Photoresist topcoat compositions and pattern formation methods

Abstract

A topcoat composition comprising a polymer including repeating units of monomers derived from one or more of formula (1); and a solvent, wherein Z1, Z2, R1, R2, and L-systems are as described herein, and P-system polymerizable groups.

Description

Technical Field

[0001] This invention relates to a photoresist topcoat composition that can be applied onto a photoresist composition. This invention is particularly suitable for forming topcoat layers in immersion lithography processes for semiconductor devices. Prior Technology

[0002] Photoresist materials are typically used to transfer images onto one or more underlying layers disposed on a semiconductor substrate, such as a metal, semiconductor, or dielectric layer. To increase the integration density of semiconductor devices and allow the formation of structures with dimensions in the nanometer range, photoresists and photolithography tools with high resolution capabilities have been and continue to be developed.

[0003] One approach to achieving nanometer (nm) level feature sizes in semiconductor devices involves using short-wavelength light (e.g., 193 nm or shorter) during photoresist exposure. To further improve lithography performance, immersion lithography tools (e.g., scanners with KrF (248 nm) or ArF (193 nm) light sources) have been developed to effectively increase the numerical aperture (NA) of the imaging device's lens. This is achieved by using a high-refractive-index fluid (typically water) between the rear surface of the imaging device and the top surface of the semiconductor wafer. ArF immersion tools are currently pushing the boundaries of lithography to dimensions below 40 nm by using multiple (secondary or higher-level) patterning.

[0004] In immersion lithography, direct contact between the immersion fluid and the photoresist layer can cause components to leach from the photoresist into the immersion fluid. This leaching can contaminate optical lenses and alter the effective refractive index and transmission characteristics of the immersion fluid. To address the problem of suppressing photoresist material migration into the immersion fluid, a photoresist topcoat layer has been introduced as a barrier layer between the immersion fluid and the underlying photoresist layer. Preferably, the topcoat layer is insoluble in the immersion liquid, transparent to the exposure wavelength, and does not mix with the photoresist layer. Furthermore, it is preferable that the topcoat layer is readily soluble in an alkaline developer, allowing both the topcoat layer and the photoresist layer to be removed simultaneously.

[0005] Typically, improved hydrophobicity of the immersion fluid interface is achieved through the use of fluoropolymers. The use of highly hydrophobic materials can negatively impact certain defect types, such as coating defects and patterning defects. These defects can prevent proper formation of the resist pattern and its transfer to the underlying layer, thus negatively affecting device yield. These defects may take the form of one or more of the following: microbridges, missing contact holes, line pinching, or CD displacement. Therefore, a topcoat layer that balances good hydrophobicity with low levels of coating and patterning defect rates is desirable.

[0006] There is an ongoing need in the art for improved photoresist topcoat compositions that address one or more problems associated with prior art. Summary of the Invention

[0007] A topcoat composition is provided, comprising a polymer including repeating units derived from one or more monomers of formula (1); and a solvent. [] (1) In formula (1), Z1 and Z2 are each independently a single bond or a divalent linking group containing one or more of the following: substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 heteroalkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C1-30 heteroaryl, -O-, -C(O)-, -N(R3)-, -S-, or -S(O)2-, wherein R3 is hydrogen, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C R1-30 is a C1-30 heteroaryl group, or a substituted or unsubstituted C2-30 heteroarylalkyl group. Wherein, Z1 and Z2 form a ring together via single or double bonds between Z1 and Z2. R1 and R2 are each independently a substituted or unsubstituted C1-30 alkyl group, a substituted or unsubstituted C1-30 heteroaryl group, a substituted or unsubstituted C3-30 cycloalkyl group, a substituted or unsubstituted C2-30 heterocycloalkyl group, a substituted or unsubstituted C2-30 alkenyl group, a substituted or unsubstituted C6-30 aryl group, a substituted or unsubstituted C7-30 arylalkyl group, a substituted or unsubstituted C7-30 alkylaryl group, a substituted or unsubstituted C1-30 heteroaryl group, a substituted or unsubstituted C2-30 heteroarylalkyl group, a substituted or unsubstituted C2-30 alkyl heteroaryl group, -OR4, or -N(R5)2, wherein R R1 and R2 are each independently a substituted or unsubstituted C1-30 alkyl, a substituted or unsubstituted C1-30 heteroalkyl, a substituted or unsubstituted C3-30 cycloalkyl, a substituted or unsubstituted C2-20 heterocycloalkyl, a substituted or unsubstituted C6-30 aryl, a substituted or unsubstituted C7-30 arylalkyl, a substituted or unsubstituted C7-30 alkylaryl, a substituted or unsubstituted C1-30 heteroaryl, a substituted or unsubstituted C2-30 heteroarylalkyl, or a substituted or unsubstituted C2-30 alkylheteroaryl. Where desired, R1 and R2 form a ring together by a single or divalent linking group. L is a single or polyvalent linking group; where desired, L is a polyvalent linking group, further including additional groups of the following formula: ,and P-based polymerizable groups.

[0008] A coated substrate is also provided, comprising a photoresist layer on the substrate; and a topcoat layer formed on the photoresist layer, wherein the topcoat layer is derived from the topcoat composition of the present invention.

[0009] A further pattern forming method is provided, comprising forming a photoresist layer on a substrate; forming a topcoat layer on the photoresist layer, wherein the topcoat layer is formed of the topcoat composition of the present invention; exposing the topcoat layer and the photoresist layer to activation radiation in a patterned manner; and contacting the exposed topcoat layer and the exposed photoresist layer with a developer to form a resist pattern. Simple Explanation of the Diagram

[0010] none Implementation

[0011] Reference will now be made in detail to exemplary embodiments, examples of which are shown in this specification. In this respect, these exemplary embodiments may take different forms and should not be construed as limited to the description shown herein. Therefore, the exemplary embodiments are described below only with reference to the accompanying drawings to explain various aspects of this specification. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items. When a statement such as "at least one / of..." precedes the list of elements, it modifies the entire list of elements and does not modify any individual element in the list.

[0012] As used herein, the terms "a / an" and "the" do not indicate a limitation of quantity and are to be construed as including both the singular and plural unless otherwise indicated herein or clearly contradicted by the context. Unless otherwise explicitly stated, "or" means "and / or". The modifier "about" used in conjunction with quantity includes the stated value and has the meaning specified by the context (e.g., including the degree of error associated with a particular quantity of measurement). The full scope disclosed herein includes endpoints, and such endpoints can be independently combined with each other. The suffix "(s)" is intended to include both the singular and plural of the term it modifies, thereby including at least one of the terms. "As needed" or "as required" means that an event or situation subsequently described may or may not occur, and the description includes examples of the event occurring as well as examples of its non-occurrence. The terms "first," "second," and similar terms herein do not indicate order, quantity, or importance, but are used to distinguish one element from another. When an element is referred to as being "on" another element, it may be in direct contact with or inserted between the other element. In contrast, when one element is referred to as being "directly on" another element, there is no inserted element. It should be understood that the components, elements, limitations, and / or features of the described aspects can be combined in any suitable manner in the aspects.

[0013] Unless otherwise defined, all terms used herein (including technical and scientific terms) shall have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. It will be further understood that terms (such as those defined in common dictionaries) shall be interpreted as having the same meaning as they have in the relevant field and in the context of this disclosure, and shall not be construed as having an idealized or overly formal meaning unless expressly defined herein.

[0014] As used herein, the term "alkyl group" refers to an organic compound having at least one carbon atom and at least one hydrogen atom, which is substituted with one or more substituents at the indicated location as required; "alkyl" refers to a straight-chain or branched saturated hydrocarbon having a specified number of carbon atoms and a valence of 1; "alkylene" refers to an alkyl group having a valence of 2; "hydroxyalkyl" refers to an alkyl group substituted with at least one hydroxyl group (-OH); "alkoxy" refers to "alkyl-O-"; "carboxylic acid group" refers to a group having the formula "-C(=O)-OH"; "cycloalkyl" refers to a monovalent group having one or more saturated rings in which all ring members are carbon atoms; "alkylenecycloalkyl" refers to a cycloalkyl group having a valence of 2; "alkenyl" refers to a straight-chain or branched monovalent alkyl group having at least one carbon-carbon double bond; "alkenyloxy" refers to "alkenyl-O-"; "alkylene" refers to an alkyl group having a valence of 2 The valence of alkenyl groups is defined as follows: "cycloalkenyl" refers to a non-aromatic cyclic hydrocarbon group having at least three carbon atoms and at least one carbon-carbon double bond; "alkynyl" refers to a monovalent hydrocarbon group having at least one carbon-carbon triple bond; the term "aromatic group" refers to a monocyclic or polycyclic ring system that satisfies Hückel's rule and includes a carbon atom in the ring, and may include one or more heteroatoms selected from N, O, and S that replace the carbon atoms in the ring, as needed; "aryl" refers to a monovalent aromatic monocyclic or polycyclic ring system in which each ring member is carbon, and may include a group having an aromatic ring fused to at least one cycloalkyl or heterocyclic alkyl ring; "extrinyl" refers to an aryl group having a valence of 2; "alkylaryl" refers to an aryl group that has been substituted with an alkyl group; "arylalkyl" refers to an alkyl group that has been substituted with an aryl group; "aryloxy" refers to "aryl-O-"; and "arylthio" refers to "aryl-S-".

[0015] The prefix "hetero" means that the compound or group includes at least one member (e.g., 1, 2, 3, or 4 or more heteroatoms) as a heteroatom replacing a carbon atom, wherein each heteroatom is independently N, O, S, Si, or P; "heteroatom-containing group" refers to a substituent including at least one heteroatom; "heteroalkyl" refers to an alkyl group having 1 to 4 or more heteroatoms replacing a carbon atom; "heterocyclic alkyl" refers to a cycloalkyl group having 1 to 4 or more heteroatoms as a ring member replacing a carbon atom; "heterocyclic alkyl" refers to a heterocyclic alkyl group having a valence of 2; "heteroaryl" refers to an aryl group having 1 to 4 or more heteroatoms as a ring member replacing a carbon atom; and "heteroaryl" refers to a heteroaryl group having a valence of 2.

[0016] The term "halogen" refers to a monovalent substituent of fluorine (fluorinated), chlorine (chloroinated), bromine (brominated), or iodine (iodinated). The prefix "halogenated" indicates a group that includes one or more of the fluorine, chlorine, bromine, or iodine substituents that replace a hydrogen atom. Combinations of halogen groups (e.g., bromine and fluorine) or only fluorine groups may be present.

[0017] "Fluorinated" should be understood to mean having one or more fluorine atoms incorporated into a group. For example, when indicating a C1-18 fluoroalkyl group, the fluoroalkyl group can include one or more fluorine atoms, such as a single fluorine atom, two fluorine atoms (e.g., 1,1-difluoroethyl), three fluorine atoms (e.g., 2,2,2-trifluoroethyl), or fluorine atoms at each free valence of carbon (e.g., perfluorinated groups such as -CF3, -C2F5, -C3F7, or -C4F9). "Substituted fluoroalkyl" should be understood to mean a fluoroalkyl group further substituted with additional substituents.

[0018] As used herein, an "acid-indestructible group" refers to a group in which the bond is broken by the catalytic action of an acid (as desired and typically in conjunction with heat treatment), resulting in the formation of a polar group (such as a carboxylic acid or alcohol group) on the polymer, and, as desired and typically, a portion attached to the broken bond that is disconnected from the polymer. Such acids are typically photogenerated acids where bond breaking occurs during post-exposure baking. Suitable acid-indestructible 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, secondary or tertiary ether groups, acetal groups, or ketal groups. Acid-indestructible groups are also commonly referred to in the art as "acid-crackable groups," "acid-crackable protecting groups," "acid-indestructible protecting groups," "acid-degradable groups," "acid-sensitive groups," and "acid-decomposable groups."

[0019] As used herein, the term "immersion fluid" refers to the fluid, typically water, inserted between a lens of an exposed tool and a photoresist-coated substrate for immersion lithography.

[0020] "Substituted" means that at least one hydrogen atom on a group is replaced by another group, provided that the normal valence of the specified atom is not exceeded. When the substituent is a side oxygen group (i.e., α=O), then both hydrogen atoms on the carbon atom are replaced. Combinations of substituents or variables are permissible. Exemplary groups that may be present at the "substituted" position include, but are not limited to, nitro (-NO 2), cyano (-CN), hydroxy (-OH), sero-oxy (=O), amino (-NH 2), mono- or di-(C 1-6)alkylamino, alkylyl (such as C 2-6 alkylyl such as acetyl), methylamino (-C(=O)H), carboxylic acid or its alkali metal or ammonium salt; esters (including acrylates, methacrylates and lactones) such as C 2-6 alkyl esters (-C(=O)O-alkyl or -OC(=O)-alkyl) and C 7-13 aryl esters (-C(=O)O-aryl or -OC(=O)-aryl); acetamino (-C(=O)NR 2, wherein R is hydrogen or C 1-6 alkyl), methylamino (-CH 2C(=O)NR 2, wherein R is hydrogen or C 1-6 alkyl). C1-6 alkyl), halogen, mercapto (-SH), C1-6 alkylthio (-S-alkyl), thiocyano (-SCN), C1-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, C1-6 haloalkyl, C1-9 alkoxy, C1-6 haloalkoxy, C3-12 cycloalkyl, C5-18 cycloalkenyl, C6-12 aryl having at least one aromatic ring (e.g., phenyl, biphenyl, naphthyl, etc., each ring system substituted or unsubstituted aromatic), C7-19 arylalkyl having 1 to 3 single or fused rings and 6 to 18 cyclic carbon atoms, arylalkoxy having 1 to 3 single or fused rings and 6 to 18 cyclic carbon atoms, C7-12 alkylaryl, C2-12 heterocyclic alkyl, C1-12 heteroaryl, C 1-6 alkylsulfonyl (-S(=O) 2-alkyl), C 6-12 arylsulfonyl (-S(=O) 2-aryl), or toluenesulfonyl (CH 3C 6H 4SO 2-). When the group is substituted, the indicated carbon number is the total number of carbon atoms in the group, excluding those with any substituents. For example, the group -CH 2CH 2CN is a C 2 alkyl group substituted with a cyano group.

[0021] The topcoat composition of the present invention comprises a matrix polymer, a surfactant polymer, and a solvent mixture, and may include one or more additional optional components. The preferred topcoat composition of the present invention, applied over a photoresist layer, minimizes or prevents the migration of components of the photoresist layer into the immersion fluid used in immersion lithography processes. In the preferred topcoat composition of the present invention, the surfactant polymer is self-isolating. As used herein, the term "immersion fluid" means the fluid, typically water, inserted between a lens of an exposure tool and a photoresist-coated substrate for immersion lithography.

[0022] As used herein, if a reduced amount of acid or organic material is detected in the immersion fluid when using a topcoat composition, compared to the same photoresist system processed in the same manner but without a topcoat composition layer, the topcoat layer is considered to inhibit the migration of photoresist material into the immersion fluid. Before exposure to the photoresist (with and without an externally coated topcoat composition layer) and then after photolithographic processing of the photoresist layer (with and without an externally coated topcoat composition layer) in the immersion fluid under exposure, the photoresist material in the immersion fluid can be detected by mass spectrometry (MS). Typically, compared to the same photoresist without a topcoat layer (i.e., the immersion fluid is in direct contact with the photoresist layer), the topcoat composition provides a reduction of at least 10% in the amount of photoresist material present in the immersion fluid (e.g., acids or organics as detected by MS), and more preferably, compared to the amount of photoresist material in the immersion fluid of the same photoresist without a topcoat layer, the topcoat composition provides a reduction of at least 20%, or 50%, or 90%, or 99%, or 100% in the amount of photoresist material in the immersion fluid.

[0023] The preferred topcoat composition of the present invention allows for improvement of one or more distinct water contact angle characteristics (e.g., static contact angle, retreat contact angle, advance contact angle, and slip angle) that are important in immersion lithography processes. The topcoat composition provides a topcoat layer that exhibits excellent developer solubility, for example, in aqueous alkaline developers, for both exposed and unexposed areas of the layer. The preferred topcoat composition can exhibit a beneficial level of pattern defect.

[0024] The composition can be used in dry lithography processes or, more typically, immersion lithography processes. Additionally, the composition can be advantageous from the perspective of minimizing or preventing degassing, given that degassing can be detrimental to void formation and / or defect generation. Aside from limitations imposed by the photoresist composition, there are no particular limitations on the exposure wavelength, typically wavelengths less than 300 nm, such as 248 nm, 193 nm, or EUV wavelengths (e.g., 13.4 nm). Particularly preferred is the use of the composition in 193 nm immersion lithography processes.

[0025] The polymers used in this invention are soluble in alkaline aqueous solutions, allowing the topcoat layer formed by the composition to be removed using an aqueous alkaline developer (e.g., a quaternary ammonium hydroxide solution, such as tetramethylammonium hydroxide (TMAH), typically a 0.26 N TMAH aqueous solution) during the resist development step. Different polymers may be present in suitable relative amounts.

[0026] Various polymers can be used in the topcoat compositions of the present invention, including polymers comprising: polymerized acrylate groups, polyesters, or other repeating units and / or polymer backbone structures provided by, for example, poly(epoxide), poly(meth)acrylic acid, poly(meth)acrylamide, polymerized aromatic (meth)acrylates, and polymerized vinyl aromatic monomers. Typically, the polymer comprises at least two different repeating units. Different polymers may suitably be present in different relative amounts.

[0027] The polymer of the topcoat composition of the present invention may contain a variety of repeating units, including, for example, one or more: hydrophobic groups; weak acid groups; strong acid groups; branched alkyl or cycloalkyl groups that are substituted as needed; fluoroalkyl groups; or polar groups, such as esters, ethers, carboxyl groups, or sulfonyl groups. The presence of specific functional groups on the repeating units of the polymer will, for example, depend on the desired polymer functionality.

[0028] In some preferred aspects, one or more polymers of the coating composition will contain one or more reactive groups during photolithography, such as one or more photoacid-acid unstable groups that can undergo pyrolysis reactions in the presence of acid and heat, such as acid-instable ester groups (e.g., butyl ester groups provided by polymerization of tributyl acrylate or tributyl methacrylate, adamantane acrylate), and / or acetal groups provided by polymerization of vinyl ether compounds. The presence of such groups may result in the associated one or more polymers being more soluble in the developer solution, thereby facilitating developability and removal of the topcoat layer during the development process.

[0029] Polymers can be advantageously selected to customize the characteristics of the topcoat layer, where each characteristic typically serves one or more purposes or functions. Such functions include, for example, one or more of the following: photoresist profile adjustment, topcoat surface conditioning, defect reduction, and reduction of interfacial mixing between the topcoat and photoresist layers.

[0030] The topcoat composition comprises one or more, preferably two or more (two being typical) matrix polymers, which may contain one or more repeating units of different types, typically two or three different repeating units. The matrix polymer should provide a sufficiently high developer dissolution rate to reduce the overall defect rate due to, for example, microbridging. The matrix polymer may contain monomers, for example, containing sulfonylureas, to improve the polymeric developer dissolution rate. Typical developer dissolution rates of the matrix polymer are greater than 300 nm / s, preferably greater than 500 nm / s, more preferably greater than 1000 nm / s, and even more preferably greater than 3000 nm / s. The matrix polymer can be fluorinated or non-fluorinated. For some photoresist materials, fluorinated topcoat matrix polymers can reduce or minimize interfacial mixing between the topcoat layer and the underlying photoresist layer. Therefore, one or more repeating units of the matrix polymer can be fluorinated, for example, with fluoroalkyl such as C1-4 fluoroalkyl (typically desfluoromethyl), and can be present, for example, as a sulfonamide group (e.g., -NHSO 2CF 3) or a fluoroalcohol group (e.g., -C(CF 3) 2OH).

[0031] The matrix polymer has a higher surface energy than the surface-active polymer, and preferably is immiscible with the surface-active polymer to allow the surface-active polymer to separate from the matrix polymer phase and migrate to the upper surface of the topcoat layer away from the photoresist interface. The surface energy of the matrix polymer is typically from 30 to 60 millinewtons (mN / m).

[0032] Exemplary monomers of formulas (I) and (II) can be used to prepare matrix polymers; however, other monomers may also be used as described herein and as commonly used in the art. (I) (II)

[0033] In formulas (I) and (II), Ra is a hydrogen, fluorine, cyano, substituted or unsubstituted C1-10 alkyl, or substituted or unsubstituted C1-10 fluoroalkyl, typically H or methyl.

[0034] In formula (I), R100 represents a substituted or unsubstituted C1-100 or C1-20 alkyl (typically C1-12 alkyl); a substituted or unsubstituted C3-30 or C3-20 cycloalkyl; or a substituted or unsubstituted poly(C1-3 epoxy). Preferably, the substituted C1-100 or C1-20 alkyl, the substituted C3-30 or C3-20 cycloalkyl, and the substituted poly(C1-3 epoxy) are substituted by one or more of the following: halogen, fluoroalkyl such as C1-4 fluoroalkyl (typically fluoromethyl), sulfonamide group -NH-S(O)2-Y1, wherein Y1 is an F or C1-4 perfluoroalkyl (e.g. -NHSO2CF3), or fluoroalcohol group (e.g. -C(CF3)2OH).

[0035] In formula (II), L 101 represents a single bond or, for example, a polyvalent linking group selected from aliphatic groups such as C1-6 alkyl or C3-20 cycloalkyl, and aromatic hydrocarbons and combinations thereof, with one or more linking motifs selected from -O-, -S-, -C(O)-, and -NR 102-, wherein R 102 is selected from hydrogen and C1-10 alkyl groups selected for substitution; and n is an integer from 1 to 5, typically 1. For example, the matrix polymer may comprise repeating units derived from one or more monomers of formula (II), wherein L 101 is a single bond or a polyvalent linking group selected from: substituted or unsubstituted C1-20 alkyl, typically C1-6 alkyl; substituted or unsubstituted C3-20 cycloalkyl, typically C3-10 cycloalkyl; and substituted or unsubstituted C6-24 aryl, and n is 1, 2, or 3.

[0036] It is believed that units derived from monomers of formula (I) allow for good solubility of the matrix polymer in solvents used in topcoat compositions. Due to their highly polar nature, units derived from monomers of formula (II) can impart desired solubility characteristics to the matrix polymer in aqueous alkaline developers. This allows for efficient removal during photoresist development.

[0037] Based on the total polymeric units of the matrix polymer, units having general formula (I) are typically present in the matrix polymer in amounts of 0 to 100 mol%, more typically 20 to 80 mol%, or 30 to 70 mol%. Based on the total polymeric units of the matrix polymer, units having general formula (II) are typically present in the matrix polymer in amounts of 0 to 50 mol%, more typically 5 to 40 mol%, or 15 to 30 mol%.

[0038] Non-limiting examples of monomers of formula (I) include the following:

[0039] Non-limiting examples of monomers of formula (II) include the following: The Ra series is as defined above.

[0040] Other exemplary matrix polymers can be prepared from monomers such as (alkyl)acrylates (preferably acid-labile (alkyl)acrylates, such as tributyl acrylate, tributyl methacrylate, methyladamantane acrylate, methyladamantane methacrylate, ethyl urethane acrylate, ethyl urethane methacrylate, etc.) and other acyclic alkyl and alicyclic (alkyl)acrylates. Other suitable matrix polymers include, for example, those containing polymeric units of non-aromatic cyclic olefins (inner ring double bonds), such as norbornene substituted as desired; those containing polymeric anhydride units, particularly polymeric maleic anhydride units and / or itaconic anhydride units; and those containing vinyl groups, such as styrene.

[0041] Non-limiting examples of matrix polymers include the following:

[0042] Non-limiting examples of matrix polymers further include the following:

[0043] One or more matrix polymers are typically present in the composition in an amount of 70 to 99.9 wt%, or 70 to 99 wt%, more typically 85 to 95 wt%, based on the total solids of the topcoat composition. The weight-average molecular weight (Mw) of the matrix polymers is typically less than 400,000 Da, for example, 1,000 to 50,000 Da, 2,000 to 25,000 Da, or 5,000 to 25,000 Da.

[0044] Surfactant polymers are provided in topcoat compositions to provide beneficial surface properties at the topcoat / immersion fluid interface. Specifically, surfactant polymers can advantageously provide desired surface properties with respect to water, such as one or more of improved static contact angle (SCA), receding contact angle (RCA), advancing contact angle (ACA), or sliding angle (SA) at the topcoat / immersion fluid interface. In particular, surfactant polymers can allow for higher RCA, which can allow for faster scan rates and increased process throughput. Layers of topcoat compositions in a dry state typically have water receding contact angles of 60° to 95°, typically 75° to 93°, 75° to 85°, or 75° to 80°. The phrase "in a dry state" means containing 8 wt% or less of solvent based on the total composition.

[0045] The surfactant polymer is preferably soluble in alkaline aqueous solutions. The surfactant polymer preferably has a lower surface energy than the matrix polymer. Preferably, the surfactant polymer has a significantly lower surface energy than the matrix polymer and any other polymer present in the topcoat composition and is substantially immiscible with them. In this way, the topcoat composition can be self-isolating, wherein during coating, the surfactant polymer migrates to the upper surface of the topcoat layer away from other polymers. Therefore, in the case of immersion lithography, at the topcoat / immersion fluid interface, the resulting topcoat layer is enriched with surfactant polymers at the upper surface of the topcoat layer.

[0046] While the desired surface energy of a surfactant polymer will depend on the chosen matrix polymer and its surface energy, the surface energy of a surfactant polymer is typically 15 to 35 mN / m, preferably 18 to 30 mN / m. The surface energy of a surfactant polymer is typically 5 to 25 mN / m lower than that of a matrix polymer, preferably 5 to 15 mN / m lower.

[0047] Suitable surfactant polymers have polymerization units comprising, for example, those containing one or more groups selected from acid-insecure, base-insecure, sulfonamide, alkyl, and ester groups. Preferably, such acid-insecure, base-insecure, sulfonamide, alkyl, and ester groups are fluorinated.

[0048] Exemplary surfactant polymers may include, for example, those comprising repeating units derived from monomers of formula (III), formula (IV), or combinations thereof: (III) (IV) In formulas (III) and (IV), each Ra independently represents hydrogen, halogen, C1-3 alkyl, typically H or methyl; R200 represents substituted or unsubstituted C1-100 or C1-20 alkyl, typically C1-12 alkyl; substituted or unsubstituted C3-30 or C3-20 cycloalkyl; or substituted or unsubstituted poly(C1-3 epoxy); and R201 represents linear, branched or cyclic C1-20 fluoroalkyl, typically C1-12 fluoroalkyl. Preferably, the substituted C1-100 or C1-20 alkyl, the substituted C3-30 or C3-20 cycloalkyl, and the substituted poly(C1-3 epoxy) are substituted with one or more of the following: halogen, fluoroalkyl such as C1-4 fluoroalkyl (typically desfluoromethyl), sulfonamide group -NH-S(O)2-Y1, wherein Y1 is an F or C1-4 perfluoroalkyl (such as -NHSO2CF3) or fluoroalcohol group (such as -C(CF3)2OH). []

[0049] L 201 represents a single bond or, for example, a polyvalent linking group selected from aliphatic groups such as C1-6 alkyl or C3-20 cycloalkyl, and aromatic hydrocarbons and combinations thereof, with one or more linking motifs selected from -O-, -S-, -C(O)-, and -NR 102-, wherein R 102 is selected from hydrogen and C1-10 alkyl groups selected for substitution; and m is an integer from 1 to 5, typically 1. For example, the matrix polymer may comprise repeating units derived from one or more monomers of formula (IV), wherein L 201 is a single bond or a polyvalent linking group selected from: substituted or unsubstituted C1-20 alkyl, typically C1-6 alkyl; substituted or unsubstituted C3-20 cycloalkyl, typically C3-10 cycloalkyl; and substituted or unsubstituted C6-24 aryl, and m is 1, 2, or 3.

[0050] The monomers of exemplary formula (III) include those of formula (I) above. Units derived from monomers of formula (III) are believed to allow for effective phase separation of the surfactant polymer from other polymers in the composition, improved dynamic contact angles, such as increased backlash angles and decreased slip angles. Units derived from monomers of formula (IV) are believed to contribute to phase separation, improved dynamic contact angle characteristics, and imparting beneficial hysteresis characteristics to the surfactant polymer and improved solubility in aqueous alkaline developers.

[0051] Units having general formula (III) are typically present in the surfactant polymer in an amount of 0 to 90 mol%, for example 10 to 40 mol%, based on the total repeating units of the surfactant polymer. Units having general formula (IV) are typically present in the surfactant polymer in an amount of 0 to 90 mol%, for example 50 to 80 mol%, based on the total repeating units of the surfactant polymer.

[0052] Non-limiting examples of repeating units for surface-active polymers include polymerization units of one or more of the following monomers:

[0053] Surfactant polymers may contain one or more additional types of units. For example, a surfactant polymer may contain one or more additional units comprising fluorinated groups (such as fluorinated sulfonamide groups, fluorinated alcohol groups, fluorinated ester groups, or combinations thereof), or acid-instable detachable groups, or combinations thereof. Fluorinated alcohol groups may be present in the surfactant polymer for the purpose of improving developer solubility, or allowing for increased dynamic contact angles, such as increased recoil angles and decreased slip angles, and improving developer affinity and solubility. Additional types of units (if used) are typically present in the surfactant polymer in amounts from 1 to 70 mol% based on the surfactant polymer.

[0054] The lower limit of surface-active polymers for immersion lithography is typically determined by the need to prevent the leaching of photoresist components. The surface-active polymer is present in the composition in an amount of 0.1 to 30 wt%, more typically 3 to 20 wt%, or 5 to 15 wt%, based on the total solids of the topcoat composition. The weight-average molecular weight (Mw) of the additive polymer is typically less than 400,000 Da, preferably 5,000 to 50,000 Da, and more preferably 5,000 to 25,000 Da.

[0055] The topcoat composition comprises a polymer including repeating units derived from one or more monomers of formula (1): (1) Wherein, Z1 and Z2 are each independently a single bond or a divalent linking group containing one or more of the following: substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 heteroalkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C1-30 heteroaryl, -O-, -C(O)-, -N(R3)-, -S-, or -S(O)2-, wherein R3 is hydrogen, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C 1-30 heteroaryl, or substituted or unsubstituted C2-30 heteroarylalkyl. Z1 and Z2 may form a ring together via single or double bonds between Z1 and Z2, depending on the desired arrangement.

[0056] In formula (1), R1 and R2 can each independently be a substituted or unsubstituted C1-30 alkyl, a substituted or unsubstituted C1-30 heteroalkyl, a substituted or unsubstituted C3-30 cycloalkyl, a substituted or unsubstituted C2-30 heterocycloalkyl, a substituted or unsubstituted C2-30 alkenyl, a substituted or unsubstituted C6-30 aryl, a substituted or unsubstituted C7-30 arylalkyl, a substituted or unsubstituted C7-30 alkylaryl, a substituted or unsubstituted C1-30 heteroaryl, a substituted or unsubstituted C2-30 heteroarylalkyl, a substituted or unsubstituted C2-30 alkylheteroaryl, -OR4, or -N(R5)2, wherein R4 and R5 are each independently a substituted or unsubstituted C1-30 alkyl, a substituted or unsubstituted C1-30 heteroalkyl, a substituted or unsubstituted C3-30 cycloalkyl, a substituted or unsubstituted C4-30 cycloalkyl, a substituted or unsubstituted C6-30 ... 3-30 cycloalkyl, substituted or unsubstituted C2-20 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C1-30 heteroaryl, substituted or unsubstituted C2-30 heteroarylalkyl, or substituted or unsubstituted C2-30 alkyl heteroaryl. As needed, R1 and R2 may form a ring together by a single bond or a divalent linker, the divalent linker comprising one or more of the following: substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted divalent C7-30 arylalkyl, substituted or unsubstituted C1-30 heteroaryl, or substituted or unsubstituted divalent C2-30 heteroarylalkyl, -O-, -C(O)-, -C(O)-O-, -C(O)-N(R2a)-, -S-, -S(O)2- or -N(R2a)-S(O)2-, wherein R2a is hydrogen, a straight-chain or branched C1-20 alkyl, a monocyclic or polycyclic C 3-20 cycloalkyl, or monocyclic or polycyclic C2-20 heterocyclic alkyl.

[0057] In formula (1), L-series single bonds or multivalent linkages such as divalent, trivalent, or tetravalent linkages. For example, L can be a single bond or a divalent linker selected from one or more of the following: substituted or unsubstituted C1-30 alkyl groups, substituted or unsubstituted C3-30 cycloalkyl groups, substituted or unsubstituted C2-30 heterocycloalkyl groups, substituted or unsubstituted C6-30 aryl groups, substituted or unsubstituted divalent C7-30 arylalkyl groups, substituted or unsubstituted C1-30 heteroaryl groups, or substituted or unsubstituted divalent C2-30 heteroarylalkyl groups, -O-, -C(O)-, -C(O)-O-, -C(O)-N(R2b)-, -S-, -S(O)2-, or -N(R2b)-S(O)2-, wherein R2b is hydrogen, straight-chain or branched C1-20 alkyl groups, monocyclic or polycyclic C3-20 cycloalkyl groups, or monocyclic or polycyclic C3-20 cycloalkyl groups. 2-20 heterocyclic alkyl groups.

[0058] In formula (1), P is a polymerizable group. Typically, the polymerizable group is selected from (meth)acrylic acid, vinyl, and norbornel.

[0059] In formula (1), L may further include a divalent linking group having an additional group having the following formula: Z1, Z2, R1, and R2 are as described above.

[0060] In some embodiments, the polymer may comprise repeating units derived from one or more monomers of formula (1a): (1a)

[0061] In formula (1a), Ra is a hydrogen, fluorine, cyano, substituted or unsubstituted C1-10 alkyl, or substituted or unsubstituted C1-10 fluoroalkyl. L is as defined in formula (1). For example, L can be a single bond or a divalent linker containing one or more groups selected from the following: substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C1-30 heteroaryl, -O-, -C(O)-, -C(O)O-, -OC(O)-, N(R25)-, -S-, or -S(O)2-, wherein R25 is hydrogen, straight-chain or branched C1-20 alkyl, monocyclic or polycyclic C3-20 cycloalkyl, or monocyclic or polycyclic C2-20 heterocycloalkyl.

[0062] In formula (1a), Z1 and Z2 are identical, wherein Z1 and Z2 are selected from single bonds, -O-, divalent linking groups containing the formula -C(O)-, or divalent linking groups containing the formula -C(O)-O-. R1 and R2 are each independently substituted or unsubstituted C1-30 alkyl groups; and, if necessary, R1 and R2 together form a ring by means of single bonds or divalent linking groups.

[0063] Non-limiting examples of monomers having formula (1) and / or (1a) include:

[0064] The monomers comprising a single diac(Boc)amide moiety can be referred to as single-arm monomers. Other exemplary monomers comprising more than one diac(Boc)amide moiety can be referred to as double-arm monomers. For polymers containing structural units derived from single-arm monomers, a carboxyl functional group can be generated on each structural unit derived from the single-arm monomer upon hydrolysis. For polymers containing structural units derived from double-arm monomers, two carboxyl functional groups can be generated on each structural unit derived from the double-arm monomer upon hydrolysis. Similarly, for polymers containing structural units derived from triple-arm monomers, three carboxyl functional groups can be generated on each structural unit derived from the triple-arm monomer upon hydrolysis. This can be beneficial in making the polymer more hydrophilic upon contact with aqueous solutions of alkaline developers.

[0065] The polymers of the present invention may, as desired, further comprise one or more additional repeating units other than those derived from one or more monomers of formula (1). The polymers of the present invention may be matrix polymers or surfactant polymers, and may further comprise one or more additional repeating units, for example, derived from any one or more monomers of general formulas (I), (II), (III), and (IV), described together with the matrix polymers and surfactant polymers. One or more additional units (if present in the polymer) may be used in amounts up to 90 mol% based on the total moles of repeating units in the polymer, and typically from 3 to 50 mol%.

[0066] In some preferred aspects, the polymer may contain one or more reactive groups during photolithography, such as one or more photoacid-acid unstable groups that can undergo cleavage reactions in the presence of acid and heat, such as acid-instable ester groups (e.g., tert-butyl ester groups provided by polymerization of tributyl acrylate or tributyl methacrylate, 2-methyl-2-adamantyl methacrylate), and / or acetal groups provided by polymerization of 1-butoxyethyl methacrylate. The presence of such groups may result in greater solubility of the associated one or more polymers in the developer solution, thereby facilitating developability and removal of the topcoat layer during the development process.

[0067] For example, the polymers of the present invention may comprise acid-labile repeating units of one or more monomers derived from formulas (2a), (2b), (2c), (2d), or (2e): (2a) (2b) (2c) (2d) (2e)

[0068] In formulas (2a) to (2e), Ra is a hydrogen, fluorine, cyano, substituted or unsubstituted C1-10 alkyl, or substituted or unsubstituted C1-10 fluoroalkyl. Preferably, Ra is a hydrogen, fluorine, or substituted or unsubstituted C1-5 alkyl, typically methyl.

[0069] In formula (2a), L1 comprises a divalent linking group consisting of at least one carbon atom, at least one heteroatom, or a combination thereof. For example, L1 may comprise 1 to 10 carbon atoms and at least one heteroatom. In typical examples, L1 may be -OCH 2-, -OCH 2CH 2O-, or -N(R 1a)-, wherein R 1a is hydrogen or a C1-6 alkyl group.

[0070] In formulas (2a) and (2b), R7 to R12 are each independently hydrogen, a straight-chain or branched C1-20 alkyl, a monocyclic or polycyclic C3-20 cycloalkyl, a monocyclic or polycyclic C2-20 heterocyclic alkyl, a straight-chain or branched C2-20 alkenyl, a monocyclic or polycyclic C3-20 cycloalkenyl, a monocyclic or polycyclic C3-20 heterocyclic alkenyl, a monocyclic or polycyclic C6-20 aryl, or a monocyclic or polycyclic C1-20 heteroaryl, each of which is substituted or unsubstituted; the premise being that only one of R7 to R9 is capable of being a hydrogen and only one of R10 to R12 is capable of being a hydrogen. Preferably, R7 to R12 are each independently a straight-chain or branched C1-6 alkyl group, or a monocyclic or polycyclic C3-10 cycloalkyl group, each of which is substituted or unsubstituted.

[0071] In formula (2a), any two of R7 to R9 together may form a ring as required, and each of R7 to R9 may further include as part of its structure one or more groups selected from -O-, -C(O)-, -C(O)-O-, -S-, -S(O)2-, and N(R19)-S(O)2-, wherein R19 is hydrogen, a straight-chain or branched C1-20 alkyl, a monocyclic or polycyclic C3-20 cycloalkyl, or a monocyclic or polycyclic C2-20 heterocyclic alkyl. In formula (2b), any two of R10 to R12 together may form a ring if desired, and each of R10 to R12 may further include as part of its structure one or more groups selected from -O-, -C(O)-, -C(O)-O-, -S-, --S(O)2-, and N(R20)-S(O)2-, wherein R20 is hydrogen, a straight-chain or branched C1-20 alkyl, a monocyclic or polycyclic C3-20 cycloalkyl, or a monocyclic or polycyclic C2-20 heterocyclic alkyl. For example, any one or more of R7 to R12 may independently be a group having the formula -CH2C(=O)CH(3-n)Yn, wherein each Y is independently a substituted or unsubstituted C2-10 heterocyclic alkyl and n is 1 or 2. For example, each Y can be independently a substituted or unsubstituted C2-10 heterocyclic alkyl group comprising a group having the formula -O(Ca1)(Ca2)O-, wherein Ca1 and Ca2 are each independently hydrogen or substituted or unsubstituted alkyl groups, and wherein Ca1 and Ca2 together form a ring as desired.

[0072] In formulas (2c) and (2e), R13 to R14 may each be independently hydrogen, a straight-chain or branched C1-20 alkyl, a monocyclic or polycyclic C3-20 cycloalkyl, a monocyclic or polycyclic C2-20 heterocyclic alkyl, a monocyclic or polycyclic C6-20 aryl, or a monocyclic or polycyclic C1-20 heteroaryl, each of which may be substituted or unsubstituted; and R15 is a straight-chain or branched C1-20 alkyl, a monocyclic or polycyclic C3-20 cycloalkyl, or a monocyclic or polycyclic C2-20 heterocyclic alkyl, each of which may be substituted or unsubstituted. If desired, one of R13 or R14 may form a heterocycle together with R15. Preferably, R13 and R14 can each be independently hydrogen, a straight-chain or branched C1-20 alkyl, a monocyclic or polycyclic C3-20 cycloalkyl, or a monocyclic or polycyclic C2-20 heterocyclic alkyl.

[0073] In formula (2d), R16 to R18 can each independently be a straight-chain or branched C1-20 alkyl, a monocyclic or polycyclic C3-20 cycloalkyl, a monocyclic or polycyclic C2-20 heterocyclic alkyl, a monocyclic or polycyclic C6-20 aryl, or a monocyclic or polycyclic C1-20 heteroaryl, each of which is substituted or unsubstituted. Any two of R16 to R18 together may form a ring as desired, and each of R16 to R18 may, as desired, contain one or more groups selected from -O-, -C(O)-, -C(O)-O-, -S-, -S(O)2-, and -N(R1b)-S(O)2- as part of its structure, wherein R1b may be hydrogen, a straight-chain or branched C1-20 alkyl, a monocyclic or polycyclic ... 3-20 cycloalkyl, or monocyclic or polycyclic C 2-20 heterocyclic alkyl; X a series polymerizable groups selected from vinyl and norbenzyl.

[0074] In formulas (2d) and (2e), each L2 group is a single or divalent linker, provided that when Xa is a vinyl group, L2 is not a single bond. Preferably, L2 is a monocyclic or polycyclic C6-30 aryl or monocyclic or polycyclic C6-30 cycloalkyl group, each of which may be substituted or unsubstituted. In formulas (2d) and (2e), n is 0 or 1. It should be understood that when n is 0, the L2 group is directly linked to an oxygen atom.

[0075] Non-limiting examples of monomer (2a) include:

[0076] Non-limiting examples of monomers having formula (2b) include: Wherein Rd is Ra as defined above; and R' and R'' are each independently a straight-chain or branched C1-20 alkyl, a monocyclic or polycyclic C3-20 cycloalkyl, a monocyclic or polycyclic C2-20 heterocyclic alkyl, a straight-chain or branched C2-20 alkenyl, a monocyclic or polycyclic C3-20 cycloalkenyl, a monocyclic or polycyclic C3-20 heterocyclic alkenyl, a monocyclic or polycyclic C6-20 aryl, or a monocyclic or polycyclic C1-20 heteroaryl, each of which is substituted or unsubstituted.

[0077] Non-limiting examples of monomers having formula (2c) include: Where Rd is the same as Ra as defined above.

[0078] Non-limiting examples of monomers (2d) include:

[0079] Non-limiting examples of monomer (2e) include:

[0080] In another example, the repeating unit of the first polymer having an acid-labile group can be derived from one or more monomers having cyclic acetal or cyclic ketal groups, for example, monomers having the following formula: Where Rd is the same as Ra as defined above.

[0081] In another example, the repeating unit of the first polymer having an acid-labile group can be derived from one or more monomers having a tertiary alkoxy group, such as monomers having the following formula:

[0082] The first polymer typically has a weight-average molecular weight (Mw) of 1,000 to 50,000 Da, more preferably 2,000 to 30,000 Da, even more preferably 3,000 to 20,000 Da, and still more preferably 3,000 to 10,000 Da. The polydispersity index (PDI) of the polymer (which is the ratio of Mw to the number-average molecular weight (Mn)) is typically 1.1 to 3, and more typically 1.1 to 2. The molecular weight values ​​are determined by gel permeation chromatography (GPC) using polystyrene standards.

[0083] Polymers can be prepared using any suitable method in the art. For example, one or more monomers corresponding to the repeating units described herein can be fed together or separately using suitable one or more solvents and initiators and polymerized in a reactor. For example, polymers can be obtained by polymerizing the respective monomers under any suitable conditions, such as by heating at an effective temperature, irradiation with photochemical radiation at an effective wavelength, or a combination thereof.

[0084] In some aspects, the polymers of the present invention may be matrix polymers. In other aspects, the polymers of the present invention may be surface-active polymers.

[0085] Additional polymers may be present in the topcoat composition as needed. For example, additional polymers may be provided in addition to the base polymer and the surfactant polymer for the purpose of adjusting the resist characteristic distribution and / or controlling resist top loss. The additional polymers are typically miscible with the base polymer and substantially immiscible with the surfactant polymer, allowing the surfactant polymer to self-isolate from the other polymers to the topcoat surface away from the topcoat / photoresist interface.

[0086] Typical solvent materials used in formulating and casting topcoat compositions are any solvent materials that dissolve or disperse the components of the topcoat composition but do not significantly dissolve the underlying photoresist layer (if the topcoat composition is applied to the photoresist layer). Preferably, the total solvent is based on organic matter (i.e., greater than 50 wt% organic matter), typically 90 to 100 wt%, more typically 99 to 100 wt%, or 100 wt% organic solvent, excluding residual water or other contaminants that may be present, for example, in amounts of 0.05 to 1 wt% based on the total solvent. Preferably, different solvents, such as mixtures of two, three, or more solvents, can be used to achieve effective phase separation of the surfactant polymer from one or more other polymers in the composition. Solvent mixtures can also effectively reduce the viscosity of the formulation, which allows for a reduction in dispensing volume.

[0087] In an exemplary aspect, a two-solvent system or a three-solvent system can be used in the topcoat composition of the present invention. A preferred solvent system comprises a primary solvent and an additive solvent and may include a diluent solvent. The primary solvent typically exhibits superior solubility characteristics relative to the non-solvent components of the topcoat composition. While the desired boiling point of the primary solvent will depend on the other components of the solvent system, it is typically lower than that of the additive solvent, with boiling points of 100°C to 200°C, such as about 130°C, being typical.

[0088] Suitable primary solvents include, for example, C4-10 monovalent alcohols such as n-butanol, isobutanol, 2-methyl-1-butanol, isoamyl alcohol, 2,3-dimethyl-1-butanol, 4-methyl-2-pentanol, isohexanol, isohepanol, 1-octanol, 1-nonanol, and 1-decanol, and mixtures thereof. Primary solvents are typically present in amounts ranging from 30 wt% to 80 wt% based on the solvent system.

[0089] Additive solvents can promote phase separation between one or more polymers in the topcoat composition. Additionally, higher boiling point additive solvents can reduce end-drying effects during application. Typically, additive solvents have a higher boiling point than the other components of the solvent system. While the desired boiling point of the additive solvent will depend on the other components of the solvent system, boiling points from 170°C to 250°C, such as about 190°C, are typical. Suitable additive solvents include, for example, hydroxyalkyl ethers, such as those having the following general formula (V): R 24-OR 25-OR 26-OH (V) [, , ] R24 is a C1-2 alkyl group to be substituted, and R25 and R26 are each independently selected from C2-4 alkyl groups to be substituted, and mixtures of such hydroxyalkyl ethers include mixtures of isomers. Exemplary hydroxyalkyl ethers include dienyl glycol monoalkyl ethers and their isomers, such as diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, their isomers, and mixtures thereof. The additive solvent is typically present in an amount of 3 to 15 wt% based on the solvent system.

[0090] Diluent solvents can be used to reduce viscosity and improve coating coverage at lower partition volumes. Compared to the primary solvent, the diluent solvent is typically a less desirable solvent for the non-solvent components of the composition. While the desired boiling point of the diluent solvent will depend on the other components of the solvent system, boiling points of 100°C to 200°C, such as about 170°C, are typical. Suitable diluent solvents include, for example, alkanes, such as C8-12 n-alkanes, such as n-octane, n-decane, and dodecane, their isomers, and mixtures thereof; and / or alkyl ethers, such as those having the formulas R27-OR28, wherein R27 and R28 are each independently selected from C2-8 alkyl, C2-6 alkyl, and C2-4 alkyl groups. The alkyl ether group can be straight-chain or branched and symmetrical or asymmetrical. Particularly suitable alkyl ethers include, for example, isobutyl ether, isopentyl ether, isobutylisohexyl ether, and mixtures thereof. Other suitable diluent solvents include ester solvents, such as those represented by general formula (VI): (VI) Wherein, R29 and R30 are each independently selected from C3-8 alkyl groups; and the total number of carbon atoms of R29 and R30 together is greater than 6. Suitable solvents for such esters include, for example, propyl valerate, isopropyl valerate, isopropyl 3-methylbutyrate, isopropyl 2-methylbutyrate, isopropyl neovalerate, isobutyl isobutyrate, 2-methylbutyl isobutyrate, 2-methylbutyrate-2-methylbutyl 2-methylhexanoate, 2-methylbutyl heptanoate, hexyl heptanoate, n-butyl butyrate, isoamyl butyrate, and isoamyl isovalerate. If used, the diluent solvent is typically present in an amount of 10 to 70 wt% based on the solvent system. []

[0091] A particularly preferred solvent system comprises 4-methyl-2-pentanol, dipropylene glycol methyl ether, and isobutyl isobutyrate. Although exemplary solvent systems have been described with respect to two-component and three-component systems, it should be understood that additional solvents may be used. For example, one or more additional primary solvents, diluent solvents, additive solvents, and / or other solvents may be employed.

[0092] The topcoat composition may contain one or more other optional components. For example, the composition may contain one or more of photochemical dyes and contrast dyes, anti-striking agents, etc., to enhance antireflective properties. If used, such optional additives are typically present in the composition in small amounts, such as 0.1 to 10 wt%, based on the total solids of the topcoat composition.

[0093] Including acid-generating compounds such as photoacid generators (PAGs) and / or thermal acid generators (TAGs) in the topcoat composition may be beneficial. Suitable photoacid generators are known in the field of chemically enhanced photoresists and include, for example: onium salts, such as triphenylstronium trifluoromethanesulfonate, (p-tributoxyphenyl)diphenylstronium trifluoromethanesulfonate, tri(p-tributoxyphenyl)stronium trifluoromethanesulfonate, triphenylstronium p-toluenesulfonate; nitrobenzyl derivatives, such as 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate, and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonates, such as 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene. Benzene; diazomethane derivatives, such as bis(benzenesulfonyl)diazomethane and bis(p-toluenesulfonyl)diazomethane; dioxime derivatives, such as bis-O-(p-toluenesulfonyl)-α-dimethyldioxime and bis-O-(n-butanesulfonyl)-α-dimethyldioxime; sulfonate derivatives of N-hydroxyaceimine compounds, such as N-hydroxysuccinimine methane sulfonate and N-hydroxysuccinimine trifluoromethane sulfonate; and halogen-containing tri compounds, such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-tri, and 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-tri. One or more of these PAGs may be used.

[0094] Suitable hot acid generators include, for example, nitrobenzyl toluenesulfonate, such as 2-nitrobenzyl toluenesulfonate, 2,4-dinitrobenzyl toluenesulfonate, 2,6-dinitrobenzyl toluenesulfonate, and 4-nitrobenzyl toluenesulfonate; benzenesulfonates, such as 2-trifluoromethyl-6-nitrobenzyl tetrachlorobenzenesulfonate and 2-trifluoromethyl-6-nitrobenzyl 4-nitrobenzenesulfonate; phenolsulfonates, such as phenyl 4-methoxybenzenesulfonate; alkylammonium salts of organic acids, such as 10-camphorsulfonic acid, trifluoromethylbenzenesulfonic acid, and triethylammonium salts of perfluorobutanesulfonic acid; and specific onium salts. A variety of aromatic (anthracene, naphthalene, or benzene derivative) sulfonate amine salts can be used as TAGs, including those disclosed in U.S. Patent Nos. 3,474,054, 4,200,729, 4,251,665, and 5,187,019. Examples of these tags include those sold by King Industries, Norwalk, Conn. USA under the names NACURE™, CDX™, and K-PURE™, such as NACURE 5225, CDX-2168E, K-PURE™ 2678, and KPURE™ 2700. One or more of these tags may be used.

[0095] If used, the one or more acid-generating agents can be used in a relatively small amount in the topcoat composition, for example, 0.1 to 8 wt% based on the total solids of the composition. This use of one or more acid-generating agent compounds can advantageously affect the photolithographic properties, particularly the resolution, of the developed image patterned in the underlying resist layer.

[0096] The topcoat layer formed from this composition typically has a refractive index of 1.4 or greater at 193 nm, preferably 1.47 or greater at 193 nm. The refractive index can be adjusted by changing the composition of the matrix polymer, surfactant polymer, additive polymer, or other components of the topcoat composition. For example, increasing the relative amount of organic contents in the topcoat composition can provide an increased layer refractive index. At the target exposure wavelength, a preferred topcoat composition layer will have a refractive index between that of the immersion fluid and the photoresist.

[0097] The photoresist topcoat composition can be prepared according to known procedures. For example, the composition can be prepared by dissolving the solid components of the composition in a solvent component. The desired total solids content of the composition will depend on various factors such as the specific polymer in the composition and the required final layer thickness. Preferably, the solids content of the topcoat composition is based on 1 to 10 wt% of the total weight of the composition, more preferably 1 to 5 wt%. The viscosity of the entire composition is typically 1.5 to 2 centipoise (cP).

[0098] Photoresist compositions usable in the methods of the present invention include chemically reinforced photoresist compositions comprising a matrix polymer that is acid-sensitive, meaning that as part of a layer of the photoresist composition, the polymer and composition layer undergo changes in solubility in the developer due to reactions with acids generated by photoacid generators after soft baking, exposure to activating radiation, and post-exposure baking. The resist formulation can be positive or negative, but typically positive. In positive photoresists, changes in solubility are typically caused by acid-insecure groups in the matrix polymer, such as photoacid-insecure ester groups or acetal groups, undergoing photoacid-promoted deprotection reactions upon exposure to activating radiation and heat treatment. Suitable photoresist compositions usable in the present invention are commercially available.

[0099] For imaging at wavelengths such as 193 nm, the matrix polymer is typically substantially free (e.g., less than 15 mole%) or completely free of phenyl, benzyl, or other aromatic groups, which highly absorb radiation. Suitable polymers substantially or completely free of aromatic groups are disclosed in European application EP 930542 A1 and U.S. Patent Nos. 6,692,888 and 6,680,159 (all belonging to Shipley Company). Preferred acid-labile groups include, for example, acetal or ester groups containing a tertiary acyclic alkyl carbon (e.g., tertiary butyl) or a tertiary alicyclic carbon (e.g., methyladamantyl) covalently linked to the carboxyl oxygen of an ester in the matrix polymer.

[0100] Suitable matrix polymers further include polymers containing: (alkyl)acrylate units, preferably including acid-labile (alkyl)acrylate units such as tert-butyl acrylate, tert-butyl methacrylate, methyladamantane acrylate, methyladamantane methacrylate, ethyl urethane acrylate, ethyl urethane methacrylate, etc.; and other noncyclic alkyl and alicyclic (alkyl)acrylates. Such polymers have been described, for example, in U.S. Patent No. 6,057,083, European Publications EP 01008913 A1 and EP 00930542 A1, and U.S. Patent No. 6,136,501. Other suitable matrix polymers include, for example, those containing polymeric units of non-aromatic cyclic olefins (inner ring double bonds), such as norcamphene substituted as desired, for example, polymers described in U.S. Patent Nos. 5,843,624 and 6,048,664. Other suitable matrix polymers include polymers containing polymeric anhydride units, particularly polymeric maleic anhydride units and / or itaconic anhydride units, as disclosed in European application EP 01008913 A1 and U.S. Patent No. 6,048,662.

[0101] Also suitable as matrix polymers are resins containing repeating units that contain heteroatoms, particularly oxygen and / or sulfur (but not anhydrides, i.e., the unit does not contain ketone ring atoms). Heterocyclic units can be fused to the polymer backbone and can comprise fused carbocyclic units (such as those provided by polymerization of norcamphene groups) and / or anhydride units (such as those provided by polymerization of maleic anhydride or itaconic anhydride). Such polymers are disclosed in PCT / US 01 / 14914 and U.S. Patent No. 6,306,554. Other suitable matrix polymers containing heteroatom-containing groups include polymers containing polymeric carbocyclic aryl units substituted with one or more heteroatom-containing (e.g., oxygen or sulfur) groups such as hydroxynaphthyl groups, as disclosed in U.S. Patent No. 7,244,542.

[0102] Blends of two or more of the matrix polymers described above can be suitably used in photoresist compositions.

[0103] Suitable matrix polymers for photoresist compositions are commercially available and can be readily prepared by those skilled in the art. The matrix polymer is present in the photoresist composition in an amount sufficient to make the exposed coating of the photoresist developable in a suitable developer solution. Typically, the matrix polymer is present in the composition in an amount of 50 to 95 wt% based on the total solids of the photoresist composition. The weight-average molecular weight Mw of the matrix polymer is typically less than 100,000 Da, for example, 5,000 to 100,000 Da, more typically 5,000 to 15,000 Da.

[0104] The photoresist composition further includes a photoactive component, such as a photoacid generator (PAG), used in an amount sufficient to produce a latent image in the coating of the composition upon exposure to activating radiation. For example, the photoacid generator will suitably be present in an amount of about 1 to 20 wt% based on the total solids of the photoresist composition. Typically, a smaller amount of PAG will be suitable for chemically reinforced photoresists compared to non-chemically reinforced materials. Suitable PAGs are known in the field of chemically reinforced photoresists and include, for example, those described above regarding topcoat compositions.

[0105] Suitable solvents for photoresist compositions include, for example: glycol ethers, such as 2-methoxyethyl ether (diethylene glycol dimethyl ether), ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; propylene glycol monomethyl ether acetate; lactates, such as methyl lactate and ethyl lactate; propionates, such as methyl propionate, ethyl propionate, ethoxypropionate, and methyl-2-hydroxyisobutyrate; cellosolve esters, such as methyl cellosolve acetate; aromatic hydrocarbons, such as toluene and xylene; and ketones, such as acetone, methyl ethyl ketone, cyclohexanone, and 2-heptanone. Blends of solvents, such as blends of two, three, or more of the solvents described above, are also suitable. The solvents are typically present in the composition in an amount of 90 to 99 wt%, more typically 95 to 98 wt%, based on the total weight of the photoresist composition.

[0106] The photoresist composition may also contain other materials as desired. For example, the composition may contain one or more of photochemical dyes and contrast dyes, anti-stripping agents, plasticizers, speed enhancers, sensitizers, etc. If used, such optional additives are typically present in the composition in small amounts, such as 0.1 to 10 wt%, based on the total solids of the photoresist composition.

[0107] A preferred additive system for the resist composition is an added base. Suitable bases are known in the art and include, for example, linear and cyclic amides and their derivatives, such as N,N-bis(2-hydroxyethyl)palmitoylamine, N,N-diethylacetamide, N1,N1,N3,N3-tetrabutylpropanediamide, 1-methylazacycloheptane-2-one, 1-allylazacycloheptane-2-one, and tributyl 1,3-dihydroxy-2-(hydroxymethyl)propane-2-ylaminocarbamate; aromatic amines, such as pyridine and di- and tributylpyridine; aliphatic amines, such as triisopropanolamine, n-tri-... Butyl diethanolamine, tris(2-acetoxy-ethyl)amine, 2,2',2'',2'''-(ethane-1,2-diylbis(azanetriyl))tetraethanol, 2-(dibutylamino)ethanol, and 2,2',2''-nitrotriethanol; cyclic aliphatic amines, such as 1-(tributoxycarbonyl)-4-hydroxypiperidine, tributyl 1-pyrrolidinecarboxylate, tributyl 2-ethyl-1H-imidazolium-1-carboxylate, di-tributyl piperazine-1,4-dicarboxylate, and N(2-acetoxy-ethyl)line. The added base is suitably used in a relatively small amount, for example, 0.01 to 5 wt%, preferably 0.1 to 2 wt%, based on the total solids of the photoresist composition.

[0108] Alternatively or additionally, the photoresist composition may further comprise one or more additive polymers other than those described above. For example, the photoresist composition may comprise additional polymers described above but with different compositions. Alternatively or additionally, the one or more additional polymers may include those well known in the field of photoresists, such as those selected from: polyacrylates, polyvinyl ethers, polyesters, polynorcampene, polyacetals, polyethylene glycol, polyamide, polyacrylamide, polyphenols, phenolic varnishes, styrene polymers, polyvinyl alcohol, or combinations thereof.

[0109] The resist composition may further include one or more additional optional additives. For example, optional additives may include photochemical dyes and contrast dyes, anti-stripping agents, plasticizers, accelerators, sensitizers, photodegradable quenchers (PDQ) (and also referred to as photodegradable bases), alkaline quenchers, hot acid generators, surfactants, etc., or combinations thereof. If present, optional additives are typically present in the resist composition in an amount of 0.01 to 10 wt% based on the total solids of the resist composition.

[0110] Photoresists can be prepared according to known procedures. For example, photoresists can be prepared as a coating composition by dissolving the solid components of the photoresist in a solvent component. The desired total solids content of the photoresist will depend on various factors such as the specific polymer in the composition, the final layer thickness, and the exposure wavelength. Typically, the solids content of the photoresist varies from 1 to 10 wt% based on the total weight of the photoresist composition, and more typically from 2 to 5 wt%.

[0111] The photoresist composition used in the method of the present invention is suitably applied to a substrate using conventional methods for applying photoresist. The liquid photoresist composition can be applied to the substrate by means of spin coating, dip coating, roll coating, or other conventional coating techniques, with spin coating being typical. When spin coating, the solids content of the coating solution can be adjusted to provide the desired film thickness based on the specific spinning equipment used, the viscosity of the solution, the speed of the spin coater, and the amount of time allowed for rotation. For example, the application of a photoresist layer and / or topcoat can be accomplished by spin coating the photoresist in a solvent using a coating track, wherein the photoresist is dispensed onto a rotating wafer. During dispensing, the wafer is typically rotated at a speed up to 4000 rpm, for example 200 to 3000 rpm, for example 1000 to 2500 rpm, for 15 to 120 seconds to obtain a photoresist layer on the substrate. Those skilled in the art will understand that the thickness of the coated layer can be adjusted by changing the rotation speed and / or the solids content of the composition. The photoresist layer typically has a dry layer thickness of 10 to 500 nanometers (nm), preferably 15 to 200 nm, and even more preferably 20 to 120 nm.

[0112] Suitable substrates on which photoresist compositions can be coated include electronic device substrates. A wide variety of electronic device substrates can be used in this invention, such as: semiconductor wafers; polycrystalline silicon substrates; packaging substrates, such as multi-wafer modules; flat panel display substrates; substrates for light-emitting diodes (LEDs) including organic light-emitting diodes (OLEDs); etc., wherein semiconductor wafers are typical. Such substrates are typically composed of one or more of silicon, polycrystalline silicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanide, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. Suitable substrates can be in the form of wafers, such as those used for manufacturing integrated circuits, optical sensors, flat panel displays, integrated optical circuits, and LEDs. Such substrates can be of any suitable size. Typical wafer substrate diameters are 200 to 300 millimeters (mm), although wafers with smaller and larger diameters can be suitably used according to the invention. The substrate may include one or more layers or structures, which may include, as needed, active or operable portions of the formed device. Typically, a photoresist composition is applied to an antireflective layer, such as an organic antireflective layer.

[0113] Typically, one or more photolithographic layers, such as hard mask layers (e.g., spin-coated carbon (SOC), amorphous carbon, or metal hard mask layers), CVD layers (e.g., silicon nitride (SiN), silicon oxide (SiO), or silicon oxynitride (SiON) layers), organic or inorganic underlayers, or combinations thereof, are provided on the upper surface of the substrate before coating the photoresist composition. These layers, together with the externally coated photoresist layers, form a photolithographic material stack.

[0114] If desired, an adhesion promoter layer can be applied to the substrate surface before coating the photoresist topcoat composition. If desired, any suitable adhesion promoter for polymer films can be used, such as silanes, typically organosilanes like trimethoxyvinylsilane, triethoxyvinylsilane, hexamethyldisilazane, or aminosilane coupling agents like γ-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those sold from DuPont Electronics & Imaging (Marlborough, Massachusetts) under the names AP 3000, AP 8000, and AP 9000S.

[0115] The topcoat composition of the present invention can be applied onto the photoresist composition by any suitable method (as described above with respect to the photoresist composition), wherein spin coating is typical.

[0116] After the photoresist is coated onto a surface, it can be heated (soft-baked) to remove the solvent until the photoresist coating is typically non-sticky, or the photoresist layer can be dried after the topcoat composition has been applied and the solvent from both the photoresist composition layer and the topcoat composition layer has been substantially removed in a single heat treatment step. Soft baking is performed, for example, on a heated plate or in an oven, with the heated plate being typical. The soft baking temperature and time will depend, for example, on the specific photoresist composition and thickness. Soft baking temperatures are typically 90 to 170°C, and more typically 90 to 150°C. Soft baking times are typically 10 seconds to 20 minutes, more typically 1 minute to 10 minutes, and still more typically 1 minute to 5 minutes. Those skilled in the art can easily determine the heating time based on the composition of the composition.

[0117] Next, a photoresist layer with an outer coating is patterned and exposed to activating radiation to create a solubility difference between exposed and unexposed areas. The exposure of the photoresist topcoat composition to radiation that activates the composition, as described herein, demonstrates that radiation can form a latent image within the photoresist composition. Exposure is typically performed using a patterned photomask with optically transparent and optically opaque regions corresponding to the areas of the resist layer to be exposed and the areas of the resist layer to be unexposed, respectively. Alternatively, this exposure can be performed without a photomask in a direct-write method, typically used in electron beam lithography. The activating radiation typically has wavelengths less than 400 nm, less than 300 nm, or less than 200 nm, with 248 nm (KrF), 13.5 nm (EUV), or electron beam lithography being preferred. This method can be used in immersion or dry (non-immersion) lithography techniques. The energy of the exposure is typically 1 to 200 millijoules per square centimeter (mJ / cm²), preferably 10 to 100 mJ / cm², and even more preferably 20 to 50 mJ / cm², depending on the composition of the exposure tool and the photoresist topcoat. Exposure is typically performed using an immersion scanner, but can alternatively be performed using a dry (non-immersion) exposure tool.

[0118] Following exposure and photoactivation of the photoresist layer (and topcoat composition, if photosensitive), the exposed photoresist layer undergoes post-exposure baking (PEB). PEB can be performed, for example, on a heated plate or in an oven, with the heated plate being typical. The conditions of PEB will depend, for example, on the specific photoresist topcoat composition and layer thickness. PEB is typically performed at temperatures between 80°C and 150°C for 30 to 120 seconds. A latent image is formed in the photoresist, defined by polarity-converted regions (exposed regions) and non-polarity-converted regions (unexposed regions).

[0119] The film is then developed. In summary, development is performed according to procedures generally accepted in the art. In the case of a positive development (PTD) process, exposed areas of the photoresist layer and topcoat layer are removed during development, while unexposed areas are retained. Conversely, in a negative development (NTD) process, exposed areas of the photoresist layer are retained during development, while unexposed areas and the topcoat layer are removed. The developer can be applied by any suitable method (as described above regarding the application of the photoresist and topcoat composition), with spin coating being typical. The development time is the period of time during which the soluble areas of the photoresist are effectively removed, typically 5 to 60 seconds. Development is typically performed at room temperature.

[0120] Suitable developers for PTD processes include aqueous alkaline developers, such as quaternary ammonium hydroxide solutions, such as tetramethylammonium hydroxide (TMAH) (preferably 0.26 standard (N) TMAH), tetraethylammonium hydroxide, tetrabutylammonium hydroxide, amine solutions, such as ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, or methyldiethylamine; alkanolamines, such as diethanolamine or triethanolamine; and cyclic amines, such as pyrrole or pyridine; sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. Suitable developers for NTD processes are based on organic solvents, meaning that the cumulative content of organic solvents in the developer is 50 wt% or more, typically 95 wt% or more, 98 wt% or more, or 100 wt% based on the total weight of the developer. Suitable organic solvents for NTD developers include, for example, those selected from ketones, esters, ethers, hydrocarbons, and mixtures thereof. Developers are typically 2-heptanone or n-butyl acetate.

[0121] After the photoresist layer is developed, the developed substrate can be selectively processed in areas lacking photoresist, for example by chemical etching or plating of the photoresist-deficient substrate areas according to procedures known in the art. Following such processing, the photoresist remaining on the substrate can be removed using known stripping procedures.

[0122] The coated substrate can be formed from the topcoat composition of the present invention. Such a coated substrate includes: (a) a photoresist layer on the substrate; and (b) a topcoat layer formed on the photoresist layer, wherein the topcoat layer is derived from the topcoat composition.

[0123] Photoresist patterns can be used, for example, as etching masks to transfer patterns to one or more sequentially arranged underlying layers using known etching techniques, typically dry etching (such as reactive ion etching). Photoresist patterns can also be used, for example, to transfer patterns to an underlying hard mask layer, which in turn serves as an etching mask for transferring patterns to one or more layers below the hard mask layer. If the photoresist pattern is not lost during pattern transfer, it can be removed from the substrate using known techniques (such as oxygen plasma ashing). When used in one or more such patterning processes, photoresist topcoat compositions can be used to manufacture semiconductor devices such as memory devices, processor wafers (CPUs), graphics wafers, optoelectronic wafers, LEDs, OLEDs, and other electronic devices.

[0124] The invention is further illustrated by the following examples. Example

[0125] [monomer] [1] Synthesis of [Methacrylamide]: Methacrylamide (10.0 g, 1.0 equivalent) and dimethylaminopyridine (1.45 g, 0.1 equivalent) were dissolved in 250 mL of dichloromethane. Dibutyl dicarbonate (53.9 g, 2.1 equivalent) was slowly added, and the reaction was stirred at room temperature for 16 hours. The reaction mixture was then washed with saturated sodium bicarbonate, water, and brine, and then dried over magnesium sulfate. The solvent was removed under reduced pressure to yield monomer 1. Monomer 1

[0126] [monomer] [2] Synthesis of [ ]: N-hydroxy-5-norbornene-2,3-dicarboxylic acid amide (15.8 g, 1.0 equivalent) and triethylamine (13.2 g, 1.5 equivalent) were dissolved in 200 mL of dichloromethane. The reaction mixture was cooled to 0°C and methacrylamide chloride (10.0 g, 1.1 equivalent) was slowly added. The reaction mixture was stirred at 23°C–25°C for 16 hours. The reaction mixture was then washed with saturated sodium bicarbonate, water, and brine, and then dried over magnesium sulfate. The solvent was removed under reduced pressure to yield monomer 2. Monomer 2

[0127] [monomer] [13A] [、] [13B] [、] [13C] [,and] [13D] [Synthesis]: Monomer 13A was prepared as shown in Scheme 1: [, plan , ] [, 1 , ] Monomer 13A Among them, R = CH 3, n = 2, (Boc) 2O is dibutyl dicarbonate and DMAP is 4-dimethylaminopyridine.

[0128] Similarly, monomers 13B (R = CH 3, n = 1), 13C (R = H, n = 2), and 13D (R = H, n = 1) were prepared as shown in Scheme 1, wherein (Boc) 2O and DMAP were as defined above.

[0129] [5-] [Synthesis of 5-hydroxypentylamine]: A solution of tetrahydro-2H-piperan-2-one (80.0 g, 799.04 mmol) in ethanol (200 mL, 2.5 vol) was loaded into a 2-L autoclave. The contents of the autoclave were cooled to below -30°C, and liquid ammonia (400 mL, 5 vol) was added. The autoclave was sealed, and the reaction mixture was heated to 90–100°C at 500–575 psi for 24 h. The reaction mixture was then cooled to room temperature, and the resulting solid was filtered from the mixture. The wet filter cake of the resulting solid was washed with ethyl acetate (300 mL, 3.75 vol) and dried under vacuum to yield 5-hydroxypentylamine (64.0 g, 68%) as a white solid. ¹H NMR δ (ppm): 7.20 (bs, ¹H), 6.67 (bs, ¹H), 4.36 (t, J = 8.0 Hz, ¹H); 3.39 (t, J = 12 Hz, 2H), 1.53–1.47 (m, 2H), and 1.46–1.39 (m, 2H); FT-IR: 3400.56 cm⁻¹ (-OH, strong), 1643.3 cm⁻¹ (-C=O, acetylamine), and 3183.57 cm⁻¹ (-NH, acetylamine); UPLC-ELSD: 99.84% purity (1.49 RT); MS: m / z = 118.13 [M+H]⁺.

[0130] [5-] [Amine] [-5-] [Synthesis of oxypentyl methacrylate]: 5-hydroxypentylamine (5.0 g, 42.68 mmol) in 100 mL of dry dichloromethane was added to a 250 mL three-necked round-bottom flask equipped with a magnetic stir bar, internal thermometer, and nitrogen bubbler at room temperature. N,N-dimethyl-4-aminopyridine (521 mg, 4.27 mmol) and triethylamine (11.9 mL, 85.36 mmol) were added, and the resulting suspension was stirred for 15 minutes. Then, methacryl chloride (5 mL, 51.21 mmol) was added dropwise, and the resulting mixture was stirred at room temperature for 16 h. The reaction mixture was diluted with 100 mL of dichloromethane and washed with quenched water (100 mL) and a brine solution (50 mL). The organic layer was separated, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude material was ground with 10% dichloromethane in hexane to produce 5-amino-5-methacrylate oxyamyl ester (6.0 g, 75%) as a pale yellow solid. ¹H NMR δ(ppm): 7.25 (bs, ¹H), 6.71 (bs, ¹H), 6.02–6.01 (m, ¹H), 5.67–5.66 (m, ¹H); 4.13–4.07 (m, 2H), 1.88 (s, 3H), 1.64–1.57 (m, 4H); FT-IR: 2955.0 cm⁻¹ (-C=CH, stretching), 1649.17 cm⁻¹ (-C=O, acetylamine), 1717.64 cm⁻¹ (-C=O, ester) and 3193.21 cm⁻¹ (-NH, acetylamine); LCMS-ELSD: 92.7% purity (1.40 RT); MS: m / z = 186.23 [M+H]⁺.

[0131] [[5-[] [pair] [(] [Level 3] [-] [Butoxycarbonyl] [)] [Amine] []-5-] [Side group] [-] [Pentyl] []2-] [Methylpropane] [-2-] [Occult acid (monomer)] [13A] Synthesis of [ ):] 5-amino-5-sideoxypentyl methacrylate (200 mg, 1.08 mmol), N,N-dimethyl-4-aminopyridine (26.5 mg, 0.21 mmol), and acetonitrile (4 mL) were added to a 25 mL three-necked round-bottom flask equipped with a magnetic stir bar and a nitrogen bubbler at room temperature. (Boc)₂O (0.99 mL, 4.32 mmol) was added, and the resulting mixture was stirred at room temperature for 16 h. The mixture was diluted with ethyl acetate (4 mL) and washed with water (2 mL) and brine (2 mL). The organic layer was separated, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude material was purified by rapid column chromatography on silica gel (100-200 mesh) using a 0-3 vol% ethyl acetate elution gradient in hexane to produce [5-[bis(tert-butoxycarbonyl)amino]-5-sideoxy-pentyl]-2-methylprop-2-enoate (13.50 mg, 12%) as a pale yellow liquid. ¹H NMR δ (ppm): 6.02 (t, J = 1.6 Hz, ¹H), 5.67 (t, J = 3.2 Hz, ¹H), 4.11 (t, J = 12 Hz, 2H), 2.82 (t, J = 14 Hz, 2H), 1.88 (s, 3H), 1.66–1.61 (m, 4H), 1.60 (s, 18H); FT-IR: 2982.9 cm⁻¹ (-C=CH, stretching), 1711.8 cm⁻¹ (-C=O, acetylamine), 1787.0 cm⁻¹ (-CC=O, ester); UPLC-ELSD: 99.55% purity (2.85 RT). No ionization was observed in either LCMS or GCMS. The structure of monomer 13A was confirmed by 2D NMR. Monomer 13A

[0132] [monomer]

[17] [Synthesis:] Bilateral monomer 17 was prepared as shown in Scheme 2: [, plan , ] [, 2 , ]

[0133] [Polymer synthesis, scheme] [1]: An exemplary polymer A2 was prepared as follows. A monomer feed solution was prepared using 23.4 g of propylene glycol monomethyl ether acetate (PGMEA), 10.0 g of monomer 1, and 1.6 g of monomer 4. Separately, an initiator feed solution was prepared using 8.3 g of PGMEA and 0.84 g of V-601. In a reactor, 9.4 g of PGMEA was heated to 80°C, and then the monomer feed solution was added dropwise over 240 minutes, followed by the initiator feed solution over 90 minutes. After 4 hours, the reaction mixture was cooled to room temperature at 1°C / min, and then the polymer was precipitated by direct addition to 1 L of 9 / 1 methanol / water (v / v). The polymer was collected by filtration and dried under vacuum to produce polymer A2.

[0134] [Polymer synthesis, scheme] [2]: An exemplary polymer B2 was prepared as follows. A monomer feed solution was prepared by combining 10 g of propylene glycol monomethyl ether (PGME), 7.0 g of monomer-6, 3.0 g of monomer-7, and 0.50 g of V-601 initiator in a container and stirring the mixture to dissolve the components. Next, 8.6 g of PGME was introduced into the reaction vessel and the vessel was purged with nitrogen for 30 minutes. The reaction vessel was then heated to 95°C with stirring. The feed solution was then introduced into the reaction vessel and fed over 1.5 hours. The reaction vessel was maintained at 95°C with stirring for an additional three hours and then cooled to room temperature. The polymer was precipitated by adding the reaction mixture dropwise to 1 / 5 methanol / water (v / v), collected by filtration, and dried under vacuum. The obtained polymer B2 was a white solid powder. Mw = 12640 Da, PDI = 1.8

[0135] Each polymer in Table 1 was prepared using the synthetic scheme. Note that polymers "A" and "CA" in Table 1 were prepared according to synthetic scheme 1. Polymer "B" was prepared according to the general synthetic scheme 2. The amounts in Table 1 are mole percentages (mol%) of the total moles of repeating units derived from each specific monomer based on the polymer's repeating units. [Table 1] polymer First Single Unit Second single unit Third single unit A1 1 (100%) - - A2 1 (80%) 4 (20%) - A3 2 (100%) - A4 2 (80%) 5 (20%) - A5 13A (100%) - - A6 13A (90%) 4 (10%) - B1 6 (60%) 7 (30%) 4 (10%) B2 6 (70%) 7 (30%) -

[0136] The structures of monomers 1 to 7 and 13 are as follows:

[0137] The chemical structures of compounds C1 and D1 are shown below.

[0138] [Topcoat Composition.] Formulations (topcoat compositions) T1 to T6 were prepared using the components and amounts shown in Table 2. In Table 2, the numbers in parentheses indicate the weight percentage of each component based on 100 wt% of the topcoat composition. Each mixture was filtered through a 0.2 μm PTFE filter prior to coating. The solvents were propylene glycol methyl ether acetate (S1), methyl 2-hydroxyisobutyrate (S2), and dipropylene glycol methyl ether (S3). [Table 2] Topcoat composition Polymer 1 Polymer 2 Additive 1 Additive 2 Solvent system T1 B2[1.14] A1[0.16] C1[0.013] D1[0.007] S1 / S2 / S3[32.6 / 60.2 / 5.9] T2 B1[1.14] A2[0.16] C1[0.013] D1[0.007] S1 / S2 / S3[32.6 / 60.2 / 5.9] T3 B1[1.14] A3[0.16] C1[0.013] D1[0.007] S1 / S2 / S3[32.6 / 60.2 / 5.9] T4 B2[1.14] A4[0.16] C1[0.013] D1[0.007] S1 / S2 / S3[32.6 / 60.2 / 5.9] T5 B1[1.14] A5[0.16] C1[0.013] D1[0.007] S1 / S2 / S3[32.6 / 60.2 / 5.9] T6 B2[1.14] A6[0.16] C1[0.013] D1[0.007] S1 / S2 / S3[32.6 / 60.2 / 5.9]

[0139] [Coating Defect Testing.] Coating defect testing was performed by applying a topcoat composition to a 300 mm exposed silicon wafer using the TEL Lithius wafer trace. The composition was coated to a thickness of 385 Å using a 2.6-second dispensing time and a soft bake at 90°C for 60 seconds. The coated topcoat layer was inspected using a KLA-Tencor Surfscan SP2 wafer surface inspection tool to detect particles of 60 nm and larger.

[0140] [Pattern Defect Test.] A 300 mm exposed silicon wafer was coated with AR™ 40A Bottom Anti-Reflective Coating (BARC) material (DuPont Electronics & Imaging) on ​​a TEL Lithius 300 mm wafer trace and cured at 205°C for 60 seconds to form an 800 Å first BARC layer. AR™ 104 BARC material (DuPont Electronics & Imaging) was coated on top of the first BARC layer and cured at 205°C for 60 seconds to form a 400 Å second BARC layer. EPIC™ 2099 photoresist (DuPont Electronics & Imaging) was coated on top of the BARC stack and soft-baked at 95°C for 60 seconds to form a 950 Å photoresist layer. The topcoat composition shown in Table 2 was coated on top of the photoresist layer and soft-baked at 90°C for 60 seconds to form a 385 Å topcoat layer. A 45 nm 1:1 line / spacer pattern was formed by exposing a wafer to a photomask using an ASML 1900i immersion scanner with 1.35 NA, 0.85 / 0.75 inner / outer σ, X-polarized diode 35Y illumination. The wafer was then exposed to post-exposure baking (PEB) at 95°C for 60 seconds. The wafer was developed with a 0.26 N TMAH developer aqueous solution, rinsed with distilled water, and spin-dried to form the photoresist pattern. Pattern defects on the patterned wafer were inspected using a KLA-Tencor 2800 defect inspection tool.

[0141] The photoresist topcoat compositions invented in T1 to T6 are expected to achieve lower pattern defect density and reduced coating defect density.

[0142] While this disclosure has been described in conjunction with exemplary embodiments now considered to be practical, it should be understood that the invention is not limited to the disclosed embodiments, but rather is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

[0143] none

[0144] none

Claims

1. A topcoat composition comprising: a polymer including repeating units derived from one or more monomers of formula (1); a matrix polymer including repeating units derived from monomers of formula (I) and repeating units derived from monomers of formula (II); and a solvent, wherein, In formula (1), Z1 and Z2 are each independently a single bond or a divalent linking group containing one or more of the following: substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 heteroalkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C1-30 heteroaryl, -O-, -C(O)-, -N(R3)-, -S-, or -S(O)2-, wherein R3 is hydrogen, substituted or unsubstituted C1-30 alkyl The substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C1-30 heteroaryl, or substituted or unsubstituted C2-30 heteroarylalkyl, Z1 and Z2 may form a ring together via single or double bonds between Z1 and Z2 as needed, and R1 and R2 may be independently substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 heteroalkyl, substituted or unsubstituted C3-30 cycloalkyl, or substituted or unsubstituted C2-30 heteroarylalkyl. Substituted C2-30 heterocyclic alkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C1-30 heteroaryl, substituted or unsubstituted C2-30 heteroarylalkyl, substituted or unsubstituted C2-30 alkylheteroaryl, -OR4, or -N(R5)2, wherein R4 and R5 are each independently substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 heteroalkyl, substituted or unsubstituted The C3-30 cycloalkyl, substituted or unsubstituted C2-20 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C1-30 heteroaryl, substituted or unsubstituted C2-30 heteroarylalkyl, or substituted or unsubstituted C2-30 alkylheteroaryl, wherein, if desired, R1 and R2 form a ring together by a single bond or divalent linking group, and L is a single bond or polyvalent linking group, wherein, if desired, L is a polyvalent linking group, further including additional groups of the following formula: And P is a polymerizable group; wherein, in formula (I) and formula (II), Ra is hydrogen, fluorine, cyano, substituted or unsubstituted C1-10 alkyl, or substituted or unsubstituted C1-10 fluoroalkyl; in formula (I), R100 represents substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C3-30 cycloalkyl, or substituted or unsubstituted poly(C1-3 epoxyalkane); in formula (II), L101 represents a single bond or polyvalent linking group, and n is an integer from 1 to 5.

2. The topcoat composition as described in claim 1, wherein, The polymer comprises repeating units derived from one or more monomers of formula (1a): wherein Ra is hydrogen, fluorine, cyano, substituted or unsubstituted C1-10 alkyl, or substituted or unsubstituted C1-10 fluoroalkyl; L is a single bond or polyvalent linker; and, if desired, L is a polyvalent linker further comprising additional groups of the following formula: Z1 and Z2 are identical, wherein Z1 and Z2 are selected from single bonds, -O-, divalent linkers including groups of formula -C(O)-, or divalent linkers including groups of formula -C(O)-O-; R1 and R2 are each independently substituted or unsubstituted C1-30 alkyl; and, if desired, R1 and R2 together form a ring by means of single bonds or divalent linkers.

3. The topcoat composition as described in claim 1 or 2, wherein, L-series single bonds or divalent linking groups selected from one or more of the following: substituted or unsubstituted C1-30 alkyl groups, substituted or unsubstituted C3-30 cycloalkyl groups, substituted or unsubstituted C2-30 heterocycloalkyl groups, substituted or unsubstituted C6-30 aryl groups, substituted or unsubstituted divalent C7-30 arylalkyl groups, substituted or unsubstituted C1-30 heteroarylyl groups, or substituted or unsubstituted divalent C2-30 heteroarylalkyl groups, -O-, -C(O)-, -C(O)-O-, -C(O)-N(R2b)-, -S-, -S(O)2-, or -N(R2b)-S(O)2-, wherein R2b is hydrogen, a straight-chain or branched C1-20 alkyl group, a monocyclic or polycyclic C3-20 cycloalkyl group, or a monocyclic or polycyclic C2-20 heterocycloalkyl group.

4. The topcoat composition as described in claim 1, wherein, L-series -C(O)-C1-10 alkyl-O- groups; Z1 and Z2 are each -O-; and R1 and R2 are each independently substituted or unsubstituted C1-30 alkyl groups.

5. The topcoat composition as described in claim 1, wherein, The polymer further comprises: a polymer having repeating units derived from one or more monomers of formula (2a), (2b), (2c), (2d), or (2e): wherein Ra is hydrogen, fluorine, cyano, substituted or unsubstituted C1-10 alkyl, or substituted or unsubstituted C1-10 fluoroalkyl; R7 to R12 are each independently hydrogen, straight-chain or branched C1-20 alkyl, monocyclic or polycyclic C3-20 cycloalkyl, monocyclic or polycyclic C2-20 heterocyclic alkyl, straight-chain or branched C2-20 alkenyl, monocyclic or polycyclic C3-20 cycloalkenyl, monocyclic or polycyclic C3-20 heterocyclic alkenyl. The aryl group is a C6-20 aryl group, monocyclic or polycyclic, or a C1-20 heteroaryl group, each of which may be substituted or unsubstituted; the prerequisite is that there is only one energetic hydrogen in R7 to R9 and only one energetic hydrogen in R10 to R12; any two of R7 to R9 together may form a ring as required, and each of R7 to R9 may further include, as part of its structure, a hydrogen selected from -O-, -C(O)-, -C(O)-. R10 may contain one or more groups selected from -O-, -S-, -S(O)2-, and -N(R19)-S(O)2-, wherein R19 is hydrogen, a straight-chain or branched C1-20 alkyl, a monocyclic or polycyclic C3-20 cycloalkyl, or a monocyclic or polycyclic C2-20 heterocyclic alkyl; any two of R10 to R12 may be used together to form a ring, and each of R10 to R12 may be used to further include, as part of its structure, one or more groups selected from -O-, -C(O)-, -C(O)-O-, -S-, -S(O)2-, and -N(R20)-S(O)2-, wherein R20 is hydrogen, a straight-chain or branched C1-20 alkyl, a monocyclic or polycyclic C3-20 cycloalkyl, or a monocyclic or polycyclic C2-20 heterocyclic alkyl; L1 may contain a divalent linking group comprising at least one carbon atom, at least one heteroatom, or a combination thereof. R13 to R14 are each independently hydrogen, a straight-chain or branched C1-20 alkyl, a monocyclic or polycyclic C3-20 cycloalkyl, a monocyclic or polycyclic C2-20 heterocyclic alkyl, a monocyclic or polycyclic C6-20 aryl, or a monocyclic or polycyclic C1-20 heteroaryl, each of which may be substituted or unsubstituted except for hydrogen; R15 is a straight-chain or branched C1-20 alkyl, a monocyclic or polycyclic C3-20 cycloalkyl, or a monocyclic or polycyclic C2 -20 heterocyclic alkyl groups, each of which is substituted or unsubstituted, wherein one of R13 or R14 forms a heterocycle together with R15 as needed; R16 to R18 are each independently a straight-chain or branched C1-20 alkyl group, a monocyclic or polycyclic C3-20 cycloalkyl group, a monocyclic or polycyclic C2-20 heterocyclic alkyl group, a monocyclic or polycyclic C6-20 aryl group, or a monocyclic or polycyclic C1-20 heteroaryl group, each of which is substituted or unsubstituted;Any two of R16 to R18 together may form a ring as required, and each of R16 to R18 may further include, as part of its structure, one or more groups selected from -O-, -C(O)-, -C(O)-O-, -S-, -S(O)2-, and -N(R21)-S(O)2-, wherein R21 is hydrogen, a straight-chain or branched C1-20 alkyl, a monocyclic or polycyclic C3-20 cycloalkyl, or a monocyclic or polycyclic C2-20 heterocyclic alkyl; Xa is a polymerizable group selected from norbornene and vinyl; n is 0 or 1; and L2 is a single-bonded or divalent linking group, provided that when Xa is vinyl, L2 is not a single bond.

6. The topcoat composition as described in claim 1, wherein, The polymer further comprises repeating units of monomers derived from formula (III), monomers of formula (IV), or combinations thereof: wherein Ra is hydrogen, fluorine, cyano, substituted or unsubstituted C1-10 alkyl, or substituted or unsubstituted C1-10 fluoroalkyl; R200 is substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C3-30 cycloalkyl; or substituted or unsubstituted poly(C1-3 epoxy); R201 is linear, branched or cyclic C1-20 fluoroalkyl; L201 is a single bond or polyvalent linking group; and m is an integer from 1 to 5.

7. The topcoat composition as described in claim 1, further comprising: a photoacid generator or a thermal acid generator.

8. A coated substrate comprising: A photoresist layer on the substrate; and a topcoat layer formed on the photoresist layer, wherein the topcoat layer is derived from the topcoat composition described in any one of claims 1 to 7.

9. A method for forming a pattern, comprising: A photoresist layer is formed on the substrate; A topcoat layer is formed on the photoresist layer, wherein the topcoat layer is formed from a topcoat composition as described in any one of claims 1 to 7; the topcoat layer and the photoresist layer are exposed to activation radiation in a patterned manner; and the exposed topcoat layer and the exposed photoresist layer are brought into contact with a developer to form a resist pattern.

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