Coating compositions and methods

Abstract

Coating compositions comprise: a first polymer comprising a first repeat unit formed from an oxirane monomer comprising a substituent having 3 or more carbon atoms, wherein the oxirane monomer is free of CF2 and CF3 groups that are bonded to a carbon atom; a second polymer that is different from the first polymer; and a solvent.

Description

COATING COMPOSITIONS AND METHODS CROSS REFERENCE TO RELATED APPLICATIONS The application claims priority to U.S. provisional application No.63 / 623089, filed January 19, 2024, the entire disclosure of which is incorporated herein by reference. BACKGROUND OF THE INVENTION 1. Field of the Invention

[0001] The invention relates generally to coating compositions. More specifically, this invention 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. 2. Description of the Related Art

[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 A1). 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. It is 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 patterning defects in photoresist patterning owing to their low surface energy (greater hydrophobicity) and resulting poor solubility in the developer. For example, to impart desired surface energy properties to SLAs, theinclusion 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 OF THE INVENTION

[0006] In accordance with a first aspect of the invention, coating compositions are provided. The coating compositions comprise: a first polymer comprising a first repeat unit formed from an oxirane monomer comprising a substituent having 3 or more carbon atoms, wherein the oxirane monomer is free of CF2 and CF3 groups that are bonded to a carbon atom; a second polymer that is different from the first polymer; and a solvent.

[0007] In accordance with a preferred aspect, the first repeat unit is of formula (1): wherein: independently -H, deuterium, substituted or unsubstituted C1-20 alkyl,substituted or C3-20 cycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C4-30heteroaryl, optionally including one or more of -O-, -S-, -N-, -S(O)-, -S(O)2-, -C(O)-, -C(O)O-, -OC(O)O-, -NC(O)-, -or -C(O)NR5-, wherein R5is H, deuterium, or substituted or unsubstituted C1-C6 alkyl, and any two or more of R1, R2, R3, and R4together optionally forming a ring, and wherein at least one of R1, R2, R3, and R4has 3 or more carbon atoms.

[0008] In accordance with a further aspect of the invention, a method is provided. The method comprises: (a) providing a substrate; and (b) coating a coating composition over the substrate, wherein the coating composition comprises: a polymer comprising a first repeat unit formed from an oxirane monomer comprising a substituent having 3 or more carbon atoms, wherein the oxirane monomer is free of CF2and CF3 groups that are bonded to a carbon atom; and a solvent.

[0009] In accordance with a further aspect of the invention, the coating composition is a photoresist composition, the method further comprising: (c) patternwise exposing a layer of the photoresist composition to activating radiation; and (d) developing the exposed photoresist layer to provide a resist relief image.

[0010] In accordance with a further aspect of the invention, the coating composition is photoresist underlayer composition, the method further comprising: (c) forming a photoresist layer over theunderlayer; (d) patternwise exposing the photoresist layer to activating radiation; and (e) developing the exposed photoresist layer to provide a resist relief image.

[0011] In accordance with a further aspect of the invention, the substrate comprises a photoresist layer or a photoresist pattern on which the coating composition is directly applied.

[0012] In accordance with a further aspect of the invention, the coating composition is an imprint lithography composition, the method further comprising: (c) imprinting the coating composition with a template to form a pattern.

[0013] In accordance with a further aspect of the invention, the substrate is an electronic device substrate and the coating composition is a surfactant rinse solution or a developer.

[0014] In accordance with a further aspect of the invention, the coating composition is a gap-fill composition, wherein coating the composition fills a plurality of gaps on the substrate surface. DETAILED DESCRIPTION OF THE INVENTION

[0015] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular forms "a", "an" and "the" are intended to include singular and plural forms, unless the context indicates otherwise. All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. When an element is referred to as being "on" or "over" 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.

[0016] Unless otherwise indicated, a group that is "substituted" refers to a group having one or more of its hydrogen atoms replaced with one or more substituents. Exemplary substituent groups include, but are not limited to, isotopes of hydrogen such as deuterium, hydroxy (OH), halogen (e.g., F, Cl, I, Br), C1-18 alkyl, C1-8 haloalkyl, C3-12 cycloalkyl, C6-12 aryl having at least one aromatic ring (e.g., phenyl, biphenyl, naphthyl, or the like, each ring either substituted or unsubstituted aromatic), C719 arylalkyl having at least one aromatic ring, C7-12alkylaryl, and combinations thereof. For purposes of carbon number determination, when a group is substituted, the number of carbon atoms of the group is the total number of carbon atoms in such group excluding those of any substituents.

[0017] The coating compositions of the invention comprise: a first polymer comprising a first repeat unit formed from an oxirane monomer comprising a substituent having 3 or more carbon atoms, wherein the oxirane monomer is free of CF2 and CF3 groups that are bonded to a carbon atom; a second polymer that is different from the first polymer; and a solvent. The first polymer 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 first polymer can be blended with a wide variety of solutions, waxes, polishes, coatings, blends, and the like. In an embodiment, the surface leveling agent may be used in floor polish formulations, painting, powder coating compositions, or the like. The coatingcompositions find particular benefit in semiconductor manufacturing such as for lithography applications. Coating compositions comprising the first polymer, 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.

[0018] The polyoxirane-containing backbone can provide the first polymer with hydrophilic properties for miscibility with water and aqueous base developers, while the carbon-containing substituent can provide hydrophobic properties allowing for the first polymer to migrate to the layer / air surface of the coated layer of the coating composition. In a first aspect, the first polymer can be sufficiently hydrophilic to be miscible with water or an aqueous base developer. In another aspect, the surface leveling agent 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.

[0019] The first polymer is preferably free of silicon- and fluorine-containing moieties. The absence of such silicon- and fluorine-containing moieties in the surface leveling agent 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 CF2and CF3groups that are bonded to a carbon atom in the first polymer may further be desired from the standpoint of providing sustainable alternative chemistries.

[0020] The first polymer can be a homopolymer formed from one type of oxirane monomer, or can be a copolymer having a plurality of distinct repeat units, for example, two, three, four, or more distinct repeat units. The copolymer may, for example, include two or more distinct repeat units formed from different oxirane monomers, or may include one or more repeat units formed from a non-oxirane monomer. The copolymer may be a random copolymer, alternating copolymer, a block copolymer, a star block copolymer, a hyperbranched polymer, a comb copolymer, a dendrimer, a gradient copolymer, or the like, with a random copolymer or a block copolymer being typical. Combinations of random copolymers and block copolymers may also be used for the first polymer.

[0021] The first repeat unit is preferably of formula (1): independently -H, deuterium, substituted or unsubstituted C1-20 alkyl,20 cycloalkyl, substituted or unsubstituted C2-20 alkenyl, substituted or unsubstituted C3-20cycloalkenyl, substituted or unsubstituted C2-20alkynyl, substituted or unsubstituted C3-20cycloalkynyl, substituted or unsubstituted C6-30aryl, substituted or unsubstituted C4-30heteroaryl, optionally including one or more of -O-, -S-, -Si(R5)2-, -N(R5)-, -S(O)-, -S(O)2-, -C(O)-, -C(O)O-, -C(O)S-, -OC(O)O-, -N(R5)C(O)-, or -C(O)N(R5)-, any two or more of R7together may optionally form a ring; R5is H, deuterium, or substituted or unsubstituted C1-C6 alkyl. Any two or more of R1, R2, R3, and R4together may optionally form a ring, and at least one of R1, R2, R3, 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 with partial or full deuteration.

[0022] In addition to the ether linkages that are part of the first polymer backbone, there may be additional functional linkages present in pendent groups (side chains) that are covalently bonded to the polymer backbone. In an embodiment, these side chains may comprise only carbon-carbon linkages. In another embodiment, these side chains may comprise carbon-carbon linkages in addition to other functional linkages or functional groups, including but not limited to, ether, ester, amide, sulfonate, hydroxy, thiol, cyano, amine, thiol, aldehyde, carboxyl, alkyl halide, ketone, allyl, allenyl, norbornyl, ethynyl, acrylates, methacrylates, itaconates, maleimides, maleic anhydrides, carbonate, carbamate, and the like. In other words, the side chain may contain heteroatoms such as nitrogen, sulfur, oxygen, and the like. The side chain can be linear, branched, or may have one or more ring structures as linkages.

[0023] 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, R2, R3, and R4can comprise an acid-labile group, a base-labile group, a base-soluble group, or a base switchable group.

[0024] 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," "acid-leaving 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).

[0025] 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 post-exposure baking steps. Thebase-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.

[0026] Suitable base-soluble groups include, for example, hydroxyl, carboxyl, phenols, imides, or - NHS(O)2Y1groups, where Y1is substituted or unsubstituted C1-10alkyl.

[0027] The first repeat unit is formed from an oxirane monomer. For example, a first repeating unit of formula (1) is formed from an oxirane monomer of formula (2): and R4are as defined above with respect to formula (1).polymerized unit is typically present in the first polymer in an amount of from 40 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 polymer. In an embodiment, the first polymer is a homopolymer having the polymerized units of formula (1) in an amount of 100 mol% based on the total repeating units of the polymer. When the first polymer is a copolymer, the first polymerized unit may typically be present in an amount up to 99 mol%, more typically up to 95 mol% or up to 90 mol%.

[0029] Non-limiting examples of the first repeating unit include the following:The polymer can optionally include one or more additional and distinct repeat units from the first repeat unit. The polymer can, for example, include additional repeat units formed from a structurally different oxirane monomer than the first repeat unit and / or from a non-oxirane monomer. Suitable additional oxirane monomers include those described above with reference to the first repeating unit, 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, and amino acid N- carboxyanhydrides. Suitable additional repeat from heterocyclic monomers capable of ring-opening copolymerization with the above-described oxirane monomers include those of formulas (3a) and (3b): , -S(O)2-, or -Por C6-12heteroarylene; each R7independently represents H, deuterium, substituted or unsubstituted C1-20alkyl, substituted or unsubstituted C3-20 cycloalkyl, substituted or unsubstituted C2-20 alkenyl, substituted or unsubstituted C3-20 cycloalkenyl, substituted or unsubstituted C2-20 alkynyl, substituted or unsubstituted C3-20 cycloalkynyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C4-30 heteroaryl, optionally including one or more of -O-, -S-, -Si(R5)2-, -N(R5)-, -S(O)-, -S(O)2-, -C(O)-, -C(O)O-, -C(O)S-, -OC(O)O-, -N(R5)C(O)-, or -C(O)N(R5)-, any two or more of R7together may optionally form a ring; R5is H, deuterium, or substituted or unsubstituted C1-C6alkyl; 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 end functional group such as for example, a hydroxyl, a thiol, a cyano, an amine, or a sulfonate. Preferably, at least one R7is a substituted or unsubstituted C1-C6alkyl optionally containing a heteroatom chosen from O, S, N, or P. In an embodiment, the first polymer can be free of repeat units formed from unsubstituted oxirane monomers.

[0030] If present, the repeat units of formula (4) can be present in the first polymer in an amount of from 2 to 90 mol%, more typically from 5 to 50 mol%, and still more typically from 25 to 50 mol%, based on the total repeating units of the first polymer. Non-limiting examples of repeat units of formulae (4a) and (4b) include the following:.embodiment, the first polymer can be free of repeat units formed from substituted or unsubstituted oxetane monomers.

[0032] If present, the repeat units formed from such cyclic monomers can be present in the first polymer in an amount of from 2 to 90 mol%, more typically from 5 to 50 mol%, and still more typically from 25 to 50 mol%, based on the total repeating units of the first polymer. Non-limiting examples of repeat units include the following:O O OOO O an enol ethercan, for example, be of formula (5): wherein: R9each independently including as part of its structure oneor more groups chosen from -O-, -S-, - -, - -, - , or -C(O)N(R11)-, wherein R11represents hydrogen or substituted or unsubstituted C1-10 alkyl, and any two R9groups together optionally forming a ring; and R10represents a C1-10 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(R12)-, -C(O)-, -C(O)O-, or -C(O)N(R12)-, wherein R12represents -H or substituted or unsubstituted C1-10alkyl.

[0034] Suitable enol ether compounds include, for example, the following:

[0035] If present,present in the first polymer in an amount of from 2 to 90 mol%, more typically from 5 to 50 mol%, and still more typically from 25 to 50 mol%, based on the total repeating units of the first polymer. Suitable enol ether monomers are commercially available and / or can readily be made by persons skilled in the art.

[0036] Other suitable additional repeat units include, for example, one or more repeat units chosen from olefin sulfides, cyclic carbonates, and lactones.

[0037] The first polymer can further comprise one or more spacers in the polymer backbone between 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 (6) or may itself be of formula (6):4; and R13is each independently chosen from -H, deuterium, substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C3-20 cycloalkyl, substituted or unsubstituted C6-30aryl, substituted or unsubstituted C4-30heteroaryl, optionally including one or more of -O-, -S-, -N-, -S(O)-, -S(O)2-, -C(O)-, -C(O)O-, -OC(O)O-, -NC(O)-, -or -C(O)NR14-, wherein R14is H, deuterium, or substituted or unsubstituted C1-C6 alkyl. The aforementioned alkyl substituents 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 an ether, an ester, an amide, an imide, a urethane or a urea.

[0038] Suitable spacers include, for example, the following:n = anSuitable spacers are commercially available and / or can readily be made by persons skilled in the art.

[0039] The first polymer may contain one or more functional end groups. The functional end group can be, for example, one or more of -OR6, -N(R6)2, -COOH, -SO3, C6-30 aryl, or C4-30 heteroaryl, wherein R6is independently chosen from -H, deuterium, substituted or unsubstituted C1-20alkyl, substituted or unsubstituted C3-20cycloalkyl, substituted or unsubstituted C6-30aryl, or substituted or unsubstituted C4-30heteroaryl.

[0040] Non-limiting examples of the first polymer include homopolymers of the first repeat unit structures shown above, and the following copolymers:DI83813 DPN11136PCTa, c

[0041] The first polymer typically has a weight average molecular weight (Mw) of 500 to 50,000 Daltons, more typically from 5000 to 30,000 Daltons, or from 10,000 to 30,000 Daltons. The polydispersity index (PDI) of the first polymer, 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. The first polymer may be present in thecoating composition in an amount of from 0.001 to 50 wt%, 0.001 to 10 wt%, 0.001 to 2 wt%, based on total solids of the coating composition.

[0042] The polymers of the invention can be prepared by various methods. For example, the polymers can be made by polymerization of one or more oxirane monomers of the invention as described above, together with one or more optional comonomers and spacers as described above. The polymers can be prepared using any suitable method in the art, for example, free-radical polymerization, anionic polymerization, cationic polymerization, and the like. One or more monomers corresponding to the repeating units of the precursor polymer 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 polymer 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.

[0043] 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 above-described 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.

[0044] The coating compositions further include a solvent for dissolving the first 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, 1propanol, 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, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), hydroxyisobutyrate methyl ester (HBM) and ethyl acetoacetate; lactones such as gamma-butyrolactone (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 coating composition. The solids content of the coating composition is the non-solvent component of the composition. The desired solvent content 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.

[0045] The coating compositions comprises the surface leveling agent and the organic-based solvent, and may include one or more additional components depending on the application. 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. It may be desired that a plurality of such compositions include the surface leveling agents described herein. Such compositions and their components are known to those skilled in the art. Coating compositions of the invention 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.

[0046] The coating compositions can be prepared following known procedures. For example, the compositions can be prepared by dissolving the first 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.

[0047] Methods of forming semiconductor devices using the above-described compositions are described below. A substrate comprising a semiconductor material is provided and a coating composition as described herein that contains the first polymer derived from an oxirane monomer is applied to the substrate by spin-coating. Suitable substrates on which the above-described 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 orspin-on-carbon (SOC)), antireflective coating, and patterned or unpatterned 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 according to the present invention.

[0048] By way of illustration, a preferred coating composition comprising the first polymer is one or more lithography materials. Typically, the substrate will include one or more lithographic material layers such as a hardmask layer, for example, a spin-on-carbon (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.

[0049] 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).

[0050] The photoresist composition is coated on the substrate by spin-coating. The spin-coating 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 compositions of the invention can have 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.

[0051] 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 ingredients of the composition.

[0052] 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 sub400 nm, sub-300 nm or sub200 nm, with 248 nm (KrF laser), 193 nm (ArF laser) or 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.

[0053] Following exposure of the photoresist layer, a postexposure bake (PEB) 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 ºC, 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.

[0054] 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 the remaining 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.

[0055] Suitable developers for a PTD process include aqueous base developers, for example, quaternary ammonium hydroxide solutions such as tetramethylammonium hydroxide (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.

[0056] 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.

[0057] 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), spin-on-carbon (SOC), and hardmask compositions, or the developer composition may contain the first polymer.

[0058] In accordance with a further aspect of the invention, the coating composition containing the first polymer is a photoresist topcoat composition. Topcoat compositions can be used in immersion or non-immersion 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. Topcoat compositions typically include a surface-active polymer that is self- segregating from other polymers of the composition during the coating process. The first polymer 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 (non-immersion) exposure tool.

[0059] In accordance with a further aspect of the invention, the coating composition containing the first polymer 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 a thermal acid generator, and other optional components. A layer of the photoresist pattern trimming composition is formed over the photoresist pattern by spin-coating. The solids content of the coating solution can be adjusted to provide a desiredfilm thickness. A typical thickness for the pattern trimming composition layer is from 200 to 1500 Å. 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 of from 70 to160 ºC and a time of from about 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%) tetramethylammonium hydroxide (TMAH). The rinsing agent can further be or comprise water. The resist pattern after trimming treatment has a dimension (L2) that is smaller as compared with the feature size prior to trimming treatment.

[0060] The following non-limiting examples are illustrative of the invention. EXAMPLES SLA Polymer Synthesis

[0061] Example 1 6 mL Monomer M1 (2-butyloxirane) was mixed with 4.5 mL dioxane. Then, 1.10 mL potassium tert- butoxide (KtBuO) (1.0M in THF) was added to the reaction mixture. The mixture was heated to 95 °C for 20 hours and then cooled to < 50°C. The mixture was then quenched with ~0.1 mL 10M HCl (in H2O) and Na2SO4 was added to remove water. The resulting solution was diluted with methyl t-butyl ether and filtered with a 1.0-micron PTFE filter. The mixture was concentrated with a rotavap to provide a polymer. The polymer was diluted with heptane and filtered twice with a 0.2-micron PTFE filter resulting in Polymer SLA-1. Weight average and number average molecular weights (Mw and Mn, respectively) were determined by GPC calibrated with Polystyrene standards, and molar ratio of copolymers was determined by1H NMR analysis. Dispersity (Đ) of the polymer was calculated as Mw / Mn. The results are shown in Table 1.

[0062] Examples 2-12 Additional SLA polymers were prepared and characterized 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, molar ratio, and dispersity results are also shown in Table 1.TABLE 1 Example SLA Monomer / KtBuO Dioxane1(mL) (mL) Qu H NMR Mw Vol. (mL) encher Molar Ratio (Da) Đ M1 1 3 8 2 2 4 5 2 0 7 1 0 4Sample was treated by stirring with activated carbon in heptane before being concentrated and used for coating. Coating Composition Preparation Polymer A [Mw = 11k, Đ = 2.2]

[0063] An SLA polymer solution (1 wt% SLA-1 in PGMEA) was prepared in a 100 mL bottle by first charging 1 g of the polymer 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 machine-shaking overnight.12.775 g of the base polymer solution, 1.355 g of PGMEA, and 3.87 g of the SLA polymer 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 0.2µm PTFE disk filter into a clean 20 mL scintillation vial to form coating composition C3. Examples 14-37 Additional coating compositions (C2-C25) were prepared in a manner similar to that described in Example 13, using the materials and amounts set forth in Table 2.Coating Quality Evaluation

[0064] 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 µm. 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 Table 2. TABLE 2 SLA Polymer Example Coating Base Polymer PGMEA Coating Composition Solution (g) (g)SLAContent SLA Polymer QualitySLA Polymer Synthesismolar ratio, and dispersity results are also shown in Table 3. Q2 is activated charcoal. TABLE 3 Monome1Example SLA r / KtBuO Dioxane Quench H NMR Mw Vol. (mL) (mL) (mL) er Molar Ratio (Da) Đ 92 0649 59 7252Example 44

[0066] 2.09 g of Example 41 was mixed with 130 mg of 3-maleimidopropionic acid N- hydroxysuccinimide ester in 8 mL dioxane. The mixture was heated to 70°C for 16 hours and cooled to room temperature. The solvent was removed under vacuum and the mixture was redispersed in heptane. The mixture was filtered using a 0.2-micron PTFE filter and concentrated under vacuum to yield the product.1H-NMR mole ratio: 91:7:2. Mn = 10689 Da, Mw = 18141, Ð = 1.70.

[0067] 2.22 g of Example 40 was mixed with 83 mg of isopropanethiol in dioxane 4 mL with 42 mg of V601 initiator. The mixture was heated to 70°C for 16 hours. The mixture was concentrated under vacuum at 70°C to yield the product.1H-NMR mole ratio: 96:4. Mn = 13421 Da, Mw = 25671, Ð = 1.91.Example 46

[0068] 2.13 g of Example 40 was mixed with 77 mg of mercapto-acetic acid in dioxane (4 mL) with 31 mg of V601 initiator. The mixture was heated to 70°C for 16 hours. The mixture was concentrated under vacuum at 70°C to yield the product.1H-NMR mole ratio: 96:4. Mn = 13952 Da, Mw = 28431, Ð = 2.04.

[0069] 2.23 g of Example 40 was mixed with 66 mg of 3-mercapto-1-propanol in dioxane (4 mL) with 41 mg of V601 initiator. The mixture was heated to 70°C for 16 hours. The mixture was concentratedunder vacuum at 70°C to yield the product.1H-NMR mole ratio: 96:4. Mn = 12944 Da, Mw = 25986, Ð = 2.01.

[0070] 3.46 g of Example 40 was mixed with 166 mg of isopropanethiol in dioxane (5 mL) with 20 mg of V601 initiator. The mixture was heated to 70°C for 16 hours. The mixture was concentrated under vacuum at 70°C.1.16 g of the concentrated polymer was dissolved in 10 mL of dichloromethane, with 307 mg meta-chloroperoxybenzoic acid (77% in water). The mixture was stirred for 24 hours, before being diluted with heptane to 25 mL. The solution was washed with saturated aqueous Na2S2O3solution, 10 wt% aqueous K2CO3 solution, and deionized water. The organic layer was collected and concentrated to yield the product. The S-atom was partially oxidized, however, the oxidation state of which was not determined.1H-NMR mole ratio: 96:4. Mn = 9502 Da, Mw = 14396, Ð = 1.51.

[0071] 2.50 g of Example 40 was dissolved in 15 mL of dichloromethane, with 266 mg of meta- chloroperoxybenzoic acid (77% in water). The mixture was stirred for 24 hours, before being diluted with heptane to 25mL. The solution was washed with saturated aqueous Na2S2O3 solution, 10 wt% aqueous K2CO3solution, and deionized water. The organic layer was collected and concentrated to yield the product.1H-NMR mole ratio: 96:2:2. Mn = 11335 Da, Mw = 17960, Ð = 1.58.

[0073] Coating compositions (C26-C37) were prepared using the SLA polymers from Examples 38 to 49, respectively, following the same procedure to that described for Example 13, using the materials and amounts set forth in Table 4.

[0074] Coating Quality Evaluation

[0075] 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 µm. 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 Table 4. TABLE 4 SLA Polymer Example Coating Base Polymer PGMEA Coating Composition Solution (g) (g) SLA Content SLA Polymer Quality

Claims

WHAT IS CLAIMED IS:

1. A coating composition, comprising: a first polymer comprising a first repeat unit formed from an oxirane monomer comprising a substituent having 3 or more carbon atoms, wherein the oxirane monomer is free of CF2and CF3groups that are bonded to a carbon atom; a second polymer that is different from the first polymer; and a solvent.

2. The coating composition of claim 1, wherein the first repeat unit is of formula (1): wherein: independently -H, deuterium, substituted or unsubstituted C1-20 alkyl,substituted 20 cycloalkyl, substituted or unsubstituted C2-20 alkenyl, substituted or unsubstituted C3-20 cycloalkenyl, substituted or unsubstituted C2-20 alkynyl, substituted or unsubstituted C3-20 cycloalkynyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C4-30 heteroaryl, optionally including one or more of -O-, -S-, -Si(R5)2-, -N(R5)-, -S(O)-, -S(O)2-, -C(O)-, -C(O)O-, -C(O)S-, -OC(O)O-, -N(R5)C(O)-, or -C(O)N(R5)-, any two or more of R7together may optionally form a ring; R5is H, deuterium, or substituted or unsubstituted C1-C6alkyl; any two or more of R1, R2,R3, and R4together may optionally form a ring, and at least one of R1, R2, R3, and R4has 3 or more carbon atoms.

3. The coating composition of claim 2, wherein R1or R2is chosen from C3-10 alkyl optionally with one or more -O- groups.

4. The coating composition of claim 2 or 3, wherein one or more of R1, R2, R3, and R4comprise an acid-labile group, a base-labile group, or a base-soluble group.

5. The coating composition of any of claims 1 to 4, wherein the first polymer further comprises an end group chosen from one or more of -OR6, -N(R6)2, -COOH, -SO3(R6), C6-30 aryl, or C4-30 heteroaryl, wherein R6is independently chosen from -H, deuterium, substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C3-20cycloalkyl, substituted or unsubstituted C6-30aryl, or substituted or unsubstituted C4-30heteroaryl.

6. The coating composition of any of claims 1 to 5, wherein the first polymer further comprises a second repeat unit that is structurally different from the first repeat unit, wherein the second repeat unit is formed from a heterocyclic monomer.

7. The coating composition of any of claims 1 to 6, further comprising a photoacid generator.

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

9. The method of claim 8, wherein the substrate comprises a semiconductor wafer.

10. The method of claim 8 or 9, wherein the coating composition further comprises a second polymer that is different from the first polymer.

11. The method of any of claims 8 to 10, wherein the coating composition is a photoresist composition, the method further comprising: (c) patternwise exposing a layer of the photoresist composition to activating radiation; and (d) developing the exposed photoresist layer to provide a resist relief image.

12. The method of any of claims 8 to 10, wherein the coating composition is a photoresist underlayer composition, the method further comprising: (c) forming a photoresist layer over the underlayer; (d) patternwise exposing the photoresist layer to activating radiation; and (e) developing the exposed photoresist layer to provide a resist relief image.

13. The method of any of claims 8 to 10, wherein the substrate comprises a photoresist layer or a photoresist pattern on which the coating composition is directly applied.

14. The method of any of claims 8 to 10, wherein the coating composition is an imprint lithography composition, the method further comprising: (c) imprinting the coating composition with a template to form a pattern.

15. The method of any of claims 8 to 10, wherein the substrate is an electronic device substrate and the coating composition is a surfactant rinse solution or a developer.

16. The method of any of claims 8 to 10, wherein the coating composition is a gap-fill composition, wherein coating the composition fills a plurality of gaps on the substrate surface.

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