Polymers useful as surface spreading agents, methods for producing the same, and articles containing the same

Abstract

To provide a polymer useful as a surface leveling agent, a method for producing the same, and an article comprising the same.SOLUTION: Disclosed herein is a copolymer comprising first polymerized units of formula (1) [R1 is H or a C1-C6 alkyl group and R2 is a C3-C20 alkyl group that optionally includes one or more of -O-, -S-, -N-, -C(O)-, -C(O)O-, -N-C(O)-, and -C(O)-NR-] and second polymerized units of formula (2) [R3 is a substituted or unsubstituted C1-C6 alkyl group that optionally includes one or more of -O-, -N-, -S-, -C(O)-, and -C(O)O-, wherein the first polymerized units and the second polymerized units are chemically different, and the copolymer is free of fluorine.SELECTED DRAWING: None

Description

[Technical Field]

[0001] Polymers useful as surface spreading agents, methods for producing the same, and articles containing the same are disclosed herein. [Background technology]

[0002] Surface uniforming agents (SLAs) are used in compositions for producing thin films and coating solutions. Surface uniforming agents typically tend to migrate to free surfaces (surfaces in contact with air) and promote surface uniformity or smoothing. Surface uniforming agents generally contain polymers or oligomers with lower surface energy compared to other molecules in the solution, and this low surface energy selectively separates them to the free surface even at low solids content. This ability to migrate to the surface (i.e., molecular mobility) promotes flow and uniformity of the surface / interface layer, resulting in a flat, smooth surface / interface.

[0003] The most common surface levelers contain polysiloxanes, alkyl-modified acrylic polymers, polyesters, or fluorocarbons. Good surface levelers have properties such as excellent slipperiness, leveling, flowability, reduction of surface tension, dent prevention ability, fish-eye prevention ability, substrate wetting, tendency to prevent Bénard cell formation, and good bubble stability.

[0004] Surface uniformizers play a crucial role in various coating formulations, such as spin-on thin films that enable microlithography. The increasing need for higher resolution, aspect ratios, and lower defect lithographic patterns in patterned features necessitates strategies for developing novel materials for surface uniformizers.

[0005] There are numerous reasons why defects occur due to surface preparers. Some of these are listed below. Most surface preparers contain silicon or fluorine moieties and are highly hydrophobic. Unfortunately, the hydrophobic nature of these surface preparers is a major cause of defects in high-level photoresist patterning. These defects include not only surface defects but also other types such as residue precipitation, bridging defects, and defects that do not form a defined pattern.

[0006] Many lithography patterning processes use wet base developers. Insoluble species in these base developers leave insoluble residues, which can cause defects. Therefore, it is desirable that all exposed resist material be completely removable and that no insoluble residues, which may potentially form defects, are left behind.

[0007] To overcome this problem, surface smoothers are used in photoresist compositions in the smallest possible amount. Another way to use surface smoothers is to modify the agent to enable solubility by containing base-soluble units or functional groups that can be switched with a base. In other words, it is desirable to specially modify surface smoothers containing fluorine and / or silicon moieties for use in photoresist compositions.

[0008] Another issue with fluorine-containing surface conditioners is regulatory. Government regulations require fluorine-containing products to be used to the minimum extent possible.

[0009] Therefore, it is desirable to develop a surface spreading agent that can be used in compositions for lithography or coating applications, does not contain fluorocarbons, and provides good surface spreading properties without causing defects in the resulting article. [Overview of the project] [Means for solving the problem]

[0010] Formula (1): [ka] [In the formula, R1 is H or a substituted or unsubstituted C1-C6 alkyl group, and R2 is a substituted or unsubstituted C3-C6 alkyl group that optionally contains one or more of -O-, -S-, -N-, -C(O)-, or -C(O)O-, -NC(O)-, -C(O)-NR- (where R is H or a substituted or unsubstituted C1-C6 alkyl group)] 20 The first polymerization unit is an alkyl group, Formula (2): [ka] A copolymer comprising a second polymerization unit [wherein R3 is a substituted or unsubstituted C1-C6 alkyl group optionally containing one or more of -O-, -N-, -S-, -C(O)-, or -C(O)O-], wherein the first polymerization unit and the second polymerization unit are chemically distinct, and which is fluorine-free, is disclosed herein. [Modes for carrying out the invention]

[0011] As used herein, the terms “a,” “an,” and “it” do not imply a limitation of quantity and should be interpreted as encompassing both singular and plural forms unless otherwise specifically indicated herein or the context clearly contradicts this interpretation. “Or” means “and / or” unless otherwise specified.

[0012] As used herein, “acid-unstable group” refers to a group whose bond is optionally cleaved by the catalytic action of an acid, typically by heat treatment, resulting in a polar group such as a carboxylic acid or alcohol group being formed on the polymer, where the site connected to the optionally cleaved bond is detached from the polymer. Such acids are typically photogenerated acids, in which the bond is cleaved during baking after exposure. Suitable acid-unstable 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-unstable groups are also commonly referred to in the art as “acid-cleavable groups,” “acid-cleavable protecting groups,” “acid-unstable protecting groups,” “acid-eliminating groups,” “acid-unstable groups,” and “acid-sensitive groups.”

[0013] "Substitution" means that at least one hydrogen atom in a group is replaced by another atom or group, provided that the valence does not exceed the normal valence of the specified atom. When the substituent is oxo (i.e., =O), two hydrogens on the carbon atom are replaced. Combinations of substituents or variables are permitted. Exemplary groups that may be present in the "substituted" position are nitro (-NO2), cyano (-CN), hydroxy (-OH), oxo (=O), amino (-NH2), mono- or di-(C) 1~6 ) Alkylamino, alkanoyl (acyl, etc.) 2~6 Alkanoyl groups, for example, formyl (-C(=O)H), carboxylic acids or alkali metal or ammonium salts thereof, C 2~6 Alkyl esters (-C(=O)O-alkyl or -OC(=O)-alkyl) and C 7~13 Esters such as aryl esters (-C(=O)O-aryl or -OC(=O)-aryl) (including acrylates, methacrylates, and lactones), amides (-C(=O)NR2 (where R is hydrogen or C) 1~6 Alkyl)), carboxamide (-CH2C(=O)NR2(R is hydrogen or C) 1~6 Alkyl, halogen, thiol (-SH), C 1~6Alkylthio (-S-alkyl), thiocyano (-SCN), C 1~6 Alkyl, C 2~6 Alkenyl, C 2~6 Alkynyl, C 1~6 Haloalkyl, C 1~9 Alkoxy, C 1~6 Haloalkoxy, C 3~12 Cycloalkyl, C 5~18 Cycloalkenyl, C having at least one aromatic ring (e.g., phenyl, biphenyl, naphthyl, etc., each ring being a substituted or unsubstituted aromatic) 6~12 Aryl, C having 1 to 3 separated or fused rings and 6 to 18 ring carbon atoms 7~19 Arylalkyl, arylalkoxy having 1 to 3 separated or fused rings and 6 to 18 ring carbon atoms, C 7~12 Alkylaryl, C 4~12 Heterocycloalkyl, C 3~12 Heteroaryl, C 1~6 Alkylsulfonyl (-S(=O)2-alkyl), C 6~12 Arylsulfonyl (-S(=O)2-aryl) or tosyl (CH3C6H4SO2-), including but not limited to these. When the group is substituted, the indicated number of carbon atoms is the total number of carbon atoms in the group excluding the carbon atoms of any substituents.. For example, the group -CH2CH2CN is a C2 alkyl group substituted with a cyano group.

[0014] As used herein, “(meth)acrylate” represents “at least one of acrylate and methacrylate”. Further, “(meth)acrylic acid” means “at least one of acrylic acid and methacrylic acid”.

[0015] As used herein, the term "alkyl" means a branched or straight-chain saturated aliphatic hydrocarbon group having a specified number of carbon atoms, generally 1 to about 12 carbon atoms. The term C1-C6 alkyl as used herein refers to an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms. Other embodiments include alkyl groups having 1 to 8 carbon atoms, 1 to 4 carbon atoms, or 1 or 2 carbon atoms, such as C1-C6 alkyl, C1-C4 alkyl, and C1-C2 alkyl. C0-C n When alkyl is used herein in combination with another group, e.g., (cycloalkyl)C0-C4 alkyl, the indicated group, in this case cycloalkyl, is either directly attached by a single covalent bond (C0) or attached by an alkyl chain having a specified number of carbon atoms, in this case 1, 2, 3, or 4 carbon atoms. Examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, 3-methylbutyl, t-butyl, n-pentyl, and sec-pentyl.

[0016] As used herein, the term "cycloalkyl" refers to a saturated hydrocarbon ring group having only carbon ring atoms and a specified number of carbon atoms, usually 3 to about 8 ring carbon atoms, or 3 to about 7 carbon atoms. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl, as well as bridged or caged saturated ring groups such as norbornane or adamantane.

[0017] As used herein, the term "heterocycloalkyl" refers to a saturated cyclic group containing 1 to about 3 heteroatoms selected from N, O, and S, with the remaining ring atoms being carbon. The heterocycloalkyl group has 3 to about 8 ring atoms, more typically 5 to 7 ring atoms. Examples of heterocycloalkyl groups include morpholinyl, piperazinyl, piperidinyl, and pyrrolidinyl groups. The nitrogen in the heterocycloalkyl group can optionally be quaternized.

[0018] In this specification, when groups and atomic groups are cited without specifying whether they are substituted or unsubstituted, the group includes both unsubstituted and substituted groups and atomic groups. For example, "alkyl group" without specifying whether it is substituted or unsubstituted includes not only unsubstituted alkyl groups but also substituted alkyl groups.

[0019] This specification discloses a surface spreader used in surface activation applications, particularly in lithography compositions for producing spin-on thin films. The surface spreader comprises a copolymer of two or more polymer units having ether links in the chain backbone. These two or more polymer units are fluorine-free. In an optional embodiment, the polymer does not contain silicon-containing surface energy reduction moieties. While the aforementioned ether links are part of the polymer's main chain, additional functional links may be present in pendant groups (side chains) covalently bonded to the copolymer's main chain. In an embodiment, these side chains may contain only carbon-carbon bonds. In another embodiment, these side chains may contain carbon-carbon bonds in addition to other functional links or functional groups such as ethers, esters, amides, sulfonates, hydroxy, thiols, cyanos, amines, thiols, aldehydes, carboxyls, alkyl halides, ketones, allyls, allenyls, norbornyls, ethynyls, acrylates, methacrylates, itaconates, maleimides, and maleic anhydride, but are not limited to these. In other words, the side chain can contain heteroatoms such as nitrogen, sulfur, and oxygen.

[0020] Surface uniforming agents can be used not only in compositions for lithography applications, but also in other applications where good surface uniformity and glossy appearance are desirable, such as coatings, paints, inks, plating solutions, medical applications, corrosion resistance, and lubrication technologies.

[0021] In a typical embodiment, at least one polymer unit of the copolymer is a polyoxetane (hereinafter referred to as polyalkyloxetane) having at least one alkyl substituent along the chain backbone. The polyoxetane backbone imparts hydrophilicity to the surface spreader copolymer, promoting miscibility with bases and water, while the alkyl side chains impart hydrophobicity, moving the surface spreader to the interface of a thin film or coating. The interface may be between a spin-on layer and air, or alternatively, between two layers of a multilayer film. In embodiments, the polyalkyloxetane is present in the copolymer in an amount greater than 40 mole percent (mol%).

[0022] In embodiments, the polyoxetane copolymer may contain one or more terminal functional groups. The terminal functional groups may include hydroxyl, thiol, cyano, amine, or sulfonate.

[0023] The aforementioned alkyl substituents may be linear, branched, or optionally contain other atoms such as O, S, N, P, or other functional links such as ethers, esters, amides, imides, urethanes, or ureas. Furthermore, the alkyl substituents may optionally contain terminal functional groups such as hydroxyl, thiol, cyano, amine, or sulfonate.

[0024] Surface leveling agents may be hydrophobic for specific applications, but may also be sufficiently hydrophilic to be miscible with water or wet developers in other applications. The absence of fluorine or silicon-containing components in the surface leveling agent minimizes defect formation. The absence of fluorine-containing components also ensures compliance with environmental regulations.

[0025] The surface spreading agent is preferably a copolymer containing two or more different repeating units. In embodiments, the surface spreading agent may be a copolymer containing three or more different repeating units. The copolymer may be a random copolymer, an alternating copolymer, a block copolymer, a star-shaped block copolymer, a superbranched polymer, a comb copolymer, a dendrimer, a gradient copolymer, etc., but a random copolymer or a block copolymer is preferred. A combination of a random copolymer and a block copolymer can also be used in the surface spreading agent.

[0026] In this embodiment, the copolymer is of formula (1): [ka] [In the formula, R1 is H or a substituted or unsubstituted C1-C6 alkyl group, and R2 is a substituted or unsubstituted C3-C6 alkyl group that optionally contains one or more of -O-, -S-, -N-, -C(O)-, or -C(O)O-, -NC(O)-, -C(O)-NR- (where R is H or a substituted or unsubstituted C1-C6 alkyl group)] 20 The first polymerization unit is an alkyl group, and formula (2): [ka] The copolymer includes a second polymerization unit [wherein R3 is a substituted or unsubstituted C1-C6 alkyl group optionally containing one or more of -O-, -N-, -S-, -C(O)-, or -C(O)O-], wherein the first polymerization unit and the second polymerization unit are chemically distinct, and the copolymer does not contain fluorine. In a preferred embodiment, R3 is an unsubstituted C1-C5 alkyl group.

[0027] When R3 is substituted, the substituent chain has two or fewer carbon atoms. The hydrophilic polymer unit of formula (2) can provide the advantage of miscibility between surfactants and water or wet base developers.

[0028] In one embodiment, R2 has a branched structure. In another embodiment, R2 has two or more branches.

[0029] In the embodiment, the surface spreading agent comprises polymerization units of formula (1), polymerization units of formula (2), and further polymerization units of formula (3). [ka] [In the formula, R4 is a substituted or unsubstituted C2-C4 alkyl group that optionally contains one or more of -O-, -S-, -N-, -C(O)-, or -C(O)O-, -NC(O)-, -C(O)-NR- (wherein R is H or a substituted or unsubstituted C1-C6 alkyl group)].

[0030] As a specific example of the embodiments described above, the first polymerization unit is represented by formula (1-1), the second polymerization unit is represented by formula (2-1), and the third polymerization unit is represented by formula (4): [ka] (In the formula, R4 is a substituted or unsubstituted C3-C that optionally contains one or more of -O-, -S-, -N-, -C(O)-, or -C(O)O-) 20 (It is an alkyl group.) [ka] It is represented as follows.

[0031] Examples of precursors of the polymerization unit of formula (1) include 3-methyloxetane, 3-ethyloxetane, 3-propyloxetane, 3-butyloxetane, 3-neopentyloxetane, 3-pentyloxetane, 3-hexyloxetane, 3-(2,2-dimethylbutyl)oxetane, 3-methoxymethyloxetane, 3-ethoxymethyloxetane, 3-propoxymethyloxetane, 3-butoxymethyloxetane, 3-neopentoxymethyloxetane, 3-pentoxymethyloxetane, 3-hexoxymethyloxetane, 3-(2,2-dimethylbutoxy)oxetane, 3-methoxyethyloxetane, 3-ethoxyethyloxetane, 3-propoxyethyloxetane, 3-butoxyethyloxetane, 3-neopentoxyethyloxetane, 3-pent This includes oxyethyl oxetane, 3-hexoxyethyl oxetane, 3-butyloxymethyl-3-methyl oxetane, 3-butyloxymethyl-3-ethyl oxetane, 3-butyloxymethyl-3-propyl oxetane, 3-butyloxymethyl-3-butyl oxetane, 3-butyloxymethyl-3-pentyl oxetane, 3-butyloxymethyl-3-neopentyl oxetane, 3-butyloxymethyl-3-hexyl oxetane, 3,3-dimethyl oxetane, 3-ethyl-3-[(2-ethylhexyloxy)methyl]oxetane, 3-ethyl-3-hydroxymethyl oxetane, 3-ethyl-3-hydroxymethyl oxetane, 3-methyl-3-oxetane methanol, 3-(1-methylethyl)-oxetane, or combinations thereof.

[0032] Examples of precursors for the polymerization unit of formula (2) include formaldehyde, ethylene oxide, propylene oxide, tetrahydrofuran, 1,4-dioxane, or combinations thereof.

[0033] Examples of precursors for the polymerization unit of formula (3) include 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, or combinations thereof.

[0034] A preferred precursor for the polymerization unit of formula (1) is 3-butyloxymethyl-3-methyloxetane, and a preferred precursor for the polymerization unit of formula (2) is tetrahydrofuran. A preferred precursor for the polymerization unit of formula (3) is 2,2-dimethyl-1,3-propanediol.

[0035] The surface spreading agent may have a weight-average molecular weight of 500 to 30,000 grams per mole (g / mol), preferably 800 to 12,000 g / mol, and more preferably 1,000 to 10,000 g / mol.

[0036] The polymerization units of formula (1) are typically present in the copolymer in an amount of more than 40 mol%, preferably more than 50 mol%, and more preferably more than 60 mol%, based on the total number of moles in the copolymer. The polymerization units of formula (1) are present in the copolymer in an amount of less than 80 mol%, preferably less than 75 mol%, and more preferably more than 70 mol%, based on the total number of moles in the copolymer.

[0037] In the embodiment, the polymerization unit of formula (2) is present in the copolymer in an amount of more than 20 mol%, preferably more than 25 mol%, and more preferably more than 70 mol%, based on the total number of moles in the copolymer. In the embodiment, the polymerization unit of formula (2) is present in the copolymer in an amount of less than 60 mol%, preferably less than 50 mol%, and more preferably less than 40 mol%, based on the total number of moles in the copolymer.

[0038] In the embodiment, the polymerization unit of formula (3) is present in the copolymer in an amount of 0.01 mol% or more, preferably 1 mol% or more, and more preferably 2 mol% or more, based on the total number of moles in the copolymer. In the embodiment, the polymerization unit of formula (3) is present in the copolymer in an amount of 20 mol% or less, preferably 15 mol% or less, and more preferably 10 mol% or less, based on the total number of moles in the copolymer.

[0039] Surface smoothing agents can be used in a variety of different compositions. In one embodiment, a surface smoothing agent can be used in a solvent or solvent mixture alone, acting as a rinse formulation. In another embodiment, a surface smoothing agent can be used in a composition comprising a matrix polymer, a solvent, and other optional additives.

[0040] In embodiments, a surface smoothing agent can be used in a photoresist composition containing a polymer matrix resin, an optional deactivator, one or more photoacid generators, an optional additive, and a solvent. The matrix polymer is preferably a copolymer containing at least one repeating unit containing an acid-unstable group and / or a crosslinkable functional group. When used, the surface smoothing agent is present in an amount of 0.001 to 100% by weight, more preferably 0.001 to 1% by weight, based on the total solids content of the composition.

[0041] In another embodiment, the surface smoothing agent can be used in a photoresist composition that, in addition to the surface smoothing agent, contains a matrix polymer, a photoacid generator, an optional deactivator, a solvent, and other optional additives.

[0042] In another embodiment, the surface smoother can be used in a composition containing, in addition to the surface smoother, a matrix polymer, at least one thermally activated acid generator, and a solvent. Other optional additives, such as crosslinking agents, can be added to the composition, but are not limited to these. Examples of compositions containing thermally activated acid generators may include anti-reflective coating compositions, topcoats, photoresist trimming or pattern-enhancing compositions, and other undercoat compositions.

[0043] The polymer matrix used in the aforementioned compositions may include a thermoplastic polymer, a blend of thermoplastic polymers, a thermosetting polymer, or a blend of a thermoplastic polymer and a thermosetting polymer. The polymer matrix may also include a blend of polymers, copolymers, terpolymers, or at least one combination of the aforementioned polymers. Furthermore, the polymer matrix may include oligomers, homopolymers, copolymers, block copolymers, alternating copolymers, random polymers, random copolymers, random block copolymers, gradient copolymers, graft copolymers, star-shaped block copolymers, dendrimers, polyelectrolytes (polymers containing electrolytes and having several repeating groups), polyamphoteric electrolytes (polyelectrolytes having both cationic and anionic repeating groups), ionomers, or combinations thereof. Copolymers may be available as solute molecules in the form of microparticles, or as nanoparticle dispersions or suspensions in a solvent or solvent mixture.

[0044] Examples of thermoplastic polymers include polyacetal, polydiene, polyacrylic, polycarbonate, polyalkyd, polystyrene, polyolefin, polyester, polyamide, polyaramid, polyamideimide, polyarylate, polyurethane, epoxy, phenols, silicone, polyarylsulfone, polyethersulfone, polyphenylene sulfide, polysulfone, polyimide, polyetherimide, polytetrafluoroethylene, polyetherketone, polyetheretherketone, polyetherketoneketone, polybenzoxazole, polyoxadiazole, polybenzothiadinophenothiazine, polybenzothiazole, polypyradinoquinoxaline, polypyromelillimide, polyquinoxaline, This includes polybenzimidazole, polyoxyndol, polyoxoisoindoline, polydioxoisoindoline, polytriazine, polypyridazine, polypiperazine, polypyridine, polypiperidine, polytriazole, polypyrazole, polycarborane, polyoxabicyclononane, polydibenzofuran, polyphthalide, polyacetal, polyacid anhydride, polyvinyl ether, polyvinyl thioether, polyvinyl alcohol, polyvinyl ketone, polyvinyl halogenate, polyvinyl nitrile, polyvinyl ester, polysulfate, polysulfide, polythioester, polysulfone, polysulfonamide, polyurea, polyphosphazene, polysilazane, polysiloxane, etc., or combinations thereof.

[0045] Examples of thermosetting polymers include epoxy polymers, unsaturated polyester polymers, polyimide polymers, bismaleimide polymers, bismaleimide triazine polymers, cyanate ester polymers, vinyl polymers, benzoxazine polymers, benzocyclobutene polymers, acrylic resins, alkyds, phenol-formaldehyde polymers, novolac, resol, melamine-formaldehyde polymers, urea-formaldehyde polymers, hydroxymethylfuran, isocyanates, diallyl phthalates, triallyl cyanurates, triallyl isocyanurates, unsaturated polyesterimides, or combinations thereof. The composition may contain a crosslinking agent to promote the formation of the thermosetting polymer. The crosslinking agent may be self-crosslinking, acid or base-activated crosslinking agent, free radical crosslinking agent, or combination thereof.

[0046] 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, isopropanol, tert-butanol, 2-methyl-2-butanol and 4-methyl-2-pentanol, ethers such as propylene glycol monomethyl ether (PGME), diethyl ether, tetrahydrofuran, 1,4-dioxane and anisole, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone and cyclohexanone (CHO), and ethyl acetate. The solvents include esters such as n-butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), methyl hydroxyisobutyrate (HBM), and ethyl acetoacetate; lactones such as γ-butyrolactone (GBL) and ε-caprolactone; lactams such as N-methylpyrrolidone; nitriles such as acetonitrile and propionitrile; cyclic or acyclic 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 dimethylformamide; water; and combinations thereof. Of these, preferred solvents are PGME, PGMEA, EL, GBL, HBM, CHO, and combinations thereof. The total solvent content in the composition (i.e., the cumulative solvent content of all solvents) is typically 40–99% by weight, for example, 70–99% or 85–99% by weight, based on the total weight of the photoresist composition. The desired solvent content depends, for example, on the desired thickness of the coated photoresist layer and the coating conditions.

[0047] The composition is first prepared by mixing a matrix polymer, a surface spreader, and any other solid components and optional additives with a solvent. The composition may be subjected to additional processes such as filtration and ion exchange before use. The composition can be applied to a substrate by spin coating, dipping, roller coating, or other coating methods. The substrate may include electronic device substrates, metals, wood, paper, polymer substrates, or base layers. By varying the solid content of the coating solution, films of variable thickness can be provided. The solid content may also depend on the specific coating equipment used, the viscosity of the solution, the speed of the coating tool, and the amount of time used for rotation. In some embodiments, layers of the composition can be applied in a single coat. In other embodiments, layers of the composition can be applied in multiple coats.

[0048] Depending on the specific coating composition, it may be beneficial to soft-bake the layer of composition (placed on the substrate) to minimize the solvent content in the film. Soft-baking promotes the formation of a non-stick coating and improves the adhesion of the composition layer to the substrate. Soft-baking can be performed on a hot plate or in an oven, or alternatively, using ultraviolet light or a laser.

[0049] In the case of a photoresist composition, the layer is then exposed according to a pattern created by direct drawing, contact, or optical interference, enabling irradiation through a photomask and creating a difference in solubility between the exposed and unexposed areas. This irradiation forms a latent image in the layer. The photomask has optically transparent and optically opaque areas corresponding to the areas of the composition layer that are exposed or unexposed by the activating radiation.

[0050] The layers of the composition may optionally undergo a post-exposure bake process to subsequently develop and provide a resist relief image. In embodiments, exposed portions of the layers of the composition are removed using an alkaline developer. Examples of alkaline developers include aqueous solutions of tetramethylammonium hydroxide, sodium hydroxide, and potassium hydroxide. The exposed portions may form patterns such as holes (e.g., contact, via, or bump patterns) or grooves (e.g., line-space patterns).

[0051] In one embodiment, the surface uniforming agent is advantageous because it is miscible with water and wet developers. In another embodiment, the surface uniforming agent exhibits an appropriate level of hydrophobicity and is not miscible with water and wet developers, which makes the surface uniforming agent miscible with organic solvent developers. It does not contain fluorine and is therefore environmentally friendly.

[0052] Surface leveling agents can be used as wetting agents to improve flow control. These properties (surface leveling and wetting ability) provide good optical properties (e.g., high gloss and sufficient image clarity) to the coating. Therefore, surface leveling agents can be blended with a wide variety of solutions, waxes, polishes, coatings, blends, etc. In embodiments, surface leveling agents can be used in floor polishing formulations, paints, powder coating compositions, etc.

[0053] The present invention is illustrated by the following non-limiting embodiments. [Examples]

[0054] Example 1 This hypothetical example is carried out to demonstrate the synthesis of monomer repeating units used in copolymers (surface spreaders). The copolymer is prepared using 3-butyloxymethyl-3-methyloxetane and tetrahydrofuran and other monomers as one of the monomers. In other words, 3-butyloxymethyl-3-methyloxetane is used to prepare the first polymer unit of the copolymer, and tetrahydrofuran is used to prepare the second polymer unit of the copolymer. The synthesis of the 3-butyloxymethyl-3-methyloxetane monomer is carried out as follows: [ka]

[0055] A dispersion of 50 wt percent (2.8 g, 58.3 mmol) sodium hydride in mineral oil is washed twice with hexane and suspended in 35 ml of dimethylformamide. Next, 3.9 g (52.6 mmol) of butanol is added to the dispersion and the mixture is stirred for 45 minutes. A solution of 10.0 g (39 mmol) of 3-hydroxymethyl-3-methyloxetane p-toluenesulfonate in 15 ml of dimethylformamide is added and the mixture is heated at 80°C for 20 hours, during which ¹H-NMR analysis of aliquot samples shows that the starting sulfonate is completely consumed.

[0056] Next, the mixture is poured into 100 ml of ice water and extracted with 2 volumes of methylene chloride. The combined organic extract is washed twice with water, twice with a 2 wt percent aqueous hydrochloric acid solution and brine, dried over magnesium sulfate, and evaporated to produce 3-(2,2,2-trifluoroethoxymethyl)-3-methyloxetane as an oil containing less than 1 wt percent dimethylformamide. The oil is distilled under reduced pressure and analyzed to yield high-purity 3-butyloxymethyl-3-methyloxetane monomer.

[0057] The synthesis of (3-methyloxetan-3-yl)methyl 3,3-dimethylbutanoate monomer is carried out as follows. [ka] In a 100 mL four-neck flask, 10.0 g of 3,3-dimethylbutanoic anhydride (46.7 mmol) and 0.6 g of dimethylaminopyridine (4.7 mmol) are dissolved in 250 mL of dichloromethane. 6.0 g of 3-ethyl-3-hydroxymethyloxetane (51.4 mmol) is slowly added in an ice bath, and the reaction mixture is stirred at room temperature for 24 hours. Next, the reaction mixture is washed with saturated sodium bicarbonate aqueous solution, water, and brine, and then dried overnight over magnesium sulfate. After removing the solvent, the oil is distilled under reduced pressure, and analysis yields high-purity (3-ethyloxetane-3-yl)methyl 3,3-dimethylbutanoate.

[0058] Example 2 This hypothetical example is carried out to demonstrate the synthesis of polymers used as surface spreaders. The method for preparing copolymers using functionalized oxetanes and tetrahydrofurans is described in detail below.

[0059] In a 400 ml flask (equipped with a condenser, thermocouple temperature probe, and mechanical stirrer), add 100 ml of anhydrous methylene chloride and 2.03 g (22.6 mmol) of 1,4-butanediol. Next, add 29.6 g (211.7 mol) of BF3THF and 22.1 g (211.7 mmol) of 2,2-dimethyl-l,3-propanediol, and stir the mixture for 10 minutes. Next, pump a solution of 67 g (423.4 mol) of 3-butyloxymethyl-3-methyloxetane in 30 ml of anhydrous methylene chloride into the container over 5 hours. Maintain the reaction temperature between 38 and 42°C throughout the addition. Next, reflux the mixture (while stirring simultaneously) for a further 2 hours, and then... 1 ¹H-NMR showed >98% conversion. The reaction was quenched with 200 ml of 10% sodium bicarbonate aqueous solution, and the organic phase was washed with 200 ml of 3% HCl aqueous solution and 200 ml of water. The organic phase was dried over sodium sulfate, filtered, and removed from the solvent under reduced pressure to obtain (3-methyloxetan-3-yl)methyl 3,3-dimethylbutanoate monomer as a clear oil.

[0060] Example 3 This hypothetical example is performed to determine the resist coating and developing properties of the resist compositions. Formulations R1-R4 (resist compositions) and CR1-CR2 (comparative resist compositions) are prepared with the components and quantities shown in Table 1. In Table 1, the numbers in parentheses indicate the weight ratio of each component. The structures represented by C1-2, D1-2, and S1-2 are shown below in Table 2. Note that all polymers in Table 1 are prepared according to this general synthesis protocol. [ka]

[0061] [Table 1]

[0062] [Table 2]

[0063] The structures of the additives (C1, C2, D1, and D2) and solvents (S1 and S2) are shown immediately below. [ka]

[0064] Polymers A1 and A2 have a weight-average molecular weight of 8000 g / mol. E1 is as described in Synthesis Example 2. polymer That is the case.

[0065] E2 is PolyFox PF-656, which is a commercial material manufactured by Omnova Solution Incorporation. [ka]

[0066] Each formulation was prepared using the components shown in Table 2, mixed together overnight (by stirring), then passed through a 0.2 micrometer filter, and spin-coated onto a wafer. The wafer was then exposed to a 65 nm / 130 nm pitch line / space pattern under an ASML1100 scanner, increasing the focus with increasing dose, followed by post-exposure baking (PEB) at 100°C for 60 seconds. After PEB, the wafer was developed in 0.26 N TMAH wet developer for 12 seconds, rinsed with distilled water, and tumble-dried.

[0067] The evaluation of coating defects is performed on a spin-coated wafer of the above composition. After spin-coating the composition onto a hexamethyldisilazane (HDMS) primer-treated silicon wafer, measurements are performed using Hitachi CG4000 CD-SEM and SP2 tool evaluation. The total number of defects and the haze value are measured for comparison.

[0068] To evaluate patterning defects, immersion lithography was performed using a TEL Lithius 300mm wafer track and an ASML 1900i immersion scanner with 1.3 NA (numerical aperture), 0.86 / 0.61 internal / external sigma, and 35Y polarized dipole illumination. Wafers for photolithography testing were coated with an 800 Å AR40A undercoat anti-reflective coating (BARC) and cured at 205°C for 60 seconds. A 400 Å AR104 BARC was coated across the AR40A layer using a curing at 175°C / 60 seconds. A 900 Å photoresist was coated across the BARC stack using a soft bake at 90°C / 60 seconds. The wafers were exposed to a 55 nm / 110 nm pitch line / space pattern by increasing the focus and dose, and then post-exposure baked (PEB) at 100°C / 60 seconds. Following PEB, the wafers were developed with 0.26N TMAH wet developer for 12 seconds, rinsed with distilled water, and tumble-dried. Next, measurements were taken using a Hitachi CG4000 CD-SEM, and the number of defects was calculated for comparison.

[0069] It is expected that by advantageously using the surface uniforming agent described in the present invention, a photoresist composition free from numerous coating and patterning defects can be manufactured.

Claims

1. Formula (1): 【Chemistry 1】 [In the formula, R １ Is H or is C substituted or unsubstituted? １ ~C ６ It is an alkyl group, and R ２ However, -O-, -S-, -N-, -C(O)-, or -C(O)O-, -N-C(O)-, -C(O)-NR- (where R is H or substituted or unsubstituted C) １ ~C ６ A substituted or unsubstituted C molecule containing one or more alkyl groups (which are alkyl groups) in an optional manner. ３ ~C ２０ The first polymerization unit is an alkyl group, Formula (2): 【Chemistry 2】 [wherein, R ３ is a substituted or unsubstituted C １ -C ６ alkyl group optionally containing one or more of -O-, -N-, -S-, -C(O)-, or -C(O)O-] and a second polymer unit, and is a copolymer The first polymerization unit and the second polymerization unit are chemically different, The first polymerization unit of formula (1) is a fluorine-free copolymer present in the copolymer in an amount exceeding 60 mol%, based on the total number of moles in the copolymer.

2. R ２ The copolymer according to claim 1, wherein the copolymer has a branched structure.

3. Formula (3): 【Transformation 3】 [In the formula, R ４ However, -O-, -S-, -N-, -C(O)-, or -C(O)O-, -N-C(O)-, or -C(O)-NR-(where R is H or substituted or unsubstituted C) １ ~C ６ The copolymer according to claim 1, further comprising a third polymerization unit [which is a C2-C4 alkyl group that can be optionally substituted with one or more alkyl groups].

4. The copolymer according to claim 3, wherein the first polymerization unit is represented by formula (1-1) and the second polymerization unit is represented by formula (2-1), wherein formula (4): 【Chemistry 4】 (In the formula, R ４ However, substituted or unsubstituted C contains one or more of the following elements: -O-, -S-, -N-, -C(O)-, or -C(O)O-. ３ ~C ２０ (It is an alkyl group.) 【Transformation 5】 A copolymer further comprising a third polymerization unit.

5. A composition comprising the copolymer according to any one of claims 1 to 4 and a solvent.

6. A composition comprising a copolymer and a matrix polymer according to any one of claims 1 to 5.

7. The composition according to claim 6, further comprising a photoacid generator, wherein the matrix polymer comprises an acid-degradable group.

8. The composition according to claim 6, further comprising a thermal acid generator.

9. The composition according to claim 6, further comprising a crosslinking agent.

10. A coating method comprising the step of applying a layer of the composition according to any one of claims 5 to 9 onto a substrate.

11. A step of placing a layer of the composition according to any one of claims 5 to 7 on a substrate, A step of exposing the layer of the composition to activating radiation, A pattern forming method comprising the steps of developing a layer of the composition to provide a resist relief image.

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