concentrated with a rotavapor to provide the block copolymer. The block copolymer was diluted with heptane and filtered twice with a 0.2-micron PTFE filter. The solvent was then removed under a reduced pressure. Weight average and number average molecular weights (Mw and Mn, respectively) were determined by GPC calibrated with polystyrene standards. Dispersity (D) of the block copolymer was calculated as Mw / Mn. The results are shown in Table 1 . The degree of polymerization (DP) of the monomer M 1 determined by1H NMR analysis and the amount of the block copolymer that is not derived from the monomer Ml are provided in Table 2.Examples 2-24

[0103] Additional block copolymers were prepared in a manner similar to that described in Example 1, using the materials and amounts set forth in Table 1. The weight average molecular weight (Mw) and dispersity results are also shown in Table 1. The degree of polymerization (DP) of the monomer Ml and / or M2 determined by]H NMR analysis and the amount of the block copolymer that is not derived from the monomer Ml and / or M2 are provided in Table 2.Table 1PEO = poly(ethylene oxide), PPO = polypropylene oxide), Pluronic block copolymer = PEO-PPO-PEO block copolymerTable 2rationPolymer A [Mw = 11 kDa, D = 2.2]Example 25

[0104] An SLA block copolymer solution (1 wt% of the block copolymer of Example 1 in PGMEA) was prepared in a 100 mL bottle by first charging 1 g of the block copolymer and then 99 g PGMEA into the bottle, followed by machine- shaking overnight. A base polymer solution (30 wt% Polymer A in PGMEA) was prepared in a 1 L bottle by first charging 240 g of Polymer A and then 560 g PGMEA into the bottle, followed by machineshaking overnight. The solution of Example 26 was prepared as follows. 12.773 g of the base polymer solution, 1.356 g of PGMEA, and 3.869 g of the SLA block copolymer solution were charged to a 20 mL scintillation vial. The mixture was mixed on a machine-shaker for 2-3 hours and then filtered with a 0.2 pm PTFE disk filter into a clean 20 mL scintillation vial to form coating composition CL Examples 26-44

[0105] Coating compositions (C2-C20) were prepared in a manner similar to that described in Example 25, using the materials and amounts set forth in Table 3. Examples 45-49

[0106] Coating compositions (C21-C25) were prepared in a manner similar to that described in Example 25, using the materials and amounts set forth in Table 4, except the solvent was a mixture of ethyl lactate, anisole, and amyl acetate (60 / 30 / 10 w / w), hereinafter “SMX,” instead of PGMEA.Coating Quality Evaluation

[0107] Bare 8-inch silicon wafers were spin-coated with one of the coating compositions of Examples 25-49 on a TEL Clean Track ACT8 Coater / Developer using Tridak dispensing mode and a spin speed of 1500 rpm and soft-baked at 130°C for 60 seconds to provide a target film thickness of 1.6 to 1.7 m. The coating quality was visually evaluated for the presence of coating defects, for example, striation, orange peel, comets, and haze, using both a Unilamp UL-12 green light box (Midwest Scientific Co.) and a Keyence VHX7000 con- focal microscope using high dynamic range (HDR) mode. Magnifications of 20X and 100X were used to capture images both at the wafer center and wafer edge. Films with no visible defects were deemed to have acceptable coating quality as denoted by the symbol “O”. Coatings with striation were deemed to have poor coating quality and denoted by the symbol “X”. The evaluation results are shown in Tables 3 and 4.Table 3Table 4Solubility Evaluation

[0108] The solubility of the block copolymers of Examples 1 to 24 to were evaluated in different solvents at 5 wt% loading using 20 mL scintillation vials. Commercial fluorocontaining SLA, POLYFOX PF-656, from OMNOVA, was also evaluated as a control. The solubilities of the block copolymers and the comparative examples are summarized below in Table 5, where “S” denotes soluble, “NS” denotes not soluble.Table 5Poly(Ml) = homopolymer derived from monomer Ml , Poly(Ml 2) = random copolymer derived from monomers Ml and M2

[0109] The solvents in Table 5 are abbreviated as follows: PGMEA is propylene glycol methyl ether acetate, PGME is propylene glycol methyl ether, EL is ethyl lactate, HBM is methyl 2-hydroxyisobutyrate, GBL is gamma-butyrolactone, BB is benzyl benzoate, MMP is methyl 3 -methoxypropionate, CHO is cyclohexanone, and SMx is EL / anisole / amyl acetate (60 / 30 / 10 w / w).Photoresist Compositions

[0110] The synthetic reactions were performed under a nitrogen atmosphere.Ethylcyclopentyl methacrylate (ECPMA), y-butyrolacton-2-yl methacrylate (a-GBLMA), 2- oxohexahydro-2H-3,5-methanocyclopenta[b]furan-6-yl methacrylate (NLMA), triphenylsulfonium perfluoro- 1-butanesufonate (TPS-PFBS), and diphenyliodonium-2- carboxylate monohydrate (DPIC) were purchased from commercial sources and used without further purification.

[0111] The photoresist copolymer (PCI) was prepared as follows. A reactor was charged with 112 g of a degassed mixture of ethyl lactate (70 wt%) and 1,4-lactone (30 wt%), and heated to 80°C. A degassed monomer feed solution was prepared from a combination of 318.3 g of solvent (ethyl lactate / l,4-lactone, 7:3 w / w), 95.9 g of ECPMA, 88.9 g of a- GBLMA, and 58 g of NLMA. Separately, a degassed initiator feed solution was prepared using 12.4 g of V601 initiator and 125.2 g of solvent (ethyl lactate / 1,4-lactone, 7:3 w / w). The monomer feed solution and the initiator feed solution were then continuously added to the reactor at the same time, with the monomer feed solution being added over the course of 240 minutes and the initiator feed solution being added over the course of 210 minutes. The reactor was then cooled at a rate of 1 °C / min to ambient temperature. The copolymer was isolated by precipitation into methanol and the product was dried before use. The photoresist copolymer PCI was derived from the monomer combination ECPMA / a-GBLMA / NLMA (40 / 40 / 20 mole ratio) and had a Mwof 5028 Da, Mwof 8806 Da, and D of 1.75. Mw. Mn, and dispersity index (D) were determined by GPC using polystyrene standards.

[0112] The photoresist copolymer was derived from monomers having the following

[0113] Positive tone photoresist compositions PR1 to PR4 were prepared by dissolving solid components in solvents using the materials and amounts indicated in Table 6, where the amounts are expressed in wt% based on 100 wt% of total weight of the solids. The total solids content for the photoresist compositions was 3.1%. The solvent system contained PGMEA (SI) and 2-hydroxyisobutyric acid methyl ester (S2). Each mixture was shaken in a 100 mL glass container on a mechanical shaker and filtered through a PTFE disk-shaped filter having a pore size of 0.20 micrometers.

[0114] POLYFOX™ PF-656 was obtained from Synthomer:Table 6Lithographic Testing - Examples 50 to 53

[0115] 200 mm silicon wafers were spin-coated with AR™ 40A antireflectant (DuPontElectronics & Industrial) using a cure temperature of 205 °C for 60 seconds to form a first BARC layer having a thickness of 80 nm. The wafers were then spin-coated with a respective photoresist composition from Table 6 and soft-baked at 90°C for 60 seconds to provide a photoresist layer having a thickness of 90 nm. The BARC and photoresist layers were coated with a TEL CLEAN TRACK™ LITHIUS™ coating tool. The wafers were exposed to 193 nm activating radiation using a Nikon S610C immersion scanner (1.30 NA, 0.98 / 0.79 inner / outer sigma, dipole illumination with 35 Y polarization) using a mask having line-space patterns (38 nm linewidth / 80 nm pitch or 38 nm linewidth / 86 nm pitch) at various doses. The exposed wafers were post-exposure baked at 95 °C for 60 seconds and developed with a 0.26 N aqueous tetramethylammonium hydroxide (TMAH) solution (MF™-CD26, DuPont Electronics & Industrial) for 12 seconds. The wafers were then rinsed with DI water and spin- dried to form photoresist patterns. CD line width measurements of the formed patterns were made using a Hitachi High Technologies Co. CG4000 CD-SEM. The coated wafer was then exposed with an ArF excimer laser at 193 nm (ASML 1100, NA 0.75, o 0.89 / 0.64).Thereafter, the wafer was subjected to post-exposure bake (PEB) at 90°C for 60 seconds followed by development with 0.26 N tetramethylammonium hydroxide (TMAH) solution(MF™-CD26, DuPont Electronics & Industrial). The wafers were then washed with water to form a 1 : 1 L / S pattern at 90 nm. CD linewidth measurements of the formed patterns were made using a Hitachi High Technologies Co. CG9380 CD-SEM.

[0116] Line-space patterns in nanometers (nm) were analyzed for critical dimension (CD), where sizing energy “ESiZe” is the irradiation energy when the CD of the formed linespace pattern is equal to the CD of the mask pattern. ESizeis expressed in units of millijoules per square centimeter (mJ / cm2). Exposure latitude (EL%) is the difference in exposure energy required to print the line-space patterns at plus and minus 10% of the target diameter, normalized by the sizing energy. Linewidth roughness (LWR) is expressed in units of nanometers (nm) and was determined as the 3 -sigma value from the distribution of a total of 20 arbitrary points of line width measurements, followed by removing metrology noise. The Esize, EL%, and LWR data are shown in Table 7.Table 7

[0117] The photoresist compositions of Examples 50 and 51 achieved similar lithographic performance compared with the comparative photoresist composition of Example 53, which included POLYFOX PF-656.Examples 54 to 57Polymer P26

[0118] 2.65 g of Brij S20 was dried at 150°C under vacuum for 2 hours in a flask.Then, the polymer was mixed with 1.5 mL of KtBuO (1.0 M in THF), and the resulting mixture was reacted for 5 minutes at room temperature. The volatiles were removed at 125°C for 30 minutes. Monomer Ml (epoxyhexane, 20 mL) and 20 mL of dioxane were then added into the reactor, and the reaction mixture was heated at 95°C for 24 hours. After cooling to room temperature, 5 g of activated charcoal was added to the mixture with 150 mL of methyl t-butyl ether, and the resulting mixture was stirred for 16 hours. After filtration and concentration under a reduced pressure, the target material polymer P26 was obtained. GPCshowed Mn = 4,956 Da, Mw = 6,146 Da, D - 1.24. ’H NMR shows DP of epoxyhexane was about 76.Polymer P27

[0119] Step I. In a flask, 1753 mg of PPO-IOOO was dried at 120°C under a reduced pressure for 2 hours. 0.2 mL of KtBuO (1.0 M in THF) was added and reacted for 20 minutes at room temperature. The volatiles were then removed under a reduced pressure. 100 mL butyl glycidyl ether (dried with 3 A molecular sieves) was then added to the reaction mixture. The reaction mixture was heated to 100°C for 4 hours, and then at 110°C for 24 hours. After cooling to room temperature, 5 g of activated charcoal was added with 400 mL heptane, and the resulting mixture was stirred for 16 hours. After filtration and concentration under a reduced pressure, the polymer was isolated.

[0120] Step II. 7.2 g of the polymer obtained in Step I was mixed with 430 mg 4-cyano- 4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid in 30 mL dichloromethane with 20 mg of 4-pyrrolidinopyridine. After adding 300 mg of N-(3-dimethylaminopropyl)-N / - ethylcarbodiimide hydrochloride, the reaction was stirred at room temperature for 16 hours. The solution was washed with acetic acid solution (5% in water) and then K2CO3 solution (5% in water). The solution was then dried with sodium sulfate before being treated with 3.0 g of activated charcoal with constant stirring for 16 hours. The polymer was isolated by removing volatiles under a reduced pressure.

[0121] 2.62 g of the polymer from Step II was mixed with 10 mg V40 initiator, 506 mg of styrene and 2.7 g of dioxane. After sparging with nitrogen, the solution was heated to 90°C for 24 hours. The volatiles were removed under a reduced pressure and the mixture was redissolved in heptane and stirred with 1.2 g of activated charcoal. After filtration, the mixture was concentrated under a reduced pressure to yield the final product polymer P27. GPC shows Mn = 12,022 Da, Mw = 20,008 Da, D = 1.66. NMR shows the mole ratio of comonomers being DP (propylene oxide) : DP(butyl glycidyl ether) : DP (styrene) = 4.3% / 88.5% 1 7.2%Polymer P28

[0122] 2.68 g of the polymer from Step II for Polymer P27 was mixed with 10 mg ofV40 initiator, 450 mg of n-butyl acrylate and 2.82 g of dioxane. After sparging with nitrogen, the solution was heated to 90°C for 22 hours. Volatiles were removed and the mixture was redissolved in heptane and stirred with 1.1 g of activated charcoal. After filtration, the mixture was concentrated under a reduced pressure to yield the final product polymer P28.GPC shows Mn = 13015 Da, Mw = 20664 Da, D = 1.59. NMR shows the mole ratio of comonomers being DP(propylene oxide) : DP(butyl glycidyl ether) : DP (n-butyl acrylate) = 4.0% / 86.0% / 10.0%.Polymer P29

[0123] 3.0 g of the polymer from Step II for Polymer P27 was mixed with 11 mg ofV40 initiator, 635 mg of ethylcyclopentyl methacrylate and 6.63 g of dioxane. After sparging with nitrogen, the solution was heated to 90°C for 22 hours. The volatiles were removed under a reduced pressure and the mixture was redissolved in heptane and stirred with 1.2 g of activated charcoal. After filtration, the mixture was concentrated under a reduced pressure to yield the final product polymer P29. GPC shows Mn = 11477 Da, Mw = 18298 Da, D = 1.59. NMR shows the mole ratio of comonomers being DP(propylene oxide) : DP(butyl glycidyl ether) : DP (ECPMA) = 3.9% / 83.9% / 12.2%.Coating Compositions

[0124] Coating compositions C26 to C29 were prepared in a manner similar to that described in Example 25, using the materials and amounts set forth in Table 8.Coating Quality Evaluation

[0125] Bare 8-inch silicon wafers were spin-coated with coating compositions as described above on a TEL Clean Track ACT8 Coater / Developer using Tridak dispensing mode and a spin speed of 1500rpm and soft-baked at 130°C for 60 seconds to provide a target film thickness of 1.6 to 1.7 pm. The coating quality was visually evaluated for the presence of coating defects, for example, striation, orange peel, comets, and haze, using both a Unilamp UL-12 green light box (Midwest Scientific Co.) and a Keyence VHX7000 con-focal microscope using high dynamic range (HDR) mode. Magnifications of 20X and 100X were used to capture images both at the wafer center and wafer edge. A film with no visible defects was deemed as OK and denoted by the symbol “O”. Coatings with striation were deemed to have poor coating quality and denoted by the symbol “X”. The evaluation results are shown in Table 8.Table 8

[0126] While this disclosure has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the subject matter is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

CLAIMSWhat is claimed is:

1. A coating composition, comprising: a block copolymer; a second polymer that is different from the block copolymer; and a solvent, wherein the block copolymer comprises: a first block formed from an oxirane monomer comprising a substituent group comprising 3 or more carbon atoms; and a second block that is different from the first block, and wherein the block copolymer is free of CF2 and CF3 groups that are bonded to a carbon atom.

2. The coating composition of claim 1 , wherein the block copolymer has a weight average molecular weight of greater than or equal to 4,000 Daltons, as determined by gel permeation chromatography using polystyrene standards, the block copolymer satisfies Equation 1 , or a combination thereof:Mw x [1 - (2 x WP2)] > 1,500 Equation 1 wherein, in Equation 1,Mw is the weight average molecular weight of the block copolymer, andWP2 is a weight percent of the second block, based on a total weight of blocks in the block copolymer.

3. The coating composition of claim 1 or 2, wherein the first block comprises a repeating unit of Formula (1):the second block comprises one or more repeating units of Formulae (2) to (5):wherein, in Formulae (1) to (5),R1to R4are each independently hydrogen, deuterium, substituted or unsubstituted Ci-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C3-30 cycloalkenyl, substituted or unsubstituted C2-30 alkynyl, substituted or unsubstituted C3-30 cycloalkynyl, substituted or unsubstituted Ce-30 aryl, substituted or unsubstituted C4-30 heteroaryl, optionally comprising one or more of -O-, - S-, -Si(Rc)2-, -N(RC)-, -S(O)-, -S(O)2-, -C(O)-, -C(O)O-, -C(O)S-, -OC(O)O-, -N(RC)C(O)-, or-C(O)N(RC)-; Rcis hydrogen, deuterium, or substituted or unsubstituted Ci-Ce alkyl; any two or more of R1, R2, R3, and R4together may optionally form a ring, and at least one of R1, R2R3, and R4has 3 or more carbon atoms;Rais hydrogen, deuterium, halogen, substituted or unsubstituted C1-6 alkyl, or substituted or unsubstituted C3-6 cycloalkyl;L1is a single bond or a divalent linking group;R5is substituted or unsubstituted Ci-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C1-30 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C2-30 heteroaryl, substituted or unsubstituted C3-30 heteroarylalkyl, or substituted or unsubstituted C3-30 alkylheteroaryl;R6and R7are each independently hydrogen, deuterium, substituted or unsubstituted Ci -30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C1-30 heterocycloalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C3-30 cycloalkenyl, substituted or unsubstituted C2-30 alkynyl, substituted or unsubstituted C3-30 cycloalkynyl, substituted or unsubstituted Co-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C4-30 heteroaryl, substituted or unsubstituted C3-30 heteroarylalkyl, or substituted or unsubstituted C3-30 alkylheteroaryl, optionally comprising one or more of -O-, -S-, -Si(Rc)2-, -N(RC)-, - S(O)-, -S(O)2-, -C(O)-, -C(O)O-, -C(O)S-, -OC(O)O-, -N(RC)C(O)-, or -C(O)N(RC)-; Rcis hydrogen, deuterium, or substituted or unsubstituted Ci-Ce alkyl; and R6and R7together optionally form a ring;X is O, S, or NRC;Y1and Y2are each independently a single bond, -C(O)-, -S(O)-, -S(O)2-, or - P(O)ORC;Z is a single bond, -O-, -S-, -NRC-, C2-5 alkenylene, C2-5 alkynylene, C6-12 arylene, or C6-12 heteroarylene;R8and R9are each independently hydrogen, deuterium, substituted or unsubstituted Ci- 30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C3-30 cycloalkenyl, substituted or unsubstituted C2-30 alkynyl, substituted or unsubstituted C3-30 cycloalkynyl, substituted or unsubstituted Ce-30aryl, substituted or unsubstituted C4-30 heteroaryl, optionally comprising one or more of -O-, -S-, -Si(Rc)2-, -N(RC)-, -S(O)-, -S(O)2-, -C(O)-, -C(O)O-, -C(O)S-, -OC(O)O-, -N(RC)C(O)-, or -C(O)N(RC)-; and any two or more of R8and R9together may optionally form a ring;Rcis hydrogen, deuterium, or substituted or unsubstituted Ci-Ce alkyl; and a and b are each independently an integer from 0 to 9, provided that a+b is an integer from 1 to 18.

4. The coating composition of any of claims 1 to 3, wherein the second block comprises one or more repeating units of Formula (6):wherein, in Formula (6),R10is substituted or unsubstituted C1-6 alkylene, C2-6 alkenylene, C2-6 alkynylene, Ce- 12 arylene, or C6-12 heteroarylene, optionally comprising one or more of -O-, -S-, -SO-, -SO2-, -NRC-, -C(O)-, or -C(O)O- as part of its structure, wherein Rcis hydrogen, deuterium, or substituted or unsubstituted Ci-Ce alkyl.

5. The coating composition of claim 4, wherein at least one of R1to R4or R10comprises an acid-labile group, a base-labile group, or a base-soluble group.

6. The coating composition of any of claims 1 to 5, wherein the second polymer comprises a repeating unit comprising an acid labile group.

7. The coating composition of any of claims 3 to 6, wherein the block copolymer further comprises a third block, wherein the third block is different from the first block andthe second block, and wherein the third block comprises one or more repeating units ofFormulae (2) to (5).

8. The coating composition of any of claims 1 to 7, further comprising a crosslinking agent, a thermal acid generator, a photoacid generator, or a combination thereof.

9. A method, comprising:(a) providing a substrate; and(b) coating a coating composition over the substrate, wherein the coating composition comprises a block copolymer and a solvent, wherein the block copolymer comprises: a first block formed from an oxirane monomer comprising a substituent group comprising 3 or more carbon atoms; and a second block that is different from the first block, and wherein the block copolymer is free of CF2 and CF3 groups that are bonded to a carbon atom.

10. The method of claim 9, wherein the coating composition further comprises a second polymer that is different from the first polymer.

11. A pattern forming method, comprising: forming on a substrate a photoresist composition layer from the coating composition of any of claims 1 to 8; pattern-wise exposing the photoresist composition layer to activating radiation; and developing the exposed photoresist composition layer to provide a resist relief image.

12. A pattern forming method, comprising: coating the coating composition of any of claims 1 to 8 on a substrate to form an underlayer; forming a photoresist layer over the underlayer; pattern- wise exposing the photoresist layer to activating radiation; and developing the exposed photoresist layer to provide a resist relief image.

13. A pattern forming method, comprising: forming a photoresist composition layer on a substrate; coating the coating composition of any of claims 1 to 8 on the photoresist composition layer to form an overlayer; pattern-wise exposing the overlayer to activating radiation; and developing the photoresist composition layer to provide a resist relief image.

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