Photoresist compositions and methods of forming patterns

Abstract

A photoresist composition comprising a first polymer comprising first repeat units comprising groups having formula (1) or (2); a second polymer comprising first repeat units comprising acid-labile groups; a photoacid generator; and a solvent, wherein in formula (1) and formula (2), R 1 and R 2 are each independently hydrogen or an organic group; R 1 and R 2 together optionally form a ring; R 1 and R 2 each optionally further comprise one or more divalent linking groups as part of their structure; R 1 or one of R 2 is optionally bonded to the main chain of the first polymer; and represents a bonding point in the first repeat units of the first polymer.(1)(2).

Description

Cross-references to related applications This application claims priority and benefit to U.S. Provisional Application No. 63 / 797,703, filed April 30, 2025, the entire contents of which are incorporated herein by reference. Technical Field

[0001] This invention relates to photoresist compositions and to patterning methods using such photoresist compositions. The photoresist compositions and patterning methods are particularly useful for photolithography applications in the semiconductor manufacturing industry. Background Technology

[0002] Photoresist compositions are photosensitive materials used to transfer patterns onto one or more underlying layers (such as metals, semiconductors, or dielectric layers) disposed on a substrate. Chemically amplified photoresist compositions are commonly used for high-resolution processing. Such resist compositions typically contain a polymer with acid-indestructible groups and a photoacid generator (PAG). The photoresist composition layer is exposed to activating radiation in a patterned manner, and the PAG generates acid in the exposed areas. During post-exposure baking, the acid causes the acid-indestructible groups of the polymer to break down and results in a polarity reversal of the polymer in the exposed areas. This creates a difference in solubility properties between the exposed and unexposed areas of the photoresist layer in the developer solution. During positive development (PTD), the exposed areas of the photoresist layer become soluble in the developer (typically an aqueous alkaline developer) and are removed from the substrate surface, while the unexposed areas remain on the substrate to form a positive relief image. Alternatively, during negative development (NTD), unexposed areas of the photoresist layer can be removed using an organic solvent developer (typically n-butyl acetate), while the exposed areas remain on the substrate to form a negative relief image. The resulting relief image allows for selective processing of the substrate.

[0003] To improve lithography performance, immersion lithography exposure tools have been developed to effectively increase the numerical aperture (NA) of the lens of imaging devices (e.g., scanners with ArF light sources). This is achieved by using a fluid with a relatively high refractive index (i.e., an immersion fluid, typically water) between the last surface of the imaging device and the surface of the photoresist layer on the semiconductor wafer. The immersion fluid allows an increased amount of activation radiation from the light source to be directed into the photoresist layer.

[0004] Direct contact between the immersion fluid and the photoresist layer formed from conventional non-immersion photoresist compositions typically results in the leaching of photoresist components into the immersion fluid. This leaching can contaminate the optical lenses of scanners and cause changes in the effective refractive index and transmission properties of the immersion fluid. As one way to address this problem, photoresist compositions with additive polymers have been developed and are commonly used in the semiconductor manufacturing industry. These additive polymers can self-segregate from other polymers in the composition to the upper surface of the photoresist layer during spin coating. This forms a barrier layer in the photoresist layer that acts as an interface with the immersion fluid during immersion exposure. See, for example, U.S. Patent Application Publication No. 20110255061 A1. The self-segregating property of the additive polymer is due to its hydrophobic nature relative to other polymers in the photoresist composition. In the coated photoresist layer, the barrier layer (also due to the hydrophobicity of the additive polymer) allows for a desired (high) contact angle with the immersion fluid to minimize or prevent the photoresist components from leaching into the immersion fluid and to prevent the immersion fluid from entering the photoresist.

[0005] Certain fluorinated polymers, which can be used as additive polymers in immersion photoresists and simultaneously allow the formation of a barrier layer with desired properties during spin coating, are receiving increasing attention from the semiconductor manufacturing industry and government regulatory agencies for replacement with more sustainable alternatives. Therefore, photoresist compositions containing additive polymers that form the barrier layer and are independent of specific fluorine substitutions are desirable.

[0006] There is a persistent need to address one or more problems related to the prior art in photoresist compositions, and patterning methods using such photoresist compositions. Summary of the Invention

[0007] One aspect provides a photoresist composition comprising a first polymer containing a first repeating unit having a group of formula (1) or (2); a second polymer containing a first repeating unit containing an acid-indestructible group; a photoacid generator; and a solvent. (1) (2) In equations (1) and (2), R 1 and R 2 Each is independently a hydrogen or organic group; R 1 and R 2 Together they can optionally form a ring; R 1 and R 2 Each of the components may optionally further include one or more divalent linking groups as part of its structure; R1 Or R 2 One of them may be optionally bonded to the backbone of the first polymer; and This represents the bonding point in the first repeating unit of the first polymer.

[0008] Another aspect provides a patterning method comprising (a) applying a layer of a photoresist composition as described in any one of claims 1 to 10 onto a substrate; (b) exposing the photoresist composition layer in a patterned manner to activated radiation; and (c) developing the exposed photoresist composition layer to provide a photoresist relief image.

[0009] Another aspect provides a monomer comprising an olefinic unsaturated double bond and a group having formula (1A) or (2A): (1A) (2A) In equations (1A) and (2A), R 1 It is hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, or substituted or unsubstituted C 2-30 Heterene group; R 2a It is an organic group; Z 2 It is NR', O, or S; R' is hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 heteroaryl; R 1a and R 2a Together they can optionally form a ring; R 1a and R 2a Each may optionally further include one or more divalent linking groups as part of its structure; This represents the bonding site in the monomer.

[0010] Another aspect provides a polymer comprising repeating units having groups having formula (1A) or (2A): (1A) (2A) In equations (1A) and (2A), R 1 It is hydrogen, substituted or unsubstituted C1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, or substituted or unsubstituted C 2-30 Heterene group; R 2a It is an organic group; Z 2 It is NR', O, or S; R' is hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 heteroaryl; R 1 and R 2a Together they can optionally form a ring; R 1 and R 2a Each may optionally further include one or more divalent linking groups as part of its structure; R 1 Or R 2a One of them may be optionally bonded to the main chain of the polymer; and This represents the bonding point in the repeating unit of the polymer. Detailed Implementation

[0011] Reference will now be made in detail to exemplary embodiments, examples of which are shown in this specification. In this regard, exemplary embodiments of the invention may take different forms and should not be construed as limited to the description shown herein. Therefore, exemplary embodiments are described below to explain aspects of this specification. As used herein, the term “and / or” includes any and all combinations of one or more of the related 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 encompassing both the singular and plural unless otherwise specified 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 entire scope disclosed herein includes endpoints, and these 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 / a of that term. “Optional” or “optionally” means that an event or situation subsequently described may or may not occur, and the description includes examples of the event occurring and 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 that other element or inserted between the element and the other. In contrast, when an 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 described in the 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, "photochemical rays" or "radiation" refers to, for example, the bright-line spectrum of a mercury lamp, far-ultraviolet light, extreme ultraviolet light (EUV light) represented by an excimer laser, X-rays, particle rays (such as electron beams and ion beams), etc. Additionally, in this invention, "light" refers to photochemical rays or radiation. A krypton fluoride laser (KrF laser) is a specific type of excimer laser, sometimes called an excimer complex laser. "Excimer" is an abbreviation for "excited dimer," and "excimer complex" is an abbreviation for "excited complex." Excimer lasers use a mixture of rare gases (argon, krypton, or xenon) and halogen gases (fluorine or chlorine) that emit coherent stimulated emission (laser) in the ultraviolet range under suitable electrical stimulation and high voltage conditions. Furthermore, unless otherwise stated, "exposure" in this specification includes not only exposure by a mercury lamp, far-ultraviolet light represented by an excimer laser, X-rays, extreme ultraviolet light (EUV light), etc., but also writing by particle rays (such as electron beams and ion beams).

[0015] As used herein, the term "hydrocarbon" refers to an organic compound or group having at least one carbon atom and at least one hydrogen atom; "alkyl" refers to a straight-chain or branched saturated hydrocarbon group 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-"; "carboxyl" and "carboxylic acid" refer to groups having the formula "-C(=O)-OH"; "cycloalkyl" refers to a group having all of its ring members... "A" is a monovalent group of one or more saturated rings of carbon; "cycloalkylene" refers to a cycloalkyl group with a valence of 2; "alkenyl" refers to a straight-chain or branched monovalent hydrocarbon group with at least one carbon-carbon double bond; "alkenoxyl" refers to "alkenyl-O-"; "alkenylene" refers to an alkenyl group with a valence of 2; "cycloalkenyl" refers to a non-aromatic cyclic divalent hydrocarbon group with at least three carbon atoms and at least one carbon-carbon double bond; "alkynyl" refers to a monovalent hydrocarbon group with at least one carbon-carbon triple bond; the term "aromatic group" refers to a group that satisfies Hückel's rule (4n+2). A monocyclic or polycyclic aromatic ring system containing carbon atoms in the ring (π electrons); the term "heteroaromatic group" refers to an aromatic group containing one or more heteroatoms selected from N, O, and S (e.g., 1-4 heteroatoms) that replace carbon atoms in the ring; "aryl" refers to a monovalent monocyclic or polycyclic aromatic 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; "arylene" refers to an aryl group having a valence of 2; "alkylaryl" refers to an aryl group that has been substituted by an alkyl group; "arylalkyl" refers to an alkyl group that has been substituted by an aryl group; "aryloxy" refers to "aryl-O-"; and "arylthio" refers to "aryl-S-".

[0016] The term "organic group" refers to a group containing at least one carbon atom (e.g., 1 to 60 carbon atoms), and may further contain hydrogen atoms, and may also contain nitrogen, oxygen, sulfur, silicon, halogen atoms, etc. Organic groups are not limited and can be hydrocarbon groups or derivatives thereof. Derivatives of hydrocarbon groups refer to groups having one or more of N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc., at the end of a hydrocarbon group or in the molecular chain. Other examples of organic groups include cyano.

[0017] The prefix "hetero" means that a compound or group contains at least one member (e.g., 1, 2, 3, or 4 or more heteroatoms) as a heteroatom in place of a carbon atom, wherein each of the one or more heteroatoms is independently N, O, S, Si, or P; "heteroatom-containing group" refers to a substituent containing at least one heteroatom; "heteroalkyl" refers to an alkyl group having at least one heteroatom in place of a carbon atom.

[0018] The term "heterocyclic alkyl" refers to a cycloalkyl group having at least one heteroatom independently selected from N, O, or S as a ring member replacing a carbon atom; "heterocyclic alkylene" refers to a heterocyclic alkyl group having a valence of 2. Exemplary 3-membered heterocyclic alkyl groups containing one heteroatom include aziridinyl, oxetaneyl, and thiocyclic propylene. Exemplary 4-membered heterocyclic alkyl groups containing one heteroatom include azironeyl, oxetaneyl, and thiocyclic propylene. Exemplary 5-membered heterocyclic alkyl groups containing one heteroatom include tetrahydrofuranyl, dihydrofuranyl, tetrahydrothiophenyl, dihydrothiophenyl, pyrroliyl, dihydropyrroliyl, and pyrroliyl-2,5-diketone. Exemplary 5-membered heterocyclic alkyl groups containing two heteroatoms include dioxopentyl, oxetaneyl, and dithiopentaneyl. Exemplary 5-membered heterocyclic alkyl groups containing 3 heteroatoms include triazolinyl, oxadiazolinyl, and thiadiazolinyl. Exemplary 6-membered heterocyclic alkyl groups containing 1 heteroatom include piperidinyl, tetrahydropyranyl, dihydropyridinyl, and thiaalkyl. Exemplary 6-membered heterocyclic alkyl groups containing 2 heteroatoms include piperazineyl, morpholinyl, dithiaalkyl, and dioxalyl. Exemplary 6-membered heterocyclic alkyl groups containing 2 heteroatoms include triazineyl. Exemplary 7-membered heterocyclic alkyl groups containing 1 heteroatom include azirheptanyl, oxetaneheptyl, and thioheptanyl. Exemplary 8-membered heterocyclic alkyl groups containing 1 heteroatom include azirheptanyl, oxetaneheptyl, and thioheptanyl. Exemplary bicyclic heterocyclic alkyl groups include dihydroindolyl, isodihydroindolyl, dihydrobenzofuranyl, dihydrobenzothiophenyl, tetrahydrobenzothiophenyl, tetrahydrobenzofuranyl, tetrahydroindolyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, decahydroisoquinolinyl, octahydrochromenyl, octahydroisochromenyl, decahydronaphridyl, decahydro-1,8-naphridyl, octahydropyrrolo[3,2-b]pyrrole, dihydroindolyl, phthalimide, naphthalimide, chromenyl, 1H-benzo[e][1,4]diazazolyl, 1,4,5,7-tetrahydropyranolo[3,4-b]pyrrole, 5, 6-Dihydro-4H-furano[3,2-b]pyrrolithyl, 6,7-Dihydro-5H-furano[3,2-b]pyrrolithyl, 5,7-Dihydro-4H-thieno[2,3-c]pyrrolithyl, 2,3-Dihydro-1H-pyrroli[2,3-b]pyridyl, 2,3-Dihydrofurano[2,3-b]pyridyl, 4,5,6,7-Tetrahydro-1H-pyrroli[2,3-b]pyridyl, 4,5,6,7-Tetrahydrofurano[3,2-c]pyridyl, 4,5,6,7-Tetrahydrothieno[3,2-b]pyridyl, and 1,2,3,4-Tetrahydro-1,6-naphthidyl.

[0019] The term "heteroaryl" refers to a 4-8 membered monocyclic, 8-12 membered bicyclic, or 11-14 membered tricyclic aromatic ring system having 1-4 heteroatoms (if monocyclic), 1-6 heteroatoms (if bicyclic), or 1-9 heteroatoms (if tricyclic), wherein each heteroatom is independently selected from N, O, or S (e.g., for monocyclic, bicyclic, or tricyclic systems, a carbon atom and 1-3, 1-6, or 1-9 heteroatoms independently selected from N, O, or S). Exemplary 5-membered heteroaryl groups containing one heteroatom include pyrrole, furanyl, and thiophene. Exemplary 5-membered heteroaryl groups containing two heteroatoms include imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, and isothiazolyl. Exemplary 5-membered heteroaryl groups containing three heteroatoms include triazolyl, oxadiazolyl, and thiazolyl. Exemplary 5-membered heteroaryl groups containing 4 heteroatoms include tetrazolyl. Exemplary 6-membered heteroaryl groups containing 1 heteroatom include pyridyl. Exemplary 6-membered heteroaryl groups containing 2 heteroatoms include pyridazinyl, pyrimidinyl, and pyrazinyl. Exemplary 6-membered heteroaryl groups containing 3 or 4 heteroatoms include triazinyl and tetraazinyl, respectively. Exemplary 7-membered heteroaryl groups containing 1 heteroatom include aziryl, oxazinyl, and thioazinyl. Exemplary 5,6-bicyclic heteroaryl groups include indoleyl, isoindoleyl, indazoleyl, benzotriazolyl, benzothiopheneyl, isobenzothiopheneyl, benzofuranyl, benzoisofuranyl, benzoimidazolyl, benzoxazolyl, benzoisoxazolyl, benzoxadiazolyl, benzothiazolyl, benzoisothiazolyl, benzothiadiazolyl, indoleazinyl, and purineyl. Exemplary 6,6-bicyclic heteroaryl groups include naphridinyl, pteridinyl, quinolinyl, isoquinolinyl, cenolinyl, quinoxalinyl, phthalazinyl, and quinazolinyl. Exemplary tricyclic heteroaryl groups include, but are not limited to, phenanthridine, dibenzofuranyl, carbazoyl, acridineyl, phenothiazinyl, phenotoxazinyl, and phenothiazinyl.

[0020] The term "halogen" refers to a monovalent substituent of fluorine (fluorinated), chlorine (chloroinated), bromine (brominated), or iodine (iodinated). The prefix "halogenated" indicates a group containing 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. For example, the term "halogenated alkyl" refers to an alkyl group substituted with one or more halogens. As used herein, "substituted C" refers to an alkyl group substituted with one or more halogens. 1-8 "Halogenated alkyl" refers to a C that has been substituted with at least one halogen. 1-8 Alkyl groups, and further substituted by one or more other substituents that are not halogens. It should be understood that substitution of groups with halogen atoms should not be considered as heteroatom-containing groups, since halogen atoms do not substitute carbon atoms.

[0021] The term "fluorinated" refers to the presence of one or more fluorine atoms in place of hydrogen atoms in a group. For example, when indicating C... 1-18When fluoroalkyl is used, the fluoroalkyl group may contain 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 in each 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 by at least one additional substituent that does not contain a fluorine atom.

[0022] Unless otherwise explicitly stated, each of the foregoing substituents may be optionally substituted. The term “optionally substituted” means substituted or unsubstituted. “Substituted” means that at least one hydrogen atom of a chemical structure or group is substituted by another terminal substituent, typically monovalent, provided that the valence does not exceed the normal valence of the specified atom. When the substituent is an oxo group (i.e., O), the two twin hydrogen atoms on the carbon atom are replaced by the terminal oxo group. Further note that the oxo group is bonded to the carbon via a double bond to form a carbonyl group (C=O), which is represented herein as -C(O)-. Combinations of substituents or variables are permitted. Exemplary substituents that may be present at the “substituted” position include, but are not limited to, nitro (-NO2), cyano (-CN), hydroxyl (-OH), oxo (O), amino (-NH2), mono- or di-(C 1-6 )alkylamino, alkanoyl (such as C 2-6 Alkyl groups, such as acyl groups, formyl groups (-C(O)H), carboxylic acids or their alkali metal or ammonium salts; 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); amide groups (-C(O)NR2, where R is hydrogen or C). 1-6 alkyl), formamido (-CH2C(O)NR2, where R is hydrogen or C 1-6 Alkyl groups, halogens, mercapto groups (-SH), C 1-6 Alkylthio (-S-alkyl), thiocyano (-SCN), C 1-6 Alkyl, C 2-6 alkenyl, C 2-6 alkynyl group, C 1-6 Haloalkyl, C 1-9 Alkoxy, C 1-6 Halogenated alkoxy groups, C 3-12 cycloalkyl, C 5-18 Cycloalkenyl, C 2-18 Heterocyclic alkenyl groups, C groups having at least one aromatic ring 6-12Aryl (e.g., phenyl, biphenyl, naphthyl, etc., each ring being substituted or unsubstituted aromatic), having 1 to 3 individual or fused rings and 6 to 18 ring carbon atoms, C 7-19 Arylalkyl, arylalkoxy having 1 to 3 individual or fused rings and 6 to 18 ring carbon atoms, C 7-12 alkylaryl, C 2-12 Heterocyclic alkyl, C 3-12 heteroaryl, C 1-6 alkylsulfonyl (-S(O)2-alkyl), C 6-12 Arylsulfonyl (-S(O)2-aryl) or toluenesulfonyl (CH3C6H4SO2-). When the group is substituted, the indicated number of carbon atoms is the total number of carbon atoms in the group, excluding those carbon atoms of any substituents. For example, the group -CH2CH2CN is a cyano-substituted C2 alkyl group.

[0023] As used herein, unless otherwise defined, "divalent linker" means one or more of the following divalent groups: -O-, -S-, -Te-, -Se-, -C(O)-, C(O)O-, -N(R ’ )-、-C(O)N(R ’ -, -S(O)-, -S(O)2-, -C(S)-, -C(Te)-, -C(Se)-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 heteroaryl, or combinations thereof, wherein each R ’ It is independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Heteroaryl groups. Typically, the divalent linking group includes one or more of the following: -O-, -S-, -C(O)-, -N(R')-, -S(O)-, -S(O)2-, substituted or unsubstituted C-. 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 Heteroaryl groups, or combinations thereof, wherein R' is hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 1-20Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Heteroaryl groups. More typically, the divalent linking group includes at least one of the following: -O-, -C(O)-, -C(O)O-, -N(R ' -, -C(O)N(R')-, substituted or unsubstituted C 1-10 Alkylene, substituted or unsubstituted C 3-10 Cycloalkylene, substituted or unsubstituted C 2-10 Heterocyclic alkyl, substituted or unsubstituted C 6-10 aryl, substituted or unsubstituted C 3-10 Heteroaryl groups, or combinations thereof, wherein R is hydrogen, substituted or unsubstituted C. 1-10 Alkyl, substituted or unsubstituted C 1-10 Heteroalkyl, substituted or unsubstituted C 6-10 aryl, or substituted or unsubstituted C 3-10 Mixed aromatic compounds.

[0024] As used herein, an "acid-indestructible group" refers to a group in which a bond is broken by the action of an acid, optionally and typically by thermal treatment, resulting in the formation of a polar group, such as a carboxylic acid or alcohol group. When this type of group is a side group on a polymer, the formation of a polar group occurs on that polymer. Optionally and typically, the portion connected to the broken bond is disconnected from the polymer. In other systems, nonpolymeric compounds may contain an acid-indestructible group that can be broken by the action of an acid, resulting in the formation of a polar group, such as a carboxylic acid or alcohol group, on the broken portion of the nonpolymeric compound. Such an acid is typically a photogenerated acid under conditions where bond breaking occurs during post-exposure baking (PEB); however, the examples are not limited to this, and, for example, such an acid may be thermally generated. 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, acetal groups, or ketal groups. Acid-instable groups are also commonly referred to in this field as “acid-crackable groups”, “acid-crackable protecting groups”, “acid-instable protecting groups”, “acid-leaving groups”, “acid-decomposable groups”, and “acid-sensitive groups”.

[0025] The term "unsaturated bond" refers to a double or triple bond. The terms "unsaturated" or "partially unsaturated" refer to a portion that contains at least one double or triple bond. The term "saturated" refers to a portion that does not contain double or triple bonds, i.e., the portion contains only single bonds.

[0026] As used herein, the term “(meth)acrylic acid” includes both acrylic and methacrylic substances (i.e., acrylic monomers and methacrylic monomers), and the term “(meth)acrylate” includes both acrylate and methacrylate substances (i.e., acrylate monomers and methacrylate monomers).

[0027] Embedded barrier layers (EBLs) for photolithography are typically designed and developed for ArF (193 nm) immersion formulation techniques. EBLs are formed using low surface energy materials, which are added directly to the photoresist composition and can segregate to the surface of the resulting film during spin coating. These materials can be developer-convertible or base-convertible polymers that can be converted from hydrophobic to hydrophilic during the development step. The application of base-convertible polymer additives for defect reduction in formulations other than ArF photoresist compositions has created a need for developing base-convertible polymer additives to further improve photolithography performance at other exposure wavelengths, such as KrF and / or EUV.

[0028] While fluorinated polymers can be useful additive polymers in immersion photoresists because they allow the formation of an EBL, they can be suitably replaced by more sustainable alternatives. To provide a more sustainable alternative EBL, the inventors of this invention have developed a photoresist composition containing additive polymers that form a barrier layer, independent of specific fluorine substitution.

[0029] One aspect provides a photoresist composition comprising a first polymer containing a first repeating unit having a group having formula (1) or (2); a second polymer containing a first repeating unit containing an acid-indestructible group; a photoacid generator; and a solvent. The first polymer contains a first repeating unit containing a group having formula (1) or (2): (1) (2)

[0030] In equations (1) and (2), R 1 and R 2 Each is independently either hydrogen or an organic group. For example, R 1 and R 2 Each can be an independent hydrogen, substituted, or unsubstituted C. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C2-30 Heterene, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Mixed aromatic compounds.

[0031] In equations (1) and (2), R 1 and R 2 Each of them may optionally further include one or more divalent linking groups as part of its structure. For example, R 1 and R 2 Each of these may further include, as part of its structure, one or more groups selected from the following: -O-, -S-, -Si(R 3 )2-、-N(R 3 )-, -S(O)-, -S(O)2-, -C(O)-, -C(O)O-, -C(O)S-, -OC(O)O-, -N(R 3 )C(O)-、-C(O)N(R 3 -, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 heteroaryl, wherein each R 3 It is independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 heteroaryl. For example, R 1 and R 2 Each of these may further include, as part of its structure, one or more groups selected from the following: -O-, -S-, -Si(R 3 )2-、-N(R 3 )-, -S(O)-, -S(O)2-, -C(O)-, -C(O)O-, -C(O)S-, -OC(O)O-, -N(R 3 C(O)- or -C(O)N(R) 3 )-.

[0032] In equations (1) and (2), R 1 and R 2 They can optionally form a ring together. This ring can be formed via one or more divalent linking groups. For example, R 1 and R 2A ring can be formed together via one or more of the following: -O-, -S-, -Te-, -Se-, -C(O)-, C(O)O-, -N(R) 4 )-,-C(O)N(R 4 -, -S(O)-, -S(O)2-, -C(S)-, -C(Te)-, -C(Se)-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 heteroaryl, or combinations thereof, wherein each R 4 It is independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Mixed aromatic compounds.

[0033] In equations (1) and (2), R 1 Or R 2 One of them may optionally be bonded to the backbone of the first polymer. For example, R 1 Or R 2 Optionally, it can be bonded to the backbone of the first polymer via one or more divalent linking groups selected from: -O-, -S-, -Si(R) 5 )2-、-N(R 5 )-, -S(O)-, -S(O)2-, -C(O)-, -C(O)O-, -C(O)S-, -OC(O)O-, -N(R 5 )C(O)-、-C(O)N(R 5 -, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 heteroaryl, wherein each R 5 It is independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Mixed aromatic compounds.

[0034] In equations (1) and (2), This represents the bonding site in the first repeating unit of the first polymer. As noted above, R 1 Or R 2 It can be optionally bonded to the backbone of the first polymer. Therefore, groups having formula (1) or (2) can be... R 1 、or R 2 Any one or more of them are bonded to the backbone of the first polymer. Typically, groups having formula (1) or (2) are bonded via... It is bonded to the main chain of the first polymer.

[0035] In some embodiments, the first repeating unit of the first polymer may comprise a group having formula (1A) or (2A): (1A) (2A)

[0036] In equations (1A) and (2A), R 1a It is hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, or substituted or unsubstituted C 2-30 Heterene group.

[0037] In equations (1A) and (2A), R 2a It is an organic group. For example, R 2a C can be substituted or unsubstituted. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Heterene, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Mixed aromatic compounds.

[0038] In equations (1A) and (2A), Z 2 It is NR', O, or S, where R' is hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Mixed aromatic compounds. Typically, Z2 It is O.

[0039] In equations (1A) and (2A), R 1a and R 2a Each may optionally further include one or more divalent linking groups as part of its structure. For example, R 1a and / or R 2a It may further include, as part of its structure, one or more groups selected from: -O-, -S-, -Si(R 3 )2-、-N(R 3 )-, -S(O)-, -S(O)2-, -C(O)-, -C(O)O-, -C(O)S-, -OC(O)O-, -N(R 3 )C(O)-、-C(O)N(R 3 -, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 heteroaryl, wherein each R 3 It is independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Mixed aromatic compounds.

[0040] In equations (1A) and (2A), R 1a Or R 2a One of them may optionally be bonded to the backbone of the first polymer. For example, R 1a Or R 2a Optionally, it can be bonded to the backbone of the first polymer via one or more divalent linking groups selected from: -O-, -S-, -Si(R) 5 )2-、-N(R 5 )-, -S(O)-, -S(O)2-, -C(O)-, -C(O)O-, -C(O)S-, -OC(O)O-, -N(R 5 )C(O)-、-C(O)N(R 5 -, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C3-30 heteroaryl, wherein each R 5 It is independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Mixed aromatic compounds.

[0041] In equations (1A) and (2A), This represents the bonding site in the first repeating unit of the first polymer. As noted above, R 1a Or R 2a It can be optionally bonded to the backbone of the first polymer. Therefore, groups having formula (1A) or (2A) can be... R 1a 、or R 2a Any one or more of them are bonded to the backbone of the first polymer. Typically, groups having formula (1A) or (2A) are bonded via... It is bonded to the main chain of the first polymer.

[0042] In other embodiments, the first repeating unit of the first polymer may comprise a group having formula (1B) or (2B): (1B) (2B)

[0043] In equations (1B) and (2B), R 1a It is hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, or substituted or unsubstituted C 2-30 Heteroalkenyl. For example, R 1a C can be substituted or unsubstituted. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, or substituted or unsubstituted C 2-30 Heterene

[0044] In equations (1B) and (2B), R 2a It is an organic group. For example, R 2a C can be substituted or unsubstituted.1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Heterene, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Mixed aromatic compounds.

[0045] In equations (1B) and (2B), Z 1 and Z 2 Each is independently a single bond, NR', O, or S, where R' is hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 heteroaryl, provided that Z 1 or Z 2 At least one of them is NR', O, or S.

[0046] In equations (1B) and (2B), R 1a and R 2a Each may optionally further include one or more divalent linking groups as part of its structure. For example, R 1a and / or R 2a It may further include, as part of its structure, one or more groups selected from: -O-, -S-, -Si(R 3 )2-、-N(R 3 )-, -S(O)-, -S(O)2-, -C(O)-, -C(O)O-, -C(O)S-, -OC(O)O-, -N(R 3 )C(O)-、-C(O)N(R 3 -, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 heteroaryl, wherein each R 3 It is independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Mixed aromatic compounds.

[0047] In equations (1B) and (2B), R 1a Or R 2a One of them may optionally be bonded to the backbone of the first polymer. For example, R 1a Or R 2a Optionally, it can be bonded to the backbone of the first polymer via one or more divalent linking groups selected from: -O-, -S-, -Si(R) 5 )2-、-N(R 5 )-, -S(O)-, -S(O)2-, -C(O)-, -C(O)O-, -C(O)S-, -OC(O)O-, -N(R 5 )C(O)-、-C(O)N(R 5 -, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 heteroaryl, wherein each R 5 It is independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Mixed aromatic compounds.

[0048] In equations (1B) and (2B), This represents the bonding site in the first repeating unit of the first polymer. As noted above, R 1a Or R 2a It can be optionally bonded to the backbone of the first polymer. Therefore, groups having formula (1B) or (2B) can be... R 1a 、or R 2a Any one or more of them are bonded to the backbone of the first polymer. Typically, groups having formula (1B) or (2B) are bonded via... It is bonded to the main chain of the first polymer.

[0049] In some embodiments, the first repeating unit of the first polymer is formed from a monomer comprising an olefinic unsaturated double bond. As used herein, an olefinic unsaturated double bond refers to a polymerizable group containing a vinyl group, and typically may be selected from substituted or unsubstituted C2- 20Alkenyl, substituted or unsubstituted norbornene, substituted or unsubstituted (meth)acrylic acid group, substituted or unsubstituted vinyl ether group, substituted or unsubstituted vinyl ketone group, substituted or unsubstituted vinyl ester group, or substituted or unsubstituted vinyl aromatic group.

[0050] In some embodiments, the first polymer does not contain -CF2- and -CF3 groups bonded to carbon atoms. In some embodiments, the first polymer is fluorine-free. It should be understood that "free of -F, -CF3, or -CF2- groups" means that the first polymer does not contain groups such as -CH2CF3 and -CH2CF2CH3.

[0051] Non-limiting exemplary monomers for preparing a first repeating unit comprising a group having formula (1) or (2) include the following:

[0052] The total content of all repeating units having groups of formula (1) or formula (2) in the first polymer is 30 to 100 mol% based on the total number of repeating units in the first polymer. For example, the total content of all repeating units having groups of formula (1) or formula (2) in the first polymer is 40 to 100 mol%, or 50 to 100 mol%, or 60 to 100 mol% based on the total number of repeating units in the first polymer.

[0053] The first polymer may optionally further comprise one or more additional repeating units different from the first repeating unit. For example, the first polymer may optionally comprise one or more additional repeating units as described below. The one or more additional units in the first polymer (if present) may be used in an amount up to 70 mol% based on the total repeating units in the first polymer, and typically 3 to 50 mol%.

[0054] The first polymer is typically present in the photoresist composition in an amount of 0.1 to 20 wt% based on the total solids of the photoresist composition. For example, the first polymer may be present in the photoresist composition in an amount of 0.1 to 10 wt% or 5 to 15 wt%, each based on the total solids of the photoresist composition.

[0055] The first polymer typically has a weight-average molecular weight (Mn) of 1,000 to 50,000 Daltons (Da), preferably 2,000 to 30,000 Da, more preferably 4,000 to 25,000 Da, and even more preferably 5,000 to 25,000 Da. w The first polymer's polydispersity index (PDI) (which is M) w Number-average molecular weight (M n The ratio of 1.1 to 3 is typically 1.1 to 3, and more typically 1.1 to 2. Molecular weight values ​​are determined using polystyrene standards by gel permeation chromatography (GPC).

[0056] The first polymer can be prepared using any one or more suitable methods in the art. For example, one or more monomers corresponding to the repeating units described herein can be fed together or separately using one or more suitable solvents and initiators, and polymerized in a reactor. For example, the first polymer can be obtained by polymerizing the corresponding monomers under any suitable conditions, such as by heating at an effective temperature, irradiating with photochemical radiation at an effective wavelength, or a combination thereof.

[0057] The photoresist composition further comprises a second polymer containing a first repeating unit having an acid-indestructible group. 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, acetal groups, ketal groups, tertiary carbonate groups, and tertiary carbamate groups. Typically, the acid-indestructible group can be an acetal group, a ketal group, a tertiary carbonate group, a tertiary carbamate group, or a tertiary ester group. As used herein, "tertiary carbamate group" includes tertiary carbamate groups having an alkyl group, tertiary carbamate groups having an aryl group, and tertiary carbamate groups having a combination of alkyl and aryl groups. As used herein, "tertiary carbonate group" includes tertiary carbonate groups having an alkyl group, tertiary carbonate groups having an aryl group, and tertiary carbonate groups having a combination of alkyl and aryl groups. Preferably, the acid-indestructible group includes a tertiary ester group.

[0058] In one or more embodiments, the second polymer may comprise a first repeating unit containing an acid-instable repeating unit of a monomer represented by one or more of the derivative formulas (3), (4), (5), (6), or (7): (3) (4) (5) (6) (7)

[0059] In equations (3), (4), and (5), R a R b and R c Each of these can be an independent carbon group: hydrogen, deuterium, halogen, cyano, substituted or unsubstituted. 1-10 Alkyl, or substituted or unsubstituted C 3-6 Cycloalkyl. Preferably, R a R b and R c Each can be independently hydrogen, fluorine, or substituted or unsubstituted C. 1-5 Alkyl groups, typically methyl groups.

[0060] In equation (3), L 1 It is a divalent linker. For example, L 1 It can contain 1 to 10 carbon atoms and at least one heteroatom. In a typical example, L 1 It can be -OCH2-, -OCH2CH2O-, or -N(R) 3a )-, where R 3a Is it hydrogen or C? 1-6 alkyl.

[0061] In equations (3) and (4), R6 To R 11 Each is independently a hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 2-20 Heterocyclic alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 3-20 Cycloalkenyl, substituted or unsubstituted C 3-20 Heterocyclic alkenyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 3-20 heteroaryl, provided that R 6 To R 8 No more than one of them can be hydrogen and R 9 To R 11 No more than one of them can be hydrogen, provided that R 6 To R 8 One of them is hydrogen, then R 6 To R 8 At least one of the other Cs is either substituted or unsubstituted. 6-20 aryl or substituted or unsubstituted C 3-20 heteroaryl, and if R 9 To R 11 One of them is hydrogen, then R 9 To R 11 At least one of the other Cs is either substituted or unsubstituted. 6-20 aryl or substituted or unsubstituted C 3-20 heteroaryl. Preferably, R 6 To R 11 Each is independently either substituted or unsubstituted C 1-6 Alkyl or substituted or unsubstituted C 3-10 Cycloalkyl. R 6 To R 11 Each of them may optionally further include a divalent linker group as part of its structure.

[0062] For example, R 6 To R 11 Any one or more of them can independently be of the formula -CH2C(O)CH (3-n) Y n or -CH2C(O)OCH (3-n) Y n The group, wherein each Y is independently a substituted or unsubstituted C. 2-10 Heterocyclic alkyl groups, and n is 1 or 2. For example, each Y can independently be a group containing the formula -O(C a1 (C) a2 The substitution or unsubstituted C of the O- group2-10 Heterocyclic alkyl groups, wherein C a1 and C a2 Each is independently hydrogen or a substituted or unsubstituted alkyl group, and wherein C a1 and C a2 They can optionally form a ring together.

[0063] In equation (3), R 6 To R 8 Any two of them together may optionally form a ring, which may further include a divalent linking group as part of its structure, and wherein the ring may be substituted or unsubstituted. In formula (4), R 9 To R 11 Any two of them together may optionally form a ring, which may further include a divalent linking group as part of its structure, wherein the ring group may be substituted or unsubstituted.

[0064] In equations (5) and (7), R 12 R 13 R 18 and R 19 Each can be independently hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 2-20 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 3-20 heteroaryl; and R 14 and R 20 Each is independently either substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 2-20 Heterocyclic alkyl groups. Preferably, R 12 R 13 R 18 and R 19 Each can be independently hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 2-20 Heterocyclic alkyl. R 12 R 13 R 18 and R 19 Each of them may optionally further include a divalent linker group as part of its structure.

[0065] In equation (5), R 12 To R 14Any two of them together may optionally form a ring, which may further include a divalent linking group as part of its structure, wherein the ring group may be substituted or unsubstituted.

[0066] In equation (6), R 15 To R 17 Each can be either substituted or unsubstituted C independently. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 2-20 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 3-20 heteroaryl, provided that R 15 To R 17 No more than one of them can be hydrogen, provided that R 15 To R 17 One of them is hydrogen, then R 15 To R 17 At least one of the other Cs is either substituted or unsubstituted. 6-20 aryl or substituted or unsubstituted C 3-20 Mixed aromatics. R 15 To R 17 Each of them may optionally further include a divalent linker group as part of its structure.

[0067] For example, R 15 To R 17 Any one or more of them can independently be of the formula -CH2C(O)CH (3-n) Y n or -CH2C(O)OCH (3-n) Y n The group, wherein each Y is independently a substituted or unsubstituted C. 2-10 Heterocyclic alkyl groups, and n is 1 or 2. For example, each Y can independently be a group containing the formula -O(C a1 (C) a2 The substitution or unsubstituted C of the O- group 2-10 Heterocyclic alkyl groups, wherein C a1 and C a2 Each is independently hydrogen or a substituted or unsubstituted alkyl group, and wherein C a1 and C a2 They can optionally form a ring together.

[0068] In equation (6), R 15 To R 17 Any two of them may optionally form a ring together, which may further include a divalent linking group as part of its structure, wherein the ring group may be substituted or unsubstituted.

[0069] In equations (6) and (7), X a and X b Each is independently a polymerizable group containing an olefinic unsaturated double bond, preferably (meth)acrylate or C2 olefin.

[0070] In equations (6) and (7), L 2 and L 3 Each is independently a single bond or a divalent linker, provided that X is a single bond or a divalent linker. a When it is C2 alkenyl, L 2 It is not a single bond, and when X b When it is C2 alkenyl, L 3 It is not a single bond. Preferably, L 2 and L 3 Each is independently either substituted or unsubstituted C 6-30 aryl or substituted or unsubstituted C 6-30 Cycloalkylene.

[0071] In equations (6) and (7), n1 is 0 or 1, and n2 is 0 or 1. It should be understood that when n1 is 0, L 2 The group is directly attached to the oxygen atom. It should be understood that when n² is 0, L... 3 The group is directly attached to the oxygen atom.

[0072] In equation (7), R 18 To R 20 Any two of them together may optionally form a ring, which may further include a divalent linking group as part of its structure, wherein the ring group may be substituted or unsubstituted.

[0073] In some respects, R 6 To R 20 Each of these may optionally further comprise, as part of its structure, one or more divalent linking groups selected from the following: -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R ' )-, or -C(O)N(R')-, where R ' It can be hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 2-20 Heterocyclic alkyl groups.

[0074] Non-limiting examples of repeating units having acid-labile groups include the following: Where R d It is hydrogen, deuterium, halogen, substituted or unsubstituted C 1-6 Alkyl, or substituted or unsubstituted C 3-6 Cycloalkyl.

[0075] The total content of all repeating units containing acid-labile groups in the second polymer is 5 to 100 mol% based on the total number of repeating units in the second polymer. For example, the total content of all repeating units containing acid-labile groups in the second polymer is 15 to 100 mol%, or 15 to 80 mol%, or 30 to 60 mol% based on the total number of repeating units in the second polymer.

[0076] The second polymer may optionally further comprise one or more additional repeating units different from the first repeating unit. For example, the second polymer may optionally comprise one or more additional repeating units as described below. The one or more additional units in the second polymer (if present) may be used in an amount up to 80 mol% based on the total repeating units of the second polymer, and typically 3 to 60 mol%.

[0077] The second polymer is typically present in the photoresist composition in an amount of 0.1 to 80 wt% based on the total solids of the photoresist composition. For example, the second polymer may be present in the photoresist composition in an amount of 0.1 to 75 wt% or 15 to 70 wt%, each based on the total solids of the photoresist composition.

[0078] The second polymer typically has an M of 1,000 to 50,000 Da, preferably 2,000 to 30,000 Da, more preferably 4,000 to 25,000 Da, and even more preferably 5,000 to 25,000 Da. w The PDI of the second polymer is typically 1.1 to 3, and more typically 1.1 to 2. Molecular weight values ​​are determined using polystyrene standards via GPC.

[0079] The second polymer can be prepared using any one or more suitable methods in the art. For example, one or more monomers corresponding to the repeating units described herein can be fed together or separately using one or more suitable solvents and initiators, and polymerized in a reactor. For example, the second polymer can be obtained by polymerizing the corresponding monomers under any suitable conditions, such as by heating at an effective temperature, irradiating with photochemical radiation at an effective wavelength, or a combination thereof.

[0080] In addition to the first repeating unit as described above, the first polymer and / or the second polymer may further comprise one or more additional repeating units. These additional repeating units may be one or more units for purposes such as modulating the properties of the composition, such as etching rate and solubility. Exemplary repeating units may include those derived from one or more of (meth)acrylates, vinyl aromatic compounds, vinyl ethers, vinyl ketones, and / or vinyl ester monomers. The first and second polymers of the composition may be homopolymers or copolymers comprising two or more structurally different repeating units.

[0081] In some aspects, the first polymer and / or the second polymer may further comprise repeating units containing polar groups, wherein the polar groups are side-attached to the backbone of the respective polymer. For example, the polar groups may be lactone groups, sulopentalide groups, hydroxyaryl groups, carboxylic acid groups, or combinations thereof, but the embodiments are not limited thereto.

[0082] In one or more embodiments, the first polymer and / or the second polymer may further comprise repeating units derived from one or more monomers having formula (8): (8) Where R a It is hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C 1-10 Alkyl, or substituted or unsubstituted C 3-6 Cycloalkyl.

[0083] In equation (8), L 4 It is a single bond or one or more divalent linking groups. L 4 Exemplary divalent linking groups include one or more of the following: substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 Hybrid aryl, -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R 8a )-、or--C(O)N(R 8b )-, where R 8a and R 8b Each can be an independent hydrogen, substituted, or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Mixed aromatic compounds.

[0084] It should be understood that when L 4 When it is a single bond, part of -R 21 Directly attached to the oxygen atom adjacent to the carbonyl group (i.e., -C(O)OR) 21 ).

[0085] In equation (8), R 21 Is it a substituted or unsubstituted C-containing compound? 4-20 The lactone group may be substituted or unsubstituted, containing C. 4-20 The group of sulfonyl lactone. Contains C.4-20 lactone groups and C-containing groups 4-20 The functional groups of sulfonyl lactones can be monocyclic, polycyclic, or fused polycyclic.

[0086] An exemplary monomer having formula (8) may include one or more of the following: Where R f For R in equation (8) a As defined.

[0087] In some respects, the repeating unit containing the polar group can be an alkali-soluble repeating unit and / or having a pKa of less than or equal to 12. For example, such a repeating unit can contain one or more monomers having formula (9), (10), or (11): (9) (10) (11) Each R g It can be hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C. 1-10 Alkyl, or substituted or unsubstituted C 3-6 Cycloalkyl. Preferably, R g It can be hydrogen, fluorine, or substituted or unsubstituted C. 1-5 Alkyl groups, typically methyl groups.

[0088] In equation (9), R 22 C can be substituted or unsubstituted. 1-100 Or C 1-20 Alkyl, typically C 1-12 Alkyl; substituted or unsubstituted C 3-30 Or C 3-20 cycloalkyl; or substituted or unsubstituted poly(C) 1-3 Epoxides). Preferably, substituted C 1-100 Or C 1-20 Alkyl, substituted C 3-30 Or C 3-20 cycloalkyl and substituted poly(C) 1-3 Epoxides are substituted by one or more of the following: halogens, fluoroalkyl groups (such as C... 1-4 Fluorinated alkyl groups (typically fluoromethyl groups), sulfonamide groups -NH-S(O)2-Y 1 (where Y) 1 Is it F or C? 1-4 Perfluoroalkyl (e.g., -NHSO2CF3) or fluoroalcohol group (e.g., -C(CF3)2OH).

[0089] In equation (10), L 5 Indicates a single bond or a multivalent linker selected from, for example, the following: optionally substituted aliphatic groups (such as C 1-6 Alkylene or C 3-20 Cycloalkylene hydrocarbons and aromatic hydrocarbons, and combinations thereof, optionally having one or more connecting moieties selected from: -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -NR 10a -、or-C(O)N(R) 10a )-, where R 10a Selected from hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Heteroaryl. For example, the first polymer and / or the second polymer may further comprise repeating units derived from one or more monomers having formula (10), wherein L 5 It is a single bond or a polyvalent linker selected from the following: substituted or unsubstituted C 1-20 Alkylene, typically C 1-6 Alkylene; substituted or unsubstituted C 3-20 Cycloalkylene; typically C 3-10 Cycloalkylene; and substituted or unsubstituted C 6-24 Alpha-aryl.

[0090] In equation (10), n3 is an integer from 1 to 5, typically 1. It should be understood that when n3 is 1, the group L... 5 It is a divalent linker. It should be understood that when n3 is 2, the group L... 5 It is a trivalent linker. Similarly, it should be understood that when n3 is 3, the group L... 5 It is a tetravalent linker; when n3 is 4, the group L 5 It is a pentavalent linker; and when n3 is 5, the group L 5 It is a hexavalent linker. Therefore, in the context of formula (10), the term "multivalent linker" refers to any of the divalent, trivalent, tetravalent, pentavalent, and / or hexavalent linkers. In some respects, when n3 is 2 or greater, the carboxylic acid group (-C(O)OH) can be linked to the linker L. 5 The same atom. In other respects, when n3 is 2 or greater, the carboxylic acid group (-C(O)OH) can be attached to the linking group L. 5 Different atoms.

[0091] In equation (11), L 6 This represents a single bond or one or more divalent linking groups. Preferably, L6 It can be a single bond, substituted, or unsubstituted C. 6-30 aryl, or substituted or unsubstituted C 6-30 Cycloalkylene.

[0092] In equation (11), Ar is the substituted C. 5-60 An aromatic group, optionally comprising one or more aromatic cyclic heteroatoms selected from N, O, S, or combinations thereof, wherein the aromatic group may be monocyclic, non-fused polycyclic, or fused polycyclic. When C 5-60 When the aromatic group is polycyclic, the ring or cyclic group can be fused (such as naphthyl), non-fused, or a combination thereof. When the polycyclic C... 5-60 When aromatic groups are non-fused, the rings or cyclic groups can be directly connected (e.g., biaryl, biphenyl, etc.) or bridged by heteroatoms (e.g., triphenylamino or diphenylene ether). In some respects, polycyclic C 5-60 Aromatic groups can include combinations of fused rings and directly linked rings (such as binaphthyl groups).

[0093] In equation (11), y can be an integer from 1 to 12, preferably from 1 to 6, and typically from 1 to 3. Each R x It can be hydrogen or methyl independently.

[0094] Non-limiting examples of repeating units having equations (9), (10), and / or (11) include one or more of the following: Where R d It can be hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C. 1-10 Alkyl, or substituted or unsubstituted C 3-6 Cycloalkyl. Preferably, R d It can be hydrogen, fluorine, or substituted or unsubstituted C. 1-5 Alkyl groups, typically methyl groups.

[0095] When present, the first polymer and / or the second polymer typically contain repeating units comprising polar groups (side-attached to the polymer backbone) in amounts of 1 to 60 mol%, typically 5 to 50 mol%, and more typically 5 to 40 mol%, based on the total repeating units in the polymer.

[0096] The repeating units of the first and / or second polymer may contain salt groups. As used herein, a "salt group" refers to a portion having a positive and / or negative charge, such as a positively or negatively charged portion having a side-bonded portion to the backbone of the respective polymer. The repeating units of the polymer containing salt groups may contain photoacid generator (PAG) groups or photodegradable quencher (PDQ) groups. For example, the repeating units of the first and / or second polymer may contain salt groups represented by formula (12a) or (12b): (12a) (12b)

[0097] In equations (12a) and (12b), each R m It can be hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C. 1-10 Alkyl, or substituted or unsubstituted C 3-6 Cycloalkyl. Preferably, R m It is hydrogen, fluorine, or substituted or unsubstituted C. 1-5 Alkyl groups, typically methyl groups.

[0098] In equations (12a) and (12b), Q 1 and Q 2 Each can be a single bond or a divalent linker independently. Preferably, Q 1 and Q 2 Each may independently contain 1 to 10 carbon atoms and at least one heteroatom, more preferably -C(O)-O-.

[0099] In equations (12a) and (12b), A 1 and A 2 It can be one or more of the following, either substituted or unsubstituted: C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Hybrid aryl. In some embodiments, A 1 and A 2 Each can be an optional substitute for divalent C, which can be used independently. 1-30 Perfluoroalkylene groups.

[0100] In equation (12a), Z - Is it bonded to A 1 The anionic portion of Z typically has a pKa of -15 to 10. -It can be a sulfonate, carboxylate, sulfonamide anion, sulfonamide anion, or methyl anion.

[0101] In equation (12a), G + It is an organic cation as defined herein. In some embodiments, G + It is an iodonium cation substituted with two alkyl groups, two aryl groups, or a combination of alkyl and aryl groups; or a sulfonium cation substituted with three alkyl groups, three aryl groups, or a combination of alkyl and aryl groups.

[0102] In equation (12b), Z - These are anionic compounds as defined herein, whose conjugate acids typically have pKa values ​​from -15 to 10. - It can be a sulfonate, carboxylate, sulfonamide anion, sulfonamide anion, or methylated anion.

[0103] In equation (12b), G + Is it bonded to A 2 Organic cations. For example, G + It may include iodonium cations substituted with two alkyl groups, two aryl groups, or a combination of alkyl and aryl groups; or sulfonium cations substituted with three alkyl groups, three aryl groups, or a combination of alkyl and aryl groups.

[0104] In other embodiments, when the first polymer and / or the second polymer comprises repeating units having salt groups, the respective polymers may comprise zwitterionic substances. For example, the first polymer and / or the second polymer may comprise repeating units having salt groups of formula (12c): (12c) In equation (12c), each R m Independently defined as for equations (12a) and (12b).

[0105] In equation (12c), Q 1 A 1 and Z - It is as defined in equation (12a), and Q 2 A 2 and G + It is defined as in equation (12b).

[0106] An exemplary repeating unit having formula (12a) includes the following: Among them G + It is an organic cation, and each R d Independently, R is as shown in equation (12a). m As defined.

[0107] An exemplary repeating unit having formula (12b) includes the following: Z - It is an anionic group as defined in this article, and each R d Independently, R is as in equation (12b). m As defined.

[0108] The salt-containing repeating units of the first polymer and / or the second polymer can typically be present in amounts of 1 to 35 mol%, typically 1 to 25 mol%, and more typically 2 to 15 mol%, based on the total repeating units of the respective polymer.

[0109] The first polymer and / or the second polymer may contain repeating units containing base-indestructible groups. As mentioned herein, base-indestructible groups are functional groups that can undergo a cleavage reaction in the presence of an aqueous base developer after exposure and post-exposure baking steps to provide polar groups (such as hydroxyl, carboxylic acid, sulfonic acid, etc.). Base-indestructible groups will not react significantly prior to the development step of the photoresist composition containing base-indestructible groups (e.g., will not undergo bond-breaking reactions). Therefore, for example, base-indestructible groups will be substantially inert during the pre-exposure soft bake, exposure, and post-exposure baking steps. "Substantially inert" means during the pre-exposure soft bake, exposure, and post-exposure baking steps. 5%, typically 1% of the base-unstable group (or portion thereof) will decompose, cleave, or react. The base-unstable group is reactive under typical photoresist development conditions using, for example, an aqueous base photoresist developer (such as a 0.26 N standard (N) aqueous solution of tetramethylammonium hydroxide (TMAH)). For example, a 0.26 N TMAH aqueous solution can be used for single-immersion development or dynamic development, where, for example, 0.26 N TMAH developer is dispensed onto the imaged photoresist layer for a suitable duration, such as 10 to 120 seconds (s). Exemplary base-unstable groups are ester groups, typically fluorinated ester groups. In some cases, the polymer containing the base-unstable group is substantially immiscible with the first polymer and the other solid components of the composition and has a lower surface energy than them. Thus, when coated onto a substrate, the polymer containing the base-unstable group can segregate from the other solid components of the composition to the top surface of the formed photoresist layer.

[0110] The base-unstable repeating unit can be derived from one or more monomers having formula (13): (13)

[0111] In equation (13), X e It is typically selected from substituted or unsubstituted C2- 20 Polymerizable groups of alkenyl or substituted or unsubstituted (meth)acryloyl groups.

[0112] In equation (13), L 7 It can include one or more of the following divalent linking groups: substituted or unsubstituted C 1-20 Alkylene, substituted or unsubstituted C 3-20 Cycloalkylene, -C(O)-, or -C(O)O-.

[0113] In equation (13), R 23 Is it substituted or unsubstituted C? 1-20 Fluoroalkyl, provided that the carbon atom of the carbonyl group (C=O) bonded to formula (13) is replaced by at least one fluorine atom.

[0114] Exemplary repeating units derived from monomers having formula (13) may include the following: Where R d It can be hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C. 1-10 Alkyl, or substituted or unsubstituted C 3-6 Cycloalkyl. Preferably, R d It can be hydrogen, fluorine, or substituted or unsubstituted C. 1-5 Alkyl groups, typically methyl groups.

[0115] The first polymer and / or the second polymer may comprise repeating units containing two or more base-indestructible groups. For example, the respective polymer may comprise repeating units derived from one or more monomers having formula (14): (14)

[0116] In equation (14), X f Is it like X e The defined polymerizable groups.

[0117] In equation (14), R 24 Is it substituted or unsubstituted C? 1-20 Fluoroalkyl, provided that the carbon atom of the carbonyl group (C=O) bonded to formula (14) is replaced by at least one fluorine atom.

[0118] In equation (14), L 8 It includes one or more of the following multivalent linking groups: substituted or unsubstituted C 1-20 Alkylene, substituted or unsubstituted C 3-20 Cycloalkylene, -C(O)-, or -C(O)O-.

[0119] In equation (14), n3 is an integer of 2 or greater, such as 2 or 3.

[0120] Exemplary repeating units derived from monomers having formula (14) may include the following: Where R d It can be hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C. 1-10 Alkyl, or substituted or unsubstituted C 3-6 Cycloalkyl. Preferably, R d It can be hydrogen, fluorine, or substituted or unsubstituted C. 1-5 Alkyl groups, typically methyl groups.

[0121] For example, the first polymer and / or the second polymer may contain repeating units derived from one or more monomers having formula (15): (15)

[0122] In equation (15), X g Is it like X e The defined polymerizable groups.

[0123] In equation (15), R 25Is it substituted or unsubstituted C? 1-20 alkyl.

[0124] In equation (15), L 9 It is a divalent linker.

[0125] In equation (15), L 10 Is it substituted or unsubstituted C? 1-20 Fluorinated alkylene groups, wherein the carbon atom bonded to the carbonyl group (C=O) in formula (15) is replaced by at least one fluorine atom.

[0126] Exemplary repeating units derived from monomers having formula (15) may include the following: Where R d It can be hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C. 1-10 Alkyl, or substituted or unsubstituted C 3-6 Cycloalkyl. Preferably, R d It can be hydrogen, fluorine, or substituted or unsubstituted C. 1-5 Alkyl groups, typically methyl groups.

[0127] When present, repeating units with base-unstable groups may be present in the first and / or second polymers in amounts of 1 to 95 mol%, more typically 1 to 80 mol%, and even more typically 10 to 50 mol%, based on the total repeating units in the respective polymers.

[0128] The non-limiting exemplary second polymer of the present invention includes one or more of the following: Each of x, y, and z is the mole fraction of the relevant repeating unit, where the sum of the mole fractions of each polymer is 1, and where each R d Independently, it can be hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C. 1-10Alkyl, or substituted or unsubstituted C 3-6 Cycloalkyl. Preferably, R d It can be hydrogen, fluorine, or substituted or unsubstituted C. 1-5 Alkyl groups, typically methyl groups.

[0129] The photoresist composition further comprises a photoacid generator (PAG). PAG can be in ionic or nonionic form. PAG can be in polymeric or nonpolymeric form. When in polymeric form, PAG can be present as part of a repeating unit in a polymer derived from a polymerizable PAG monomer. In some embodiments, PAG is not included in the structure of the first polymer.

[0130] In some embodiments, the photoresist composition may contain two or more different photoacid generating compounds.

[0131] Suitable PAG compounds can have the formula G + Z - G + It is an electroactive cation and Z - These are anions capable of producing photoacids. Electroactive cations are preferably selected from onium cations, more preferably iodonium or sulfonium cations. Particularly suitable anions include those whose conjugate acid has a pKa of -15 to 10. Anions are typically organic anions having a sulfonate group or a non-sulfonate group such as sulfonamidate, sulfonimidate, methylate, or borate.

[0132] In some respects, the anion of PAG does not include and is free from -F, -CF3, or -CF2- groups. It should be understood that "free from -F, -CF3, or -CF2- groups" means that the anion of PAG does not contain groups such as -CH2CF3 and -CH2CF2CH3. In other respects, the anion of PAG is fluorine-free (i.e., it does not contain fluorine atoms and is not substituted by fluorine-containing groups). In some respects, the photoacid generator is fluorine-free (i.e., neither the photoactive cation nor the anion is fluorine-free).

[0133] Ionic PAG compounds contain organic cations (also referred to as G in this article). + For example, the organic cation can be a sulfonium cation or an iodonium cation. In some embodiments, the organic cation can be a sulfonium cation having formula (16) or an iodonium cation having formula (17): (16) (17)

[0134] In equations (16) and (17), R 25 To R29 Each is independently either substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 heteroaryl, substituted or unsubstituted C 7-20 arylalkyl, or substituted or unsubstituted C 4-20 Heteroaryl alkyl groups, or combinations thereof. R 25 To R 27 Each of them can be attached to R individually or via a single bond or a divalent linker. 25 To R 27 Another group in it forms a ring. R 28 and R 29 They can be individual or linked together via single or divalent connecting groups to form a ring. R 25 To R 29 Each of them may optionally contain a divalent linker as part of its structure. R 25 To R 29 Each of these groups may optionally contain an acid-labile group selected from, for example, the following: a tertiary alkyl ester group, a secondary or tertiary aryl ester group, a secondary or tertiary ester group having a combination of alkyl and aryl groups, a tertiary alkoxy group, an acetal group, or a ketal group.

[0135] Exemplary sulfonium cations having formula (16) include one or more of the following:

[0136] An exemplary iodonium cation having formula (17) may include one or more of the following:

[0137] Exemplary organic anions with sulfonate groups (also referred to herein as Z) - This includes one or more of the following:

[0138] An exemplary nonsulfonated anion (also referred to herein as Z) - This includes one or more of the following:

[0139] Commonly used onium salts may include, for example, triphenylsulfonium trifluoromethane sulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethane sulfonate, tri(p-tert-butoxyphenyl)sulfonium trifluoromethane sulfonate, triphenylsulfonium p-toluene sulfonate; di-tert-butylphenyliodomonium perfluorobutane sulfonate, and di-tert-butylphenyliodomonium camphor sulfonate. Other available PAG compounds are known in the field of chemically amplified photoresists and include, for example: nonionic sulfonyl compounds, 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; and diazomethane derivatives, such as bis(benzenesulfonyl)diazomethane and bis(p-toluenesulfonyl)diazomethane. Methane; dioxime derivatives, such as bis-O-(p-toluenesulfonyl)-α-dimethyldioxime and bis-O-(n-butanesulfonyl)-α-dimethyldioxime; sulfonate derivatives of N-hydroxyimide compounds, such as N-hydroxysuccinimide methanesulfonate and N-hydroxysuccinimide trifluoromethanesulfonate; and halogenated triazine compounds, such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine and 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine. Suitable photoacid generators are further described in U.S. Patent Nos. 8,431,325 and 4,189,323.

[0140] In some embodiments, the PAG compound may be a nonionic PAG compound. In some embodiments, a nonionic PAG may include sulfonyl esters, imino esters, imide esters, or combinations thereof.

[0141] Exemplary nonionic PAGs include one or more of the following: Where R is C, either substituted or unsubstituted. 1-10 Alkyl, or substituted or unsubstituted C 1-10 Fluorinated alkyl groups.

[0142] Typically, when the composition contains a non-polymeric PAG compound, the PAG compound is present in the composition in an amount of 0.1 to 55 wt%, more typically 1 to 25 wt%, based on the total solids of the photoresist composition. When present in polymeric form, the PAG compound is typically contained in the polymer in an amount of 1 to 25 mol%, more typically 1 to 8 mol%, or 2 to 6 mol%, based on the total repeating units in the respective polymer.

[0143] The photoresist composition further comprises a solvent for dissolving the components of the composition and promoting its coating on a substrate. Preferably, the solvent is an organic solvent commonly used in the manufacture of electronic devices. Suitable solvents include, for example: aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane (DCM), 1,2-dichloroethane, and 1-chlorohexane; alcohols such as methanol, ethanol, 1-propanol, isopropanol, tert-butanol, 2-methyl-2-butanol, 4-methyl-2-pentanol, and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone) (DAA); propylene glycol monomethyl ether (PGME); ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and anisole; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ether. Ketones, 2-heptanone, and cyclohexanone (CHO); esters, such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), methyl hydroxyisobutyrate (HBM), and ethyl acetoacetate; lactones, such as γ-butyrolactone (GBL) and ε-caprolactone; lactams, such as N-methylpyrrolidone; nitriles, such as acetonitrile and propionitrile; cyclic or acyclic carbonates, such as propylene carbonate, dimethyl carbonate, ethylene carbonate, and diphenyl carbonate; polar aprotic solvents, such as dimethyl sulfoxide and dimethylformamide; water; and combinations thereof. Among these, preferred solvents include one or more of the following: PGME, PGMEA, EL, GBL, HBM, CHO, DAA, or combinations thereof.

[0144] The total solvent content (i.e., the cumulative solvent content of all solvents) in a photoresist composition is typically 40 to 99 wt%, for example 60 to 99 wt%, or 85 to 99 wt%, based on the total solids of the composition. The desired solvent content will depend, for example, on the desired thickness of the coated (photoresist) layer and the coating conditions.

[0145] In some embodiments, the photoresist composition in a coated and dried state exhibits a receding contact angle greater than 60° (before development). For example, in the coated and dried state and before development, the photoresist composition may have a receding contact angle of 60° to 90° or 60° to 80°.

[0146] In some embodiments, the photoresist composition is fluorine-free.

[0147] Additionally, the composition may further comprise one or more polymers other than and different from the polymers described above. For example, the composition may comprise additional polymers as described above but with different compositions. Additionally, or alternatively, the one or more additional polymers may comprise those well known in the field of photoresists, for example, those selected from: polyacrylates, polyvinyl ethers, polyesters, polynorbornene, polyacetals, polyethylene glycol, polyamides, polyacrylamide, polyphenols, phenolic varnishes, styrene polymers, polyvinyl alcohol, or combinations thereof.

[0148] The composition may further comprise 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 composition in an amount of 0.01 to 20 wt% based on the total solids of the composition.

[0149] PDQ irradiation produces relatively weak acids, resulting in a pK value of the acids produced by PDQ. a The pK of the acid produced by PAG is less than that of the acid produced by PAG. a Exemplary photodegradable quenchers include, for example, photodegradable cations, and are preferably also used to prepare strong acid generating compounds, and with weaker acids (pK). a (PDQ) < pK a (PAG) anions (e.g., like C) 1-20 Those that pair with the anion of a carboxylic acid. Exemplary carboxylic acids include formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexanecarboxylic acid, benzoic acid, salicylic acid, etc. In a preferred embodiment, the photodegradable quencher is a photodegradable organic zwitterionic compound, such as diphenyliodonium-2-carboxylate.

[0150] PDQ can be in a non-polymeric or polymerically bonded form. The polymeric unit containing the photodegradable quencher is typically present in an amount of 0.1 to 30 mol%, preferably 1 to 10 mol%, and more preferably 1 to 2 mol%, based on the total repeating units of the polymer. For example, PDQ can be part of a second polymer or an additional polymer. In some embodiments, PDQ is not included in the first polymer.

[0151] Exemplary basic quenchers include, for example, straight-chain aliphatic amines such as tributylamine, trioctylamine, triisopropanolamine, tetra(2-hydroxypropyl)ethylenediamine:n-tert-butyldiethanolamine, 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-(tert-butoxy) Carbonyl)-4-hydroxypiperidine, tert-butyl 1-pyrrolidinecarboxylate, tert-butyl 2-ethyl-1H-imidazolium-1-carboxylate, di-tert-butyl piperazine-1,4-dicarboxylate, and N-(2-acetoxy-ethyl)morpholine; aromatic amines, such as pyridine, lutidine, di-tert-butylpyridine, and pyridinium; linear and cyclic amides and their derivatives, such as N,N-bis(2-hydroxyethyl)palmitamide, N,N-diethylacetamide, N... 1 N 1 N 3 N 3 -Tetrabutylmalonamide, 1-methylazacycloheptan-2-one, 1-allylazacycloheptan-2-one, and tert-butyl 1,3-dihydroxy-2-(hydroxymethyl)propyl-2-ylcarbamate; ammonium salts, such as quaternary ammonium salts of sulfonates, aminosulfonates, carboxylates, and phosphonates; imines, such as primary and secondary aldehyde imines and ketimines; diazines, such as optionally substituted pyrazines, piperazines, and phenazines; diazoles, such as optionally substituted pyrazoles, thiadiazoles, and imidazoles; and optionally substituted pyrrolidones, such as 2-pyrrolidone and cyclohexylpyrrolidine.

[0152] The alkaline quencher can be in a non-polymeric or polymerically bonded form. When in a polymeric form, the quencher can be present in repeating units of the polymer. The repeating units containing the quencher are typically present in an amount of 0.1 to 30 mol%, preferably 1 to 10 mol%, and more preferably 1 to 2 mol%, based on the total repeating units of the polymer. For example, the alkaline quencher can be part of a second polymer, or it can be part of an additional polymer. In some embodiments, the alkaline quencher is not contained in the first polymer.

[0153] Exemplary surfactants include fluorinated and nonfluorinated surfactants and can be ionic or nonionic, with nonionic surfactants being preferred. Exemplary fluorinated nonionic surfactants include perfluorinated C4 surfactants, such as FC-4430 and FC-4432 surfactants available from 3M Corporation; and fluorinated glycols, such as POLYFOX PF-636, PF-6320, PF-656, and PF-6520 fluorinated surfactants from Omnova. In one aspect, the composition further comprises a surfactant polymer containing fluorinated repeating units.

[0154] Another aspect provides a monomer comprising an olefinic unsaturated double bond and a group having formula (1A) or (2A) as defined herein, wherein This represents the bonding site in the monomer.

[0155] Another aspect provides a polymer comprising repeating units having formula (1A) or (2A) as defined herein. For example, the polymer may comprise repeating units having formula (1B) or (2B) as defined herein. Yet another aspect provides a composition comprising a polymer containing repeating units having formula (1A) or (2A), a photoacid generator, and a solvent.

[0156] A patterning method using the photoresist composition of the present invention will now be described. Suitable substrates on which the photoresist composition can be coated include electronic device substrates. A wide variety of electronic device substrates can be used in the present invention, such as: semiconductor wafers; polycrystalline silicon substrates; packaging substrates, such as multi-chip 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 the following: 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 employed according to the present invention. The substrate may comprise one or more layers or structures, which may optionally comprise active or operable portions of the formed device.

[0157] Typically, prior to coating the photoresist composition of the present invention, 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. These layers, together with the externally coated photoresist layer, form a photolithographic material stack.

[0158] Optionally, an adhesion promoter layer may be applied to the substrate surface prior to coating the photoresist composition. If an adhesion promoter is desired, any suitable adhesion promoter for polymer films may be used, such as silanes, typically organosilanes like trimethoxyvinylsilane, triethoxyvinylsilane, hexamethyldisilazane, or aminosilane coupling agents like γ-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those sold under the names AP3000, AP 8000, and AP 9000S from Qnity Electronics, Inc. (Wilmington, Delaware).

[0159] Photoresist compositions can be coated onto a substrate by any suitable method, including spin coating, spraying, dip coating, blade coating, etc. For example, applying a photoresist layer can be accomplished by spin coating a 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 speeds up to 4,000 rpm, for example 200 to 3,000 rpm, or for example 1,000 to 2,500 rpm, for a period of 15 to 120 seconds to obtain a photoresist composition layer on the substrate. Those skilled in the art will understand that the thickness of the coated layer can be adjusted by varying the rotation speed and / or the total solids of the composition. Photoresist composition layers formed from the compositions of the present invention typically have a dry layer thickness of 3 to 30 micrometers (μm), preferably greater than 5 to 30 μm, and more preferably 6 to 25 μm.

[0160] Next, the photoresist composition is typically soft-baked to minimize the solvent content in the layer, thereby forming a non-stick coating and improving the layer's adhesion to the substrate. Soft baking is typically performed, for example, on a heated plate or in an oven, with a heated plate being typical. The soft baking temperature and time will depend, for example, on the photoresist composition and thickness. Soft baking temperatures are typically 80°C to 170°C, and more typically 90°C to 150°C. Soft baking times are typically 10 seconds to 20 minutes, more typically 1 minute to 10 minutes, and even more typically 1 minute to 2 minutes. Those skilled in the art can readily determine the heating time based on the composition's components.

[0161] Next, the photoresist layer is patterned and exposed to activating radiation to create a solubility difference between exposed and unexposed areas. Exposing the photoresist composition to activating radiation, as described herein, can form a latent image in the photoresist composition. Exposure is typically performed using a patterned photomask having optically transparent and optically opaque regions corresponding to the areas of the resist layer to be exposed and the areas of the resist layer not being exposed, respectively. Alternatively, this exposure can be performed without a photomask in a direct-write method typically used for 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), 193 nm (ArF), 13.5 nm (EUV) wavelengths or electron beam lithography being preferred. Preferably, the activating radiation is 248 nm radiation. These methods can be used in immersion or dry (non-immersion) lithography techniques. Exposure energy is typically 1 to 200 millijoules per square centimeter (mJ / cm²). 2 Preferably 10 to 100 mJ / cm 2 And more preferably 20 to 50 mJ / cm 2 This depends on the composition of the exposure tool and the photoresist composition.

[0162] After the photoresist layer is exposed, post-exposure baking (PEB) of the exposed photoresist layer is performed. PEB can be performed, for example, on a heated plate or in an oven, with a heated plate being typical. The conditions of PEB will depend, for example, on the photoresist composition and the layer thickness. PEB is typically performed at temperatures of 70°C to 150°C, preferably 75°C to 120°C, for a time of 30 to 120 seconds. A latent image, defined by polarity-converted regions (exposed regions) and polarity-unconverted regions (unexposed regions), is formed in the photoresist.

[0163] The exposed photoresist layer is then developed with a suitable developer to selectively remove areas of the layer that are soluble in the developer while retaining insoluble areas, forming the resulting photoresist pattern relief image. In the case of a positive development (PTD) process, the exposed areas of the photoresist layer are removed during development, while the unexposed areas are retained. Conversely, in a negative development (NTD) process, the exposed areas of the photoresist layer are retained during development, while the unexposed areas are removed. The application of the developer can be accomplished by any suitable method, as described above regarding the application of the photoresist 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.

[0164] 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, 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. Typical developers are 2-heptanone or n-butyl acetate.

[0165] The coated substrate can be formed from the photoresist composition of the present invention. Such a coated substrate comprises: (a) a substrate having one or more layers to be patterned on its surface; and (b) a photoresist composition layer on the one or more layers to be patterned.

[0166] Photoresist patterns can be used, for example, as etch masks, allowing the pattern to be transferred to one or more sequentially arranged underlying layers via known etch techniques, typically dry etching (such as reactive ion etching). Photoresist patterns can also be used, for example, to transfer a pattern to an underlying hard mask layer, which in turn serves as an etch mask for transferring the pattern 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 (e.g., oxygen plasma ashing). When used in one or more such patterning processes, photoresist compositions can be used to manufacture semiconductor devices such as memory devices, processor chips (CPUs), graphics chips, optoelectronic chips, LEDs, OLEDs, and other electronic devices.

[0167] The subject matter of the invention is further illustrated by the following non-limiting examples. Example List of monomers in the synthesis examples (M1) (M2) (M3) (M4) (M5) (M6) (M7) (M8) (M9) (M10) (M11) (M12) (M13) (M14) (M15) (M16) (M17) (M18) (M19) Synthesis of 2,2-dimethyl-1,3-dioxane-4,5,6-trione 5-(O-methacryloyl oxime) (M1)

[0168] The monomer designated as M1 is prepared as shown below. (M1)

[0169] Under a nitrogen atmosphere, with stirring, a solution of 17.25 g (250 mmol, 1.2 equivalents) of sodium nitrite in 40 mL of water was added dropwise over a 14-minute period to a solution of 30.0 g (208 mmol) of Meldrum's acid in 210 mL of methanol (MeOH) cooled at 0°C. The reaction mixture was slowly heated to room temperature while stirring. After stirring at room temperature for another 4.5 hours, the reaction mixture was concentrated under reduced pressure. Next, 150 mL of 10% HCl aqueous solution (aq.) and approximately 200 mL of dichloromethane (DCM) were added. After stirring at room temperature for 6 minutes, 10 mL of 12.1 M HCl aqueous solution was added. The contents were extracted with dichloromethane, and the combined extracts were dried with sodium sulfate, filtered, and concentrated under reduced pressure to give 28.7 g (79.4%) of 2,2-dimethyl-1,3-dioxane-4,5,6-trione-5-oxime as a light brown solid.

[0170] To a solution of 11.7 g (67.6 mmol) of 2,2-dimethyl-1,3-dioxane-4,5,6-trione-5-oxime cooled at 0°C in 350 mL of anhydrous dichloromethane, 9.4 mL of triethylamine (67.6 mmol, Et3N) was added, and then, with stirring, 6.6 mL (67.6 mmol) of methacryloyl chloride in 36 mL of dichloromethane was added over a 3.5-minute period. After completion, the reaction solution was concentrated under reduced pressure to produce an orange solid. Ethyl acetate was added to dissolve the crude product, which was then filtered and concentrated under reduced pressure. The crude product was dissolved in dichloromethane and purified in two fractions by silica gel chromatography on a Teledyne ISCO CombiFlash system using a 330 g RediSep Silver silica gel column with dichloromethane elution at 150 mL / min to produce 4.98 g (30.6%) of product M1 as a grayish-white solid (7.3 mg of 4-methoxyphenol (MEHQ) was added for stability). Synthesis of 2,3-Butanedione-O-(methacryloyl)oxime (M2)

[0171] The synthesis scheme for the monomer designated as M2 is shown below. (M2)

[0172] A solution of 25.0 g (247 mmol) of 2,3-butanedione monooxime was prepared in 500 mL of dichloromethane and 38 mL (272 mmol, 1.1 equivalence) of triethylamine under a nitrogen atmosphere. The solution was cooled to 0°C. Then, 26.5 mL (272 mmol, 1.1 equivalence) of methacryloyl chloride was added dropwise over a 12.5-minute period with stirring. The reaction mixture was then allowed to reach room temperature. After stirring at room temperature for 19 hours, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. Ethyl acetate was added to the solid, and the mixture was filtered. The filtrate was concentrated under reduced pressure. The crude material was dissolved in dichloromethane and purified by silica gel column chromatography on a Teledyne ISCO CombiFlash system using a 330 g RediSep Silver silica gel column with elution in dichloromethane to produce 14.9 g (35.5%) of product M2 as a pale yellow solid. Synthesis of 2,4-pentanedione-O-methacryloyl oxime (M3)

[0173] The synthesis scheme for the monomer designated as M3 is shown below. (M3)

[0174] Under a nitrogen atmosphere, 158.6 g of ice was added to a solution of 30.0 g (60 mmol) acetylacetone. Then, 36 mL (87 mmol, 1.45 equivalent) of concentrated HCl aqueous solution was added, and the mixture was cooled to 0°C. A solution of 21.0 g (60.3 mmol, 1.0 equivalent) of sodium nitrite in 45 mL of water was added over 13 minutes with stirring. The reaction mixture was then allowed to reach room temperature with continuous stirring. After 1 hour, 50 mL of water was added to ensure effective stirring. After stirring for another 2.5 hours, brine was added to the reaction mixture. The contents were extracted with ethyl acetate, and the combined extracts were dried over sodium sulfate, filtered, and concentrated under reduced pressure to give 34.97 g (90%) of 3-(hydroxyimino)pentane-2,4-dione as a white solid.

[0175] A solution of 18.677 g (145 mmol) of 3-(hydroxyimino)pentane-2,4-dione in 200 mL of dichloromethane and 20.16 mL (145 mmol, 1.0 equivalent) of triethylamine was prepared under a nitrogen atmosphere. The solution was cooled to 0°C. Then, a solution of 14.13 mL (145 mmol, 1.0 equivalent) of methacryloyl chloride in 60 mL of dichloromethane was added over a 37-minute period with stirring. The reaction mixture was then heated to room temperature. After stirring at room temperature for 10.5 hours, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. Ethyl acetate (300 mL) was added, and the mixture was filtered. The filtrate was concentrated under reduced pressure. The crude material was dissolved in a 3:1 dichloromethane:hexane mixture and purified using a 330 g RediSep Silver silica gel column on a Teledyne ISCO CombiFlash system. The column was eluted with a 2:1 dichloromethane:hexane mixture at 165 mL / min for 13.5 min, followed by elution with a 5:1 dichloromethane:hexane mixture. Product M3 crystallized upon standing and was chilled for 10 min to ensure complete crystallization. Yield: 16.85 g, white solid (64.8 mg MEHQ was added for stability). Synthesis of 2-methacryloyloxyethyl-2-[O-(2-ethylhexanoyl)oxime]-3-oxobutyrate (M4)

[0176] The monomer designated as M4 is prepared as shown below. (M4)

[0177] Under a nitrogen atmosphere and with stirring, a solution of 6.44 g (93.4 mmol, 1.0 equivalent) of sodium nitrite in 50 mL of water was added dropwise over 3 minutes to a solution of 20.0 g (93.4 mmol) of 2-(methacryloyloxy)ethyl acetate in 50 mL of glacial acetic acid (HOAc) at 0°C. The reaction mixture was slowly heated to room temperature overnight with stirring, then water was added to the reaction mixture, and the contents were extracted with dichloromethane. The combined dichloromethane layers were washed once with a saturated aqueous solution of sodium bicarbonate, and the dichloromethane extract was dried over sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to give a deep golden, medium-viscosity liquid. The crude product was purified by elution with 95:5 dichloromethane:ethyl acetate on a 326 g 3-inch diameter silica column to give 9.5 g of (2-methacryloyloxy)-2-(hydroxyimino)-3-oxobutyrate in an oily form (17.2 mg MEHQ was added to maintain stability).

[0178] Under a nitrogen atmosphere, over three minutes, 40 mg (0.31 mmol, 0.008 equivalent) MEHQ, 5.5 mL (40.2 mmol, 1.03 equivalent) triethylamine, and 6.8 mL (39.7 mmol, 1.02 equivalent) 2-ethylhexanoyl chloride were added to a stirred solution of 9.5 g (39.1 mmol) (2-methacryloyloxy)-2-(hydroxyimino)-3-oxobutyrate in 200 mL of dichloromethane at 0°C. After stirring at 0°C for 25 minutes, the reaction mixture was then stirred at room temperature. After stirring at room temperature for 3 hours, the reaction mixture was concentrated to a volume of 20 mL under reduced pressure. Ethyl acetate was added, and the mixture was filtered. The filtrate was concentrated under reduced pressure to give a slightly viscous orange / gold liquid. The crude material was dissolved in a 5:1 dichloromethane:hexane mixture and purified using a 330 g RediSepSilver silica column on a Teledyne ISCO CombiFlash system. The elution was performed with 5:1 dichloromethane:hexane at 170 mL / min for 8.8 min, followed by elution at 190 mL / min for 2.2 min, and then with dichloromethane at 190 mL / min. Product M4 was obtained as a colorless oil (19.6 mg MEHQ was added for stability). Yield: 7.65 g (53%). Synthesis of N,N-dibutyl-2-((methacryloyloxy)imino)-3-oxobutyramide (M5)

[0179] In a round-bottom flask, 14.6 g of dibutylamine, 8.4 g of 2,2,6-trimethyl-4H-1,3-dioxin-4-one, and 50 mL of toluene were combined. The mixture was stirred and heated under reflux for 16 hours, then cooled to room temperature and washed with dilute aqueous HCl. The organic layer was collected and dried to produce N,N-dibutyl-3-oxobutyramide.

[0180] The amide was dissolved in 50 mL of acetic acid at approximately 10°C; and then 5.0 g of NaNO2 was slowly added to 12 mL of water over 30 minutes. After reacting for another hour at room temperature, the product was separated from the water by extraction with methyl tert-butyl ether and washing with an aqueous solution of NaHCO3 until the aqueous layer became neutral. 18.3 g of a light brown solid oxime precursor was obtained.

[0181] The oxime precursor was dissolved in 100 mL of dichloromethane containing 5.5 g of methacrylic acid and 50 mg of 4-pyrrolylpyridine at 0°C. Then, 12.0 g of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC) was slowly added over 1 hour. After reacting for another hour at room temperature with stirring, the product was separated from water by extraction with methyl tert-butyl ether and washing with aqueous HCl and NaHCO3 solutions. Concentration under reduced pressure (with 30 mg BHT) yielded a brown, honey-like product. The material was redissolved in 30 mL of methanol and added dropwise to 70 g of an ice-water mixture. The solid was collected and dried to yield 6.1 g of a reddish-yellow solid as monomer M5. Synthesis of 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione-3-(O-methacryloyl oxime) (M6)

[0182] The monomer designated as M6 is prepared as shown below. (M6)

[0183] Add 9.87 g (120 mmol, 1.0 equivalent) of sodium acetate in 21.5 mL of water to a solution of 20 g (120 mmol) (+)-camphorquinone in 100 mL of ethanol. Next, add 8.36 g (31.2 mmol, 1.0 equivalent) of hydroxylamine hydrochloride in 23.4 mL of water at room temperature. Heat the reaction mixture at 82°C for 2.25 h and then stir at room temperature. After stirring for another 17 h at room temperature, filter the reaction mixture and then concentrate it under reduced pressure to remove ethanol. Extract the contents with ethyl acetate, and dry the combined extracts with magnesium sulfate, filter, and concentrate under reduced pressure. The crude material (a combination of 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione 2-oxime (B) and 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione 3-oxime (A)) was purified on a Teledyne ISCO CombiFlash system using a 330 g RediSepSilver silica gel column eluted with 95:5 dichloromethane:ethyl acetate at 150 mL / min. The second main peak was collected to give 15.0 g (69%) of 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione 3-oxime as a white solid.

[0184] Under a nitrogen atmosphere, with stirring, 5.0 mL (50.5 mmol) of methacryloyl chloride in 50 mL of dichloromethane was added to a solution of 9.16 g (50.5 mmol) of 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione 3-oxime cooled at 0°C in 150 mL of dichloromethane and 7.1 mL (50.5 mmol, 1.0 equivalence) of triethylamine over a 23-minute period. The reaction mixture was slowly heated to room temperature. After stirring at room temperature for 18 hours, the reaction mixture was concentrated under reduced pressure. Ethyl acetate was added, and the resulting mixture was filtered. The filtrate was concentrated under reduced pressure. The crude material was purified by elution over 40 minutes using a 330 g RediSep Silver silica gel column on a Teledyne ISCO CombiFlash system with a gradient elution from 100% dichloromethane to 95:5 dichloromethane: ethyl acetate. Product M6, a yellow solid, was obtained (6.6 mg MEHQ was added to maintain stability). Yield: 4.7 g (37%). Synthesis of 2-oxopropanal-O-methacryloyl oxime (M7)

[0185] The synthesis scheme for the monomer designated as M7 is shown below. (M7)

[0186] A solution of 40 g isonitroacetone in 60 mL of dichloromethane was purified by silica gel column chromatography using 252 g silica gel and eluted with dichloromethane: ethyl acetate (95:5) to provide 31.7 g of isonitroacetone as a grayish-white solid.

[0187] Under a nitrogen atmosphere at 0°C, 35.0 mL of triethylamine was added to a solution of purified isonitroacetone in 500 mL of dichloromethane. Next, 24.6 mL of methacryloyl chloride in 25 mL of dichloromethane was added dropwise over a 30-minute period with stirring. The reaction mixture was then slowly heated to room temperature with stirring. After completion, the reaction mixture was concentrated under reduced pressure. Ethyl acetate was added to the crude material, and the mixture was filtered. The filtrate was concentrated under reduced pressure. The crude material was dissolved in dichloromethane and purified by silica gel column chromatography using a Teledyne ISCO CombiFlash system with a 330 g RediSep Silver silica gel column, eluting with dichloromethane at 150 mL / min, to produce 3.60 g (10%) of product M7 as a faint golden liquid. Synthesis of (E)-3-oxo-2-(((4-vinylbenzoyl)oxy)imino)tert-butyl butyrate (M8) (M8)

[0188] The monomer designated M8 was prepared as follows: 15.3 mL of tert-butyl acetoacetate was dissolved in 100 mL of acetic acid at 0°C; and then 7.5 g of NaNO2 was slowly added to 25 mL of water over 30 minutes (to generate O=N in situ). + After reacting at room temperature for another hour, the product was separated from water by extraction with methyl tert-butyl ether and washing with aqueous NaHCO3 solution. 17.2 g of a pale yellow solid precursor was obtained. At 0°C, 7.9 g of the solid precursor was dissolved in 100 mL of dichloromethane containing 7.5 g of vinylbenzoic acid; then, 9.1 g of EDC was slowly added over 30 minutes; after reacting at room temperature for another hour, the product was separated from water by extraction with methyl tert-butyl ether and washing with HCl and NaHCO3. Concentration (with 0.1 g of BHT) yielded a solid product. The solid was redissolved in 70 mL of heptane (approximately 60°C), the solution was filtered through a 10-micron PE filter with a Na2SO4 layer, cooled to -78°C, and the solid was collected. The recrystallization process was repeated to produce 5.8 g of a pale yellow crystalline solid product M8. Synthesis of 2,6-dimethylheptane-3,4,5-trione-4-(O-methacryloyl oxime) (M9)

[0189] The monomer designated as M9 is prepared as shown below. (M9)

[0190] Under a nitrogen atmosphere, a solution of 50.0 g (0.32 mol) of 2,6-dimethyl-3,5-heptanedione in 200 mL of glacial acetic acid was cooled to 0°C. A solution of 88.3 g (1.28 mol, 4.0 equivalent) of sodium nitrite in 130 mL of water was added in portions over approximately 13.5 minutes with stirring, maintaining the temperature between 0°C and room temperature. After the addition was complete, the reaction mixture was slowly heated to room temperature with stirring. After stirring at room temperature for 16 hours, brine was added to the reaction mixture, and the contents were extracted with ethyl acetate. The combined extracts were dried over sodium sulfate, filtered, and concentrated under reduced pressure to provide a golden-orange viscous liquid. The crude material was purified by silica gel column chromatography using 636 g of silica gel and eluted with dichloromethane. A fine golden oil of 4-(hydroxyimino)-2,6-dimethylheptane-3,5-dione was obtained. Yield: 6.1 g.

[0191] Under a nitrogen atmosphere, 4.4 mL (31.2 mmol, 1.0 equivalent) of triethylamine was added to a solution of 5.78 g (31.2 mmol) of 4-(hydroxyimino)-2,6-dimethylheptane-3,5-dione in 50 mL of dichloromethane at 0°C, followed by the addition of 3.1 mL (31.2 mmol, 1.0 equivalent) of methacryloyl chloride in 22 mL of dichloromethane over a 13-minute period with stirring. The reaction mixture was brought to room temperature. An additional 28 mL of dichloromethane was added to ensure vigorous stirring. After stirring at room temperature for 2.5 hours, the reaction mixture was concentrated under reduced pressure. Ethyl acetate (100 mL) was added and the mixture was filtered. The filtrate was concentrated under reduced pressure to give an orange / gold liquid. The crude material was dissolved in a 1:1 dichloromethane:hexane mixture and purified using a 330 g RediSep Silver silica gel column on a Teledyne ISCO CombiFlash system with elution in a 2:1 dichloromethane:hexane mixture at 165 mL / min. Product M9 was obtained as a very pale yellow liquid (4.2 mg MEHQ was added for stability). Yield: 6.1 g (51%). Synthesis of (E)-2-((methacryloyloxy)imino)-3-oxobutyrate tert-butyl ester (M10)

[0192] The monomer designated as M10 is prepared as shown below.

[0193] At 0°C, 15.3 mL of tert-butyl acetoacetate was dissolved in 100 mL of acetic acid; and then 7.5 g of NaNO2 was slowly added to 25 mL of water over 30 minutes (to generate O=N in situ). + After reacting at room temperature for another hour, the product was separated from water by extraction with methyl tert-butyl ether and washing with aqueous NaHCO3 solution. Concentration under vacuum yielded 17.2 g of a pale yellow solid precursor. The solid precursor was dissolved in 100 mL of dichloromethane containing 11.0 g of methacrylic acid and 30 mg of 4-pyrrolidinylpyridine at 0°C. Then, 19.1 g of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC) was slowly added over 1 hour. After reacting at room temperature with stirring for another hour, the product was separated from water by extraction with methyl tert-butyl ether and washing with aqueous HCl solution followed by washing with aqueous NaHCO3 solution. Concentration under reduced pressure (with 200 mg BHT) yielded a solid product. The solid was redissolved in 40 mL of heptane (approximately 60°C), the solution was filtered through a 10-micron PE filter with a Na2SO4 layer, cooled to -78°C, and the solid was collected. The recrystallization process was repeated to produce 10.3 g of pale yellow crystalline solid M10. Synthesis of ethyl 2-((methacryloyloxy)imino)-3-oxo-3-phenylpropionate (M13)

[0194] In a round-bottom flask, 25.0 g of ethyl benzoyl was dissolved in 60 mL of acetic acid and stirred at 0°C. Then, 11.6 g of NaNO₂ in 23 mL of water was slowly added over 60 minutes. After reacting at room temperature for another hour, the product was separated from the water by extraction with methyl tert-butyl ether and washing with aqueous NaHCO₃ solution until the aqueous layer became neutral. 25.3 g of a pale yellow solid oxime precursor was obtained.

[0195] At 0°C, 9.0 g of the oxime precursor was dissolved in 70 mL of dichloromethane containing 5.0 g of methacrylic acid and 50 mg of 4-pyrrolylpyridine. Then, 9.0 g of EDC was slowly added over 1 hour. After reacting for another hour at room temperature with stirring, the product was separated from water by extraction with methyl tert-butyl ether and washing with aqueous HCl and NaHCO3 solutions. The product was concentrated under reduced pressure (with 20 mg BHT) to obtain a waxy product. The material was recrystallized from 30 mL of heptane. The solid was collected and dried to yield 5.5 g of a pale yellow solid as monomer M13. Synthesis of 2-((methacryloyloxy)imino)dibutyl malonate (M14)

[0196] In a round-bottom flask, 25.0 mL of butyl malonate was dissolved in 100 mL of acetic acid and stirred at 0°C. Then, 9 g of NaNO₂ was slowly added to 20 mL of water over 2 hours. After reacting at room temperature for another hour, the product was separated by extraction from water with methyl tert-butyl ether and washing with aqueous NaHCO₃ solution until the aqueous layer became neutral. The mixture was then dissolved again in 100 mL of acetic acid and stirred at 0°C. Then, 18 g of NaNO₂ was slowly added to 50 mL of water over 3 hours. After reacting at room temperature for another hour, the product was separated by extraction from water with methyl tert-butyl ether and washing with aqueous NaHCO₃ solution until the aqueous layer became neutral. The organic layer was concentrated and found to be a mixture of 60 mol% oxime and 40 mol% starting material. The mixture was used directly without further purification.

[0197] At 0°C, the mixture from the last step was dissolved in 150 mL of dichloromethane containing 7.9 g of methacrylic acid and 130 mg of 4-pyrrolidinylpyridine. Then, 13.7 g of EDC was slowly added over 45 minutes. After reacting for another hour at room temperature with stirring, the product was separated from water by extraction with methyl tert-butyl ether and washing with aqueous HCl and NaHCO3 solutions. The organic layer was concentrated under reduced pressure and further purified by column chromatography (heptane:ethyl acetate = 10:1, v:v) to yield 16.2 g of a pale yellow oil (stabilized with 20 mg BHT) as a mixture of monomer M14 and dibutyl malonate (approximately 67:33 = mol:mol). The mixture was used directly without further purification. Synthesis of neopentyl 2-(((2-fluoroacryloyl)oxy)imino)propionate (M15)

[0198] In a round-bottom flask, 53 g of neopentyl alcohol was mixed with 61 g of pyruvic acid, 2.1 g of p-toluenesulfonic acid, and 400 mL of toluene. The reaction was carried out by heating under reflux for 6 hours, during which water was removed using a Dean-Stocker water separator. The mixture was then washed with water and an aqueous solution of NaHCO3 to obtain a crude product, which was further purified by distillation.

[0199] Add 25 g of hydroxylamine hydrochloride and 60 mL of water to a beaker; add 13 g of NaOH granules in batches to prevent overheating. Transfer the formed hydroxylamine as is to a solution containing 30.0 g of neopentyl pyruvate and 100 mL of methanol, and then stir in a cooling bath at room temperature. Stir the solution further overnight, and separate the product by extraction from a dilute aqueous HCl solution with ethyl acetate. After drying, 32.3 g of crystalline solid as an oxime precursor is obtained.

[0200] At 0°C, 14.3 g of the oxime precursor was dissolved in 100 mL of dichloromethane containing 8.1 g of 2-fluoroacrylic acid and 60 mg of 4-pyrrolidinylpyridine. Then, 16.3 g of EDC was slowly added over 60 minutes. After reacting for another hour at room temperature with stirring, the product was separated from water by extraction with methyl tert-butyl ether and washing with aqueous HCl and NaHCO3 solutions. The organic layer was concentrated and further purified by recrystallization from heptane (stabilized with approximately 60 mg of BHT from 60°C to 0°C) to yield 18.5 g of a white crystalline solid as monomer M15. Synthesis of 2,8-dimethylnonane-4,5,6-trione-5-(O-methacryloyl oxime) (M16)

[0201] Within 3 minutes, a solution of 9.32 g of sodium nitrite in 20 mL of water was added to a solution of 24.9 g of 2,8-dimethylnonane-4,6-dione in 80 mL of acetic acid, which was cooled in an ice bath. After stirring under nitrogen for 20 hours, 100 mL of water, 100 mL of brine, and 100 mL of saturated NaHCO3 solution were added, and the contents were extracted with ethyl acetate. The organic extract was dried over sodium sulfate, filtered, and concentrated under reduced pressure to give 33.2 g of crude material. The crude material was purified first on a silica gel column (hexane:ethyl acetate = 9:1, v:v) and then eluted with dichloromethane on the silica gel column. After concentration under reduced pressure, 16.7 g of a golden oily substance as an oxime precursor was obtained.

[0202] 11.0 mL of triethylamine was added to a solution of 16.7 g of the oxime precursor in 250 mL of dichloromethane, cooled in an ice bath, followed by the addition of 7.7 mL of methacryloyl chloride in 70 mL of dichloromethane over 27 minutes under nitrogen. After 2 hours, the reaction mixture was concentrated under reduced pressure. Ethyl acetate (250 mL) was added to dissolve the crude product. The triethylamine hydrochloride was filtered, and the filtrate was concentrated under reduced pressure to provide 22.2 g of crude product as a yellow liquid. The crude product was purified by elution on a silica gel column with hexane:dichloromethane (1:1 = v:v) to give 16.15 g of monomer M16 as a colorless liquid (stable with 35.8 mg MEHQ). The liquid slowly formed needle-like crystals. Synthesis of tert-butyl S-2-(O-methacryloylimino)-3-oxothiobutyrate (M17)

[0203] Under nitrogen atmosphere, a solution of 23.73 g of 2,2,6-trimethyl-1,3-dioxin-4-one and 15.02 g of tert-butylthiol was heated under reflux in 200 mL of toluene. After 20 hours, the reaction solution was concentrated under reduced pressure. The crude material was loaded onto a silica gel column and eluted with 2.5 L of hexane followed by 2 L of hexane:ethyl acetate (95:5 = v:v). The separated fraction was purified again on a silica gel column. To further purify the compound, 3.10 g of activated carbon was added and the mixture was stirred at room temperature for 15 minutes. The solid was filtered and the filtrate was concentrated under reduced pressure to give 16.9 g of a colorless oil.

[0204] Over 4 minutes, a solution of 9.96 g of sodium nitrite in 25 mL of water was added dropwise to a solution of 16.77 g of thioester in 50 mL of glacial acetic acid, cooled in an ice bath. After stirring for 18 hours, water and brine were added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic extract was dried over sodium sulfate, filtered, and concentrated under reduced pressure to produce a crude product as an orange liquid. The crude product was purified by elution on a silica gel column with hexane:ethyl acetate (5:1 = v:v). The product with slight impurities was used directly in the next step. The yield of the oxime precursor was 13.21 g.

[0205] 9.3 mL of triethylamine was added to a solution of 13.20 g of the oxime precursor cooled in an ice bath in 315 mL of dichloromethane, followed by the addition of 6.5 mL of methacryloyl chloride in 15 mL of dichloromethane over 8 minutes. After 1 hour, the reaction mixture was concentrated and ethyl acetate was added. The insoluble material was filtered, and the filtrate was concentrated under reduced pressure. The crude product (31.5 mL of deep amber liquid) was purified by elution with dichloromethane using a silica gel column. After drying, 1.50 g of pure product as a colorless solid (stable with 9.9 mg MEHQ) was obtained. The impure fractions obtained from the column were combined and purified again by elution with dichloromethane using a second silica gel column to give an additional 3.03 g of colorless solid as product (stable with 12.9 mg MEHQ). Synthesis of methyl 2-((methacryloyloxy)imino)-4,4-dimethyl-3-oxovalerate (M18)

[0206] Over 15 minutes, a solution of 13.08 g of sodium nitrite in 30 mL of water was added dropwise to a solution of methyl 4,4-dimethyl-3-oxovalerate in 60 mL of glacial acetic acid, which was in an ice bath. After 2 hours, water and brine were added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic extract was dried over sodium sulfate, filtered, and concentrated under reduced pressure to provide a turbid orange liquid. The crude material was purified on a silica gel column by elution with a 5:1 hexane:ethyl acetate (v:v) followed by elution with a 4:1 hexane:ethyl acetate (v:v). The remaining impurities were further purified on a silica gel column. Combining these fractions yielded 8.3 g of a white solid as an oxime precursor.

[0207] 6.8 mL of triethylamine was added to a solution of 8.3 g of the oxime precursor in 100 mL of dichloromethane, which was cooled in an ice bath, followed by the addition of 4.76 mL of methacryloyl chloride in 25 mL of dichloromethane over 15 minutes. After 1.25 hours, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. Ethyl acetate was added, and the insoluble material was filtered off. The filtrate was concentrated to give a crude product as a medium amber liquid. The crude product was purified by elution on a silica gel column using a 5:1 hexane:ethyl acetate (v:v). After drying, 7.5 g of a colorless liquid as product M18 (stable with 7.5 mg MEHQ) was obtained. Synthesis of 5-methyl-2,3-hexanedione-2-(methacryloyl)oxime (M19)

[0208] A solution of 9.67 g of hydroxylamine hydrochloride in 30 mL of water was added to a solution of 17.84 g of 5-methyl-2,3-hexanedione in 180 mL of ethanol at room temperature. Then, a solution of 11.42 g of sodium acetate in 25 mL of water was added. Another 20 mL of water was added, and the reaction mixture was heated under nitrogen at an external temperature of 60°C for 1 hour and 20 minutes. The mixture was then cooled to room temperature and concentrated under reduced pressure.

[0209] Then, 280 mL of saline solution was added, and the contents were extracted with ethyl acetate. The combined extracts were dried over sodium sulfate and concentrated to give a grayish-white solid. The crude product was purified by silica gel chromatography (6:1 hexane: ethyl acetate) to give 9.1 g (46%) of the oxime precursor.

[0210] 11.0 mL of triethylamine was added to a solution of 11.3 g of the oxime precursor in 150 mL of dichloromethane, which was cooled in an ice bath, followed by dropwise addition of 7.72 mL of methacryloyl chloride in 50 mL of dichloromethane over 16 minutes. After stirring for 1 hour and 50 minutes, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. Ethyl acetate was added to the residue, and the solid was filtered off. The filtrate was concentrated to give 17.5 g of amber liquid. The crude product was purified by silica gel chromatography (6:1 hexane:ethyl acetate) to give 13.2 g (79%) of product M19 as a colorless liquid (stable with 8.5 mg MEHQ). EBL polymer synthesis

[0211] Examples of EBL polymer synthesis using the following general protocol. CTA (chain transfer agent, 2-cyanopropyl dodecyl trithiocarbonate), initiator (AIBN is azobisisobutyronitrile, V601 is dimethyl 2,2'-azobis(2-methylpropionic acid)), monomer 1, optional monomer 2, and optional monomer 3 are dissolved in a solvent. Specific amounts are summarized in Table 1, where the amounts of components are in milligrams and the amounts of solvent are in grams. The mixture is degassed by bubbling with nitrogen for 10–20 minutes. The reaction solution is then heated to 70°C–72°C for 20 hours. Some samples are separated by precipitation into the solvent; others are used directly as solutions. Polymer molecular weight information (M...) n and M w / M n The results are summarized in Table 2, as determined by gel permeation chromatography (GPC) using polystyrene standards, and reported in Daltons (Da). Table 1 Table 2 Comparative polymer synthesis (CP1)

[0212] A monomer solution was prepared by combining and stirring a mixture of 192.00 g PGMEA, 133.2 g (methacryloyloxy)methylenebis(2,2-difluoro-3,3-dimethylbutyrate) and 8.51 g ethylcyclopentyl methacrylate in a flask to dissolve the components. Separately, an initiator solution was prepared by combining 10.72 g PGMEA and 6.2 g V601 initiator in a flask. 20.05 g PGMEA was introduced into a separate reaction vessel and the vessel was purged with nitrogen for 30 minutes. Next, the reaction vessel was heated to 95°C with stirring. Then, the monomer solution and initiator solution were introduced into the reaction vessel as separate feeds over a period of 2.5 hours. After 2.5 hours, the reaction vessel was maintained at 95°C with stirring for another 3 hours and then allowed to cool to room temperature. M was obtained. w / M n Products with (kDa) of 9.7 / 6.2, as determined by GPC using polystyrene standards. Preparation of the second polymer (P32)

[0213] The second polymer (ECPMA / aGBLMA / NLMA, molar ratio 40 / 40 / 20) was synthesized using the following procedure. 11.200 g of PGMEA was charged into the reactor and heated to 80°C. The monomer feed mixture was prepared as a mixture of 10.245 g ECPMA, 9.556 g GBLMA, and 6.244 g NLMA, and degassed before use. An initiator feed mixture was prepared using 1.541 g V601 initiator and 13.902 g PGMEA, and degassed before use. The monomer and initiator solutions were fed simultaneously. Five hours after the start of feeding, the reactor was cooled to ambient temperature at a rate of 1°C / min. The polymer was separated by precipitation in 10 times its volume of methanol and dried before use. The molecular weight was determined by GPC using polystyrene standards as M. w =8.5 kDa and PDI = 1.54. ECPMA aGBLMA NLMA Coating Composition

[0214] Positive photoresist compositions were prepared using the materials and amounts indicated in Table 3, where amounts are expressed as wt% of 100 wt% of the total weight of solids. The total solids content of the photoresist compositions was 3.10 wt%. The solvent system contained propylene glycol methyl ether acetate (S1) (40 wt%) and methyl 2-hydroxyisobutyrate (S2) (60 wt%). Each mixture was shaken in a 20 mL glass container on a mechanical shaker and filtered through a PTFE disc filter with a pore size of 0.20 μm. Q1 Q2 PAG2 Table 3 Indicator comparison photoresist composition. Contact angle evaluation

[0215] On the TEL ACT-8 wafer track, 8-inch silicon wafers were undercoated with hexamethyldisilazane (HMDS) at 120°C for 30 seconds, coated with the photoresist compositions listed in Table 3, and soft-baked at 90°C for 60 seconds to obtain a film layer with a thickness of approximately 80 nm. The contact angle of each polymer solution was measured using deionized Millipore filtered water on a Kruss contact angle goniometer. The backlash angle after coating and soft baking was then measured at the start of the lateral descent motion, before rapid acceleration. The backlash angle after development / DI water rinsing was measured with wafers treated with MF™ CD26 TMAH developer (Qinuodi Electronics) for 60 seconds, rinsed with DI water, and dried. For each formulation, two wafers were coated, one without TMAH development and the other with a single 60-second immersion development via TMAH. The contact angles measured before and after development are shown in Table 4. Table 4 Indicator comparison photoresist composition.

[0216] As shown in Table 4, the exemplary photoresist compositions in the coated and dried state exhibit a receding contact angle greater than 60°. Photoresist formulations and evaluation Preparation of photoresist polymers

[0217] Polymer P33 was synthesized using free radical polymerization as follows. PGMEA (10.5 g) was charged into a single-necked 100 mL reaction flask and purged under nitrogen for 30 min with stirring. The reaction flask was heated to 80°C, and monomers M10 (18.33 g, 71.8 mmol), M11 (5.67 g, 30.7 mmol), and PGMEA (40 wt% solution) were charged into the reaction mixture over 4 h. Simultaneously, V601 initiator (0.49 g, 2.13 mmol) in PGMEA (20 wt% solution) was charged into the reaction mixture over 3.5 h. The reaction mixture was then cooled to room temperature after 5 h. The reaction mixture was used directly. The molecular weight was determined by gel permeation chromatography (GPC) using polystyrene standards as Mw = 8.9 kDa and PDI = 1.80. Photoresist formulation

[0218] Positive photoresist compositions were prepared using the materials and amounts indicated in Table 5, where amounts are expressed as wt% of 100 wt% of the total weight of solids. The total solids content of the photoresist compositions was 3.10 wt%. The solvent system contained propylene glycol methyl ether acetate (S1) (40 wt%) and methyl 2-hydroxyisobutyrate (S2) (60 wt%). Each mixture was shaken in a 20 mL glass container on a mechanical shaker and filtered through a PTFE disc filter with a pore size of 0.20 μm. Table 5 Indicator comparison photoresist composition. Photoresist patterning and processing

[0219] The photoresist composition was evaluated using photolithography. A 300 mm silicon wafer was first spin-coated with a bottom antireflective coating (BARC) AR™40 (Qinuodi Electronics) and baked at 205°C for 60 seconds to form an 80 nm film. A silicon-containing antireflective coating (SiARC) was then spin-coated onto the BARC layer and baked at 240°C for 60 seconds to form a 30 nm film. The photoresist composition was then spin-coated onto the top layer to form a 90 nm film and soft-baked at 90°C for 60 seconds. The coated wafer was then exposed using an ASML 1900i immersion tool (NA 1.35, σ 0.988 / 0.9) with an ArF excimer laser at 193 nm. Afterward, the wafer was exposed at 95°C and baked for 60 seconds, followed by development with a 0.26 N TMAH solution and then rinsed with water.

[0220] Photoresist patterns were observed under a CD-SEM (CG4000, Hitachi High-Technologies Corp.). Exposure doses for 1:1 line patterns with sizes of 45 nm and 38 nm are reported as sensitivity (mJ / cm). 2 Exposure latitude (%) is the degree to which a photosensitive material can be overexposed or underexposed and still achieve acceptable results. This value is defined as the percentage of exposure dose within ±10% of the critical size (CD) relative to the exposure dose at the CD. 3σ was determined for LS patterns with target sizes of 45 nm and 38 nm, where 3σ is a scale indicating LWR. The results are shown in Table 6 as “LWR (nm)”. “3σ” indicates three times the standard deviation (σ) determined from measurements obtained at 20 line positions along the longitudinal direction of the line using CD-SEM (in nm). Table 6 Indicator comparison photoresist composition.

[0221] As shown in Table 6, the photoresist composition of the present invention achieves performance comparable to that of the comparative photoresist composition in terms of sensitivity, exposure tolerance and LWR.

[0222] 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.

Claims

1. A photoresist composition comprising: A first polymer, the first polymer comprising a first repeating unit having a group having formula (1) or (2); The second polymer, the second polymer comprising a first repeating unit containing an acid-instable group; Photoacid generator; and Solvent, (1) (2) In equations (1) and (2), R 1 and R 2 Each is independently either hydrogen or an organic group; R 1 and R 2 They can optionally form a ring together; R 1 and R 2 Each of them may optionally further include one or more divalent linking groups as part of its structure; R 1 Or R 2 One of them may be bonded to the main chain of the first polymer; and This refers to the bonding point in the first repeating unit of the first polymer.

2. The photoresist composition as claimed in claim 1, wherein, The first repeating unit of the first polymer contains a group having formula (1).

3. The photoresist composition as described in claim 1, wherein, The first repeating unit of the first polymer contains a group having formula (2).

4. The photoresist composition according to any one of claims 1 to 3, wherein, The first repeating unit of the first polymer is formed from a monomer containing an olefinic unsaturated double bond.

5. The photoresist composition according to any one of claims 1 to 4, wherein, The total content of all repeating units having groups of formula (1) or formula (2) in the first polymer is 30 to 100 mol based on the total number of repeating units in the first polymer.

6. The photoresist composition according to any one of claims 1 to 5, wherein, The first polymer is present in the photoresist composition in an amount of 0.1 to 20 wt% based on the total solids of the photoresist composition.

7. The photoresist composition according to any one of claims 1 to 6, wherein, The photoresist composition in a coated and dried state exhibits a receding contact angle greater than 60°.

8. The photoresist composition according to any one of claims 1 to 7, wherein, The first polymer does not contain -CF2- and -CF3 groups bonded to carbon atoms.

9. The photoresist composition of claim 8, wherein, The first polymer does not contain fluorine.

10. The photoresist composition according to any one of claims 1 to 9, wherein, The photoresist composition is fluorine-free.

11. The photoresist composition according to any one of claims 1 to 10, wherein, The first repeating unit of the first polymer comprises a group having formula (1A) or (2A): (1A) (2A) In equations (1A) and (2A), R 1a It is hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, or substituted or unsubstituted C 2-30 Heterene group; R 2a It is an organic group; Z 2 Is it NR', O, or S; R' is hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Mixed aromatics; R 1a and R 2a They can optionally form a ring together; R 1a and R 2a Each may optionally further include one or more divalent linking groups as part of its structure; R 1a Or R 2a One of them may be bonded to the main chain of the first polymer; and This refers to the bonding point in the first repeating unit of the first polymer.

12. A pattern forming method, the pattern forming method comprising: (a) Applying a layer of the photoresist composition as described in any one of claims 1 to 11 onto a substrate; (b) Exposing the photoresist composition layer to activated radiation in a patterned manner; as well as (c) Develop the exposed photoresist composition layer to provide a photoresist relief image.

13. A monomer comprising an olefinic unsaturated double bond and a group having formula (1A) or (2A): (1A) (2A) in, In equations (1A) and (2A), R 1 It is hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, or substituted or unsubstituted C 2-30 Heterene group; R 2a It is an organic group; Z 2 Is it NR', O, or S; R' is hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Mixed aromatics; R 1 and R 2a They can optionally form a ring together; R 1 and R 2a Each may optionally further comprise one or more divalent linking groups as part of its structure; and This indicates the bonding point in the monomer.

14. A polymer comprising repeating units having groups having formula (1A) or (2A): (1A) (2A) in, In equations (1A) and (2A), R 1 It is hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, or substituted or unsubstituted C 2-30 Heterene group; R 2a It is an organic group; Z 2 Is it NR', O, or S; R' is hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Mixed aromatics; R 1 and R 2a They can optionally form a ring together; R 1 and R 2a Each may optionally further include one or more divalent linking groups as part of its structure; R 1 Or R 2a One of them may be bonded to the main chain of the polymer; and This refers to the bonding point in the repeating unit of the polymer.

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