Photoresist composition and pattern forming method

Abstract

A photoresist composition is disclosed, the photoresist composition comprising: a first polymer comprising first repeat units, the first repeat units comprising an acid-labile group; and a second polymer comprising repeat units derived from one or more monomers having formula (4); a photoacid generator; and a solvent, wherein Z 1 , Z 2 , R 1 , R 2 , and L are as described herein, and P is a polymerizable group.

Description

TECHNICAL FIELD

[0001] The present invention relates to photoresist compositions containing a blend of a photoactive component and two different polymers and a pattern forming process using such photoresist compositions. The invention is closely related to photolithographic applications in the semiconductor manufacturing industry. BACKGROUND

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

[0003] Positive chemically amplified photoresists are commonly used for high resolution processing. Such resists typically use a polymer with acid-labile groups and a photoacid generator. Exposure in a patterned fashion through a photomask to activating radiation causes the photoacid generator to form acid, which during a post-exposure bake causes the acid-labile groups in the exposed areas of the polymer to cleave. This creates a difference in solubility characteristics between the exposed and unexposed areas of the resist in the developer solution. In a positive tone development (PTD) process, the exposed areas of the photoresist layer are soluble in the developer and are removed from the substrate surface, while the unexposed areas, which are insoluble in the developer, remain after development to form a positive image. The resulting relief image allows for selective processing of the substrate. See, for example, Uzodinma Okoroanyanwu, Chemistry and Lithography, SPIE Press and John Wiley and Sons, Inc., 2010 and Chris Mack, Fundamental Principles of Optical Lithography, John Wiley and Sons, Inc., 2007.

[0004] One method of achieving nanometer-scale feature sizes in semiconductor devices is to use short wavelength light, such as 193 nanometers (nm) or less, during the exposure process of chemically amplified photoresists. To further improve lithographic performance, immersion lithography tools (e.g., scanners with a KrF (248 nm) or ArF (193 nm) light source) have been developed to effectively increase the numerical aperture (NA) of the lens of the imaging device. This is accomplished by using a high refractive index fluid (typically water) between the last surface of the imaging device and the upper surface of the semiconductor wafer. By using multiple (dual or more) patterning, ArF immersion tools are currently pushing the boundaries of lithography to feature sizes below 40 nm.

[0005] Despite advances in resist technology, there remains a need for photoresist compositions that address one or more problems associated with current technology. In particular, there is an ongoing need for photoresist compositions for immersion lithography with improved scan speed and fewer defects. SUMMARY

[0006] A photoresist composition comprising: a first polymer comprising a first repeating unit comprising an acid labile group; and a second polymer comprising a repeating unit derived from one or more monomers of Formula (4); a photoacid generator; and a solvent,

[0007]

[0008] wherein, in Formula (1), Z 1 and Z 2 are each independently a single bond or a divalent linking group comprising one or more of substituted or unsubstituted C 1-30 alkylene, substituted or unsubstituted C 1-30 heteroalkylene, substituted or unsubstituted C 3-30 cycloalkylene, substituted or unsubstituted C 2-30 heterocycloalkylene, substituted or unsubstituted C 6-30 arylene, substituted or unsubstituted C 1-30 heteroarylene, -0-, -C(O)-, -N(R 3 )-, -S-, or -S(O)2-, wherein R 3 is hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 2-20 heterocycloalkyl, optionally, Z 1 and Z 2 are each independently a single bond or a divalent linking group comprising one or more of substituted or unsubstituted C 1With Z 2 The single or double bonds between them form a ring, R 1 and R 2 Each is a substituted or unsubstituted C independently. 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 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 1-30 heteroaryl, substituted or unsubstituted C 2-30 Heteroarylalkyl, substituted or unsubstituted C 2-30 Alkyl heteroaryl, -OR 4 、or -N(R 5 )2, where R 4 and R 5 Each is a substituted or unsubstituted C independently. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-20 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 1-30 heteroaryl, substituted or unsubstituted C 2-30 Heteroarylalkyl, or substituted or unsubstituted C 2-30 Alkyl heteroaryl, optionally, R 1 and R 2 A ring is formed together by a single bond or a divalent linker, where L is a single bond or a multivalent linker. Optionally, L is a multivalent linker that further comprises another group having the following formula:

[0009] and

[0010] P is a polymerizable group.

[0011] A patterning method is also provided, comprising (a) applying a layer of the photoresist composition of the present invention onto a substrate; (b) exposing the photoresist composition layer to activated radiation in a patterned manner; and (c) developing the exposed photoresist composition layer to provide a resist relief image. Detailed Implementation

[0012] Reference will now be made in detail to exemplary embodiments, examples of which are shown in this specification. In this respect, exemplary embodiments of the invention may take different forms and should not be construed as limiting to the description herein. Therefore, exemplary embodiments are described below only by reference to the accompanying drawings to explain aspects of this specification. As used herein, the term “and / or” includes any and all combinations of one or more of the associated listed items. When a statement such as “at least one / of…” precedes the list of elements, it modifies the entire list of elements and does not modify any individual element in the list.

[0013] As used herein, the terms “a / an” and “the” do not indicate a limitation of quantity and are to be construed as including both the singular and plural unless otherwise indicated herein or clearly contradicted by the context. Unless otherwise explicitly stated, “or” means “and / or”. The modifier “about” used in conjunction with quantity includes the stated value and has the meaning specified by the context (e.g., including the degree of error associated with a particular quantity of measurement). The full scope disclosed herein includes endpoints, and these endpoints may be independently combined with each other. The suffix “(s)” is intended to include both the singular and plural of the term it modifies, thereby including at least one of the stated terms. “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 as well as examples of its non-occurrence. The terms “first,” “second,” and similar terms herein do not indicate order, quantity, or importance, but are used to distinguish one element from another. When an element is referred to as being “on” another element, it may be in direct contact with or interposed with the other element, in which the element may exist. In contrast, when an element is referred to as being "directly on" another element, there is no inserting element. It should be understood that the components, elements, limitations, and / or features of the described aspects can be combined in any suitable manner within the aspects.

[0014] 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.

[0015] As used herein, the term "alkyl group" refers to an organic compound having at least one carbon atom and at least one hydrogen atom, optionally substituted with one or more substituents at the indicated location; "alkyl" refers to a straight-chain or branched saturated hydrocarbon having a specified number of carbon atoms and a valence of 1; "alkylene" refers to an alkyl group having a valence of 2; "hydroxyalkyl" refers to an alkyl group substituted with at least one hydroxyl group (-OH); "alkoxy" refers to "alkyl-O-"; "carboxylic acid group" refers to a group having the formula "-C(=O)-OH"; "cycloalkyl" refers to a monovalent group having one or more saturated rings in which all ring members are carbon atoms; "cycloalkylene" refers to a cycloalkyl group having a valence of 2; "alkenyl" refers to a straight-chain or branched monovalent hydrocarbon having at least one carbon-carbon double bond; "alkenyloxy" refers to "alkenyl-O-"; "alkenylene" refers to an alkyl group having a valence of 2 The valence of an alkenyl group is defined as follows: "cycloalkenyl" refers to a non-aromatic cyclic hydrocarbon group having at least three carbon atoms and at least one carbon-carbon double bond; "alkynyl" refers to a monovalent hydrocarbon group having at least one carbon-carbon triple bond; the term "aromatic group" refers to a monocyclic or polycyclic ring system that satisfies Hückel's rule and includes a carbon atom in the ring, and optionally may include one or more heteroatoms selected from N, O, and S that replace the carbon atoms in the ring; "aryl" refers to a monovalent aromatic monocyclic or polycyclic ring system in which each ring member is carbon, and may include a group having an aromatic ring fused to at least one cycloalkyl or heterocyclic alkyl ring; "arylene" refers to an aryl group having a valence of 2; "alkylaryl" refers to an aryl group that has been substituted with an alkyl group; "arylalkyl" refers to an alkyl group that has been substituted with an aryl group; "aryloxy" refers to "aryl-O-"; and "arylthio" refers to "aryl-S-".

[0016] The prefix "hetero" means that the compound or group includes at least one member (e.g., 1, 2, 3, or 4 or more heteroatoms) as a heteroatom replacing a carbon atom, wherein each heteroatom is independently N, O, S, Si, or P; "heteroatom-containing group" means a substituent including at least one heteroatom; "heteroalkyl" means an alkyl group having 1 to 4 or more heteroatoms replacing a carbon atom; "heterocyclic alkyl" means a cycloalkyl group having 1 to 4 or more heteroatoms as a ring member replacing a carbon atom; "heterocyclic alkyl" means a heterocyclic alkyl group having a valence of 2; "heteroaryl" means an aryl group having 1 to 4 or more heteroatoms as a ring member replacing a carbon atom; and "heteroaryl" means a heteroaryl group having a valence of 2.

[0017] The term "halogen" refers to a monovalent substituent of fluorine (fluorinated), chlorine (chloroinated), bromine (brominated), or iodine (iodinated). The prefix "halogenated" indicates a group that includes one or more of the fluorine, chlorine, bromine, or iodine substituents that replace a hydrogen atom. Combinations of halogen groups (e.g., bromine and fluorine) or only a single halogen group (e.g., fluorine) can be present.

[0018] "Fluorinated" should be understood as indicating the presence of fluorine atoms in one or more incorporated groups. For example, when indicating C... 1-18 When fluoroalkyl is used, the fluoroalkyl group can include one or more fluorine atoms, such as a single fluorine atom, two fluorine atoms (e.g., 1,1-difluoroethyl), three fluorine atoms (e.g., 2,2,2-trifluoroethyl), or fluorine atoms in each free valence of carbon (e.g., perfluorinated groups such as CF3, C2F5, C3F7, or C4F9). "Substituted fluoroalkyl" should be understood to mean a fluoroalkyl group further substituted with additional substituents.

[0019] As used herein, an "acid-indestructible group" refers to a group in which a bond is broken by the catalytic action of an acid (optionally and typically in conjunction with heat treatment), resulting in the formation of a polar group (such as a carboxylic acid or alcohol group) on the polymer, and optionally and typically, a portion attached to the broken bond that is disconnected from the polymer. Such acids are typically photogenerated acids that undergo bond cleavage during post-exposure baking. Suitable acid-indestructible groups include, for example, tertiary alkyl ester groups, secondary or tertiary aryl ester groups, secondary or tertiary ester groups having a combination of alkyl and aryl groups, tertiary alkoxy groups, acetal groups, or ketal groups. Acid-indestructible groups are also commonly referred to in the art as "acid-crackable groups," "acid-crackable protecting groups," "acid-indestructible protecting groups," "acid-leaving groups," "acid-decomposable groups," and "acid-sensitive groups."

[0020] "Substituted" means that at least one hydrogen atom on the stated group is replaced by another group, provided that the normal valence of the specified atom is not exceeded. When the substituent is an oxo group (i.e., =O), both hydrogen atoms on the carbon atom are replaced. Combinations of substituents or variables are permitted. Exemplary groups that may exist at the "substituted" position include, but are not limited to, nitro (-NO2), cyano (-CN), hydroxyl (-OH), oxo (=O), amino (-NH2), mono- or di-(C1-6)alkylamino, alkylacyl (such as C1-6), etc. 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 1-6Alkyl, 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 having at least one aromatic ring 6-12 Aryl (e.g., phenyl, biphenyl, naphthyl, etc., each ring being substituted or unsubstituted aromatic), having 1 to 3 single or fused rings and 6 to 18 ring carbon atoms, C 7-19 arylalkyl, arylalkoxy having 1 to 3 single or fused rings and 6 to 18 ring carbon atoms, C 7-12 alkylaryl, C 2-12 Heterocyclic alkyl, C 1-12 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 with any substituents. For example, the group -CH2CH2CN is a C2 alkyl group substituted with a cyano group.

[0021] This invention relates to photoresist compositions comprising a first polymer, a second polymer, a photoacid generator, a solvent, and may contain other optional components. The inventors have discovered that the specific photoresist compositions of this invention can be used to prepare photoresist films that achieve high contact angles during immersion scanning and can be polarized to become highly soluble in alkaline developers such as TMAH.

[0022] The first polymer comprises repeating units containing acid-labile groups, which can be cleaved by photo-generated acids under post-exposure baking conditions. The first polymer may optionally contain lactone groups.

[0023] The first repeating unit of the first polymer may be derived from one or more monomers having formula (1a), (1b), (1c), (1d), or (1e):

[0024]

[0025] In formulas (1a) to (1e), Ra is hydrogen, fluorine, cyano, substituted or unsubstituted C. 1-10 Alkyl, or substituted or unsubstituted C 1-10 Fluoroalkyl. Preferably, Ra is hydrogen, fluorine, or a substituted or unsubstituted C. 1-5 Alkyl groups, typically methyl groups.

[0026] In equation (1a), L 1 It is a divalent linking group comprising at least one carbon atom, at least one heteroatom, or a combination thereof. For example, L 1 It can include 1 to 10 carbon atoms and at least one heteroatom. In a typical example, L 1 It can be -OCH2-, -OCH2CH2O-, or -N(R) 1a )-, where R 1a Is it hydrogen or C? 1-6 alkyl.

[0027] In equations (1a) and (1b), R 7 To R 12 Each is independently a hydrogen, straight-chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 Cycloalkyl, monocyclic or polycyclic C 2-20 Heterocyclic alkyl, straight-chain or branched C 2-20 alkenyl, monocyclic or polycyclic C 3-20 Cycloalkenyl, monocyclic or polycyclic C 3-20 Heterocyclic alkenyl, monocyclic or polycyclic C 6-20 aryl, or monocyclic or polycyclic C 1-20 Heteroaryl groups, each of which is substituted or unsubstituted; provided that R 7 To R 9 Only one of them can be hydrogen and R 10 To R 12 Only one of them can be hydrogen. Preferably, R 7 To R 12 Each C is either a straight chain or a branched chain. 1-6 Alkyl, or monocyclic or polycyclic C 3-10 Cycloalkyl groups, each of which may be substituted or unsubstituted.

[0028] In equation (1a), R 7 To R 9 Any two of them can optionally form a ring, and R 7 To R 9 Each of these may optionally further include, as part of its structure, elements selected from -O-, -C(O)-, -C(O)-O-, -S-, -S(O)2-, and N(R). 19 One or more groups of )-S(O)2-, wherein R 19 It is hydrogen, straight-chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 Cycloalkyl, or monocyclic or polycyclic C 2-20 Heterocyclic alkyl groups. In formula (1b), R 10 To R12 Any two of them can optionally form a ring, and R 10 To R 12 Each of these may optionally further include, as part of its structure, elements selected from -O-, -C(O)-, -C(O)-O-, -S-, -S(O)2-, and N(R). 20 One or more groups of )-S(O)2-, wherein R 20 It is hydrogen, straight-chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 Cycloalkyl, or monocyclic or polycyclic C 2-20 Heterocyclic alkyl groups. For example, R 7 To R 12 Any one or more of them can independently be of the formula -CH2C(=O)CH (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 be independently substituted or unsubstituted, including those having the formula -O(C a1 (C) a2 The C of the O- group 2-10 Heterocyclic alkyl, 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 be arranged together to form a ring.

[0029] In equations (1c) and (1e), R 13 To R 14 Each can be an independent hydrogen, straight-chain, or branched C. 1-20 alkyl, monocyclic or polycyclic C 3-20 Cycloalkyl, monocyclic or polycyclic C 2-20 Heterocyclic alkyl, monocyclic or polycyclic C 6-20 aryl, or monocyclic or polycyclic C 1-20 Heteroaryl groups, each of which is substituted or unsubstituted; and R 15 Is it a straight chain or a branched chain? 1-20 alkyl, monocyclic or polycyclic C 3-20 Cycloalkyl, or monocyclic or polycyclic C 2-20 Heterocyclic alkyl groups, each of which may be substituted or unsubstituted. Optionally, R 13 Or R 14 One of them and R 15 Together they form a heterocyclic ring. Preferably, R 13 and R 14 Each can be an independent hydrogen, straight-chain, or branched C. 1-20 alkyl, monocyclic or polycyclic C3-20 Cycloalkyl, or monocyclic or polycyclic C 2-20 Heterocyclic alkyl groups.

[0030] In equation (1d), R 16 To R 18 Each C can be either a straight chain or a branched chain independently. 1-20 alkyl, monocyclic or polycyclic C 3-20 Cycloalkyl, monocyclic or polycyclic C 2-20 Heterocyclic alkyl, monocyclic or polycyclic C 6-20 aryl, or monocyclic or polycyclic C 1-20 Heteroaryl groups, each of which is substituted or unsubstituted, R 16 To R 18 Any two of them can optionally form a ring together, and R 16 To R 18 Each of these may optionally include, as part of its structure, a selection from -O-, -C(O)-, -C(O)-O-, -S-, -S(O)2-, and N(R 21 One or more groups of )-S(O)2-, wherein R 21 It can be hydrogen, straight-chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 Cycloalkyl, or monocyclic or polycyclic C 2-20 Heterocyclic alkyl; Xa is a polymerizable group selected from vinyl and norbornyl.

[0031] In equations (1d) and (1e), each L 2 It is a single bond or a divalent linker, provided that X is a single bond or a divalent linker. a When it is vinyl, L 2 It is not a single bond. Preferably, L 2 Is it a single-ring or multi-ring C? 6-30 aryl, or monocyclic or polycyclic C 6-30 Cycloalkylene groups, each of which may be substituted or unsubstituted. In formulas (1d) and (1e), n is 0 or 1. It should be understood that when n is 0, L 2 The group is directly attached to the oxygen atom.

[0032] Non-limiting examples of monomer (1a) include:

[0033]

[0034] Non-limiting examples of monomers having formula (1b) include:

[0035]

[0036]

[0037] Where R d As mentioned above for R a Defined, and R' and R" are each independently a straight chain or a branched chain of C. 1-20 alkyl, monocyclic or polycyclic C 3-20 Cycloalkyl, monocyclic or polycyclic C 2-20 Heterocyclic alkyl, straight-chain or branched C 2-20 alkenyl, monocyclic or polycyclic C 3-20 Cycloalkenyl, monocyclic or polycyclic C 3-20 Heterocyclic alkenyl, monocyclic or polycyclic C 6-20 aryl, or monocyclic or polycyclic C 1-20 A heteroaryl group, each of which is substituted or unsubstituted.

[0038] Non-limiting examples of monomers having formula (1c) include:

[0039]

[0040] Where R d As defined above for Ra.

[0041] Non-limiting examples of monomers (1d) include:

[0042]

[0043] Non-limiting examples of monomers (1e) include:

[0044]

[0045] In another example, the repeating unit of the first polymer having an acid-labile group can be derived from one or more monomers having cyclic acetal or cyclic ketal groups, such as monomers having the following formula:

[0046]

[0047]

[0048] Where Rd is defined as Ra as above.

[0049] In another example, the repeating unit of the first polymer having an acid-labile group can be derived from one or more monomers having a tertiary alkoxy group, such as monomers having the following formula:

[0050]

[0051] The repeating unit having an acid-labile group is typically present in the first polymer in an amount of 10 to 80 mol%, more typically 20 to 75 mol%, and even more typically 30 to 60 mol% based on the total repeating units in the first polymer.

[0052] The first polymer may optionally comprise one or more additional repeating units. These additional repeating units may include, for example, one or more units for the purpose of modulating the properties of the photoresist composition, such as etching rate and solubility. Exemplary additional units may include one or more of (meth)acrylates, vinyl aromatics, vinyl ethers, vinyl ketones, and vinyl esters. These one or more additional repeating units (if present in the first polymer) may be used in an amount up to 90 mol%, typically 3 to 50 mol%, based on the total repeating units of the first polymer.

[0053] The first polymer may further include a lactone-containing repeating unit derived from a monomer having formula (2):

[0054]

[0055] Where Rb is hydrogen, fluorine, cyano, substituted or unsubstituted C. 1-10 Alkyl, or substituted or unsubstituted C 1-10 Fluoroalkyl. Preferably, Rb is hydrogen, fluorine, or a substituted or unsubstituted C. 1-5 Alkyl group, typically methyl group. L 3 It can be a single bond or a divalent linker containing 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 7-30 Arylalkylene, substituted or unsubstituted C 1-30 heteroaryl, or substituted or unsubstituted C 2-30 Heteroarylalkylene, wherein L 3 Optionally, it may further comprise one or more groups selected from, for example, -O-, -C(O)-, -C(O)-O-, -S-, -S(O)2- and N(R23)-S(O)2-, wherein R 23 It can be hydrogen, straight-chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 Cycloalkyl, or monocyclic or polycyclic C 2-20 Heterocyclic alkyl. R 22 It is a monocyclic, polycyclic, or fused polycyclic compound containing C.4-20 Lactone groups, or monocyclic, polycyclic, or fused polycyclic groups containing C 4-20 The group of sulfonyl lactone.

[0056] Non-limiting examples of monomers having formula (2) include:

[0057]

[0058]

[0059] Rf is the same as Rb, which is disclosed in this paper.

[0060] When present, the first polymer typically contains 5 to 60 mol%, typically 10 to 55 mol%, and more typically 20 to 50 mol% of the total molar amount of the repeating units in the first polymer.

[0061] The first polymer may contain a base-soluble repeating unit having a pKa of less than or equal to 12. For example, the base-soluble repeating unit may be derived from a monomer having formula (3):

[0062]

[0063] Where R c It is a hydrogen, fluorine, cyano, substituted or unsubstituted C group. 1-10 Alkyl, or substituted or unsubstituted C 1-10 Fluoroalkyl. Preferably, R c It is hydrogen, fluorine, or substituted or unsubstituted C. 1-5 Alkyl group, typically methyl group. Q 1 It can be one or more of the following: 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 1-30 Heteroaryl, or -C(O)-O-. W contains the following alkali-soluble groups: -C(O)-OH; -C(CF3)2OH; amide; imide; or -NH-S(O)2-Y. 1 , where Y 1 Is it F or C? 1-4 Perfluoroalkyl. In formula (3), a is an integer from 1 to 3.

[0064] Non-limiting examples of monomers having formula (3) include:

[0065]

[0066] Where Rg For R c Defined and Y 1 It is as described above.

[0067] When present, the first polymer typically contains alkali-soluble repeating units in an amount of 5 to 60 mol%, typically 5 to 55 mol%, and more typically 10 to 50 mol%, based on the total repeating units in the first polymer.

[0068] 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 3,000 to 20,000 Da, and still more preferably 3,000 to 10,000 Da. w The first polymer's polydispersity index (PDI) (which is M) w Number-average molecular weight (M n The ratio of 1 / 3 to 1 / 2 is typically 1.1 to 3, and more typically 1.1 to 2. Molecular weight values ​​are determined by gel permeation chromatography (GPC) using polystyrene standards.

[0069] The photoresist composition includes a second polymer. The second polymer comprises repeating units derived from one or more monomers having formula (4):

[0070]

[0071] Among them, Z 1 and Z 2 Each is independently a single bond or contains one or more of the following divalent linking groups: 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 1-30 Hybrid aryl, -O-, -C(O)-, -N(R) 3 -, -S-, or -S(O)2-, where R 3 is hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 2-20 Heterocyclic alkyl groups. Optionally, Z 1 and Z 2 Through Z 1 With Z 2 The single or double bonds between them form a ring.

[0072] In equation (4), R 1 and R 2 Each can be either substituted or unsubstituted C independently. 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 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 1-30 heteroaryl, substituted or unsubstituted C 2-30 Heteroarylalkyl, substituted or unsubstituted C 2-30 Alkyl heteroaryl, -OR 4 、or -N(R 5 )2, where R 4 and R 5 Each is a substituted or unsubstituted C independently. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-20 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 1-30 heteroaryl, substituted or unsubstituted C 2-30 Heteroarylalkyl, or substituted or unsubstituted C 2-30 Alkyl heteroaryl. Optionally, R 1 and R 2 A ring is formed by a single bond or by a divalent linker comprising one or more of the following: 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 divalent C 7-30 arylalkyl, substituted or unsubstituted C 1-30 Heteroaryl, or substituted or unsubstituted divalent C 2-30 heteroarylalkyl, -O-, -C(O)-, -C(O)-O-, -C(O)-N(R) 2a -, -S-, -S(O)2-, or N(R) 2a)-S(O)2-, where R 2a It is hydrogen, straight-chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 Cycloalkyl, or monocyclic or polycyclic C 2-20 Heterocyclic alkyl groups.

[0073] In formula (4), L is a single bond or a multivalent linker, such as a divalent linker, a trivalent linker, or a tetravalent linker. For example, L can be a single bond or a divalent linker selected from one or more of the following: 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 divalent C 7-30 arylalkyl, substituted or unsubstituted C 1-30 Heteroaryl, or substituted or unsubstituted divalent C 2-30 heteroarylalkyl, -O-, -C(O)-, -C(O)-O-, -C(O)-N(R) 2b -, -S-, -S(O)2-, or N(R) 2b )-S(O)2-, where R 2b It is hydrogen, straight-chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 Cycloalkyl, or monocyclic or polycyclic C 2-20 Heterocyclic alkyl groups.

[0074] In formula (4), P is a polymerizable group. Typically, the polymerizable group is selected from (meth)acrylic acid, vinyl and norbornyl.

[0075] In equation (4), L is optionally a multivalent linking group that further comprises another group having the following formula:

[0076]

[0077] Z 1 Z 2 R 1 and R 2 As described above.

[0078] In some embodiments, the second polymer may comprise repeating units derived from one or more monomers having formula (4a):

[0079]

[0080] In equation (4a), R a It is a hydrogen, fluorine, cyano, substituted or unsubstituted C group.1-10 Alkyl, or substituted or unsubstituted C 1-10 Fluoroalkyl. L is as defined for formula (4). For example, L is a single bond or a divalent linker comprising one or more groups selected from: 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 1-30 Hybrid aryl, -O-, -C(O)-, -C(O)O-, -OC(O)-, -N(R 25 -, -S-, or -S(O)2-, where R 25 It is hydrogen, straight-chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 Cycloalkyl, or monocyclic or polycyclic C 2-20 Heterocyclic alkyl groups.

[0081] In equation (4a), Z 1 and Z 2 They are the same, where Z 1 and Z 2 Selected from single bonds, -O-, divalent linkers containing groups having the formula -C(O)-, or divalent linkers containing groups having the formula -C(O)-O-. R 1 and R 2 Each is a substituted or unsubstituted C independently. 1-30 Alkyl; and optionally, R 1 and R 2 A ring is formed by connecting groups together via single bonds or divalent linkages.

[0082] Non-limiting examples of monomers having formula (4) and / or (4a) include:

[0083]

[0084]

[0085] Monomers containing one bis(Boc)amide moiety can be referred to as single-arm monomers. Other exemplary monomers containing more than one bis(Boc)amide moiety can be referred to as two-arm monomers. For polymers containing structural units derived from single-arm monomers, a carboxyl functional group can be generated on each structural unit derived from the single-arm monomer upon hydrolysis. For polymers containing structural units derived from two-arm monomers, two carboxyl functional groups can be generated on each structural unit derived from the two-arm monomer upon hydrolysis. Similarly, for polymers containing structural units derived from three-arm monomers, three carboxyl functional groups can be generated on each structural unit derived from the three-arm monomer upon hydrolysis. This can be advantageous in making the polymer more hydrophilic upon contact with aqueous alkaline developers. Examples of two-arm monomers include those described below (e.g., monomer 17 from example ).

[0086] The second polymer may optionally further comprise one or more additional repeating units different from those derived from one or more monomers having formula (4). For example, the second polymer may optionally comprise one or more additional repeating units as described above for the optional additional repeating units of the first polymer, such as repeating units having acid-labile groups. Based on the total repeating units of the second polymer, one or more additional repeating units in the second polymer (if present) may be used in amounts up to 70 mol%, and typically 3 to 50 mol%.

[0087] In some aspects, the second polymer may include one or more repeating units derived from “base-insecure” monomers having the formula E1, E2 or E3 (described below).

[0088] The second polymer typically has an M value of 1,000 to 50,000 Da, preferably 2,000 to 30,000 Da, and more preferably 3,000 to 20,000 Da, still more preferably from 3,000 to 10,000 Da. w The PDI of this polymer is typically 1.1 to 3, and more typically 1.1 to 2. Molecular weight was determined by GPC using polystyrene standards.

[0089] The first and second polymers can be prepared using any suitable method in the art. For example, one or more monomers corresponding to the repeating units described herein can be fed together or separately using suitable one or more solvents and initiators and polymerized in a reactor. For example, the first and second polymers can be obtained by polymerizing the respective monomers under any suitable conditions, such as by heating at an effective temperature, irradiation with photochemical radiation at an effective wavelength, or a combination thereof.

[0090] The photoresist composition also includes a photoacid generator (PAG). A suitable PAG can generate an acid that causes the acid-indestructible groups present on the polymer of the photoresist composition to cleave during post-exposure baking (PEB). PAG can be included as a non-polymerizable PAG compound (as disclosed below), a repeating unit of a polymer having a PAG moiety derived from a polymerizable PAG compound, or a combination thereof. For example, the first polymer may optionally include a repeating unit containing PAG, such as a repeating unit derived from one or more monomers having formula (5):

[0091]

[0092] In equation (5), R h It is a hydrogen, fluorine, cyano, substituted or unsubstituted C group. 1-10 Alkyl, or substituted or unsubstituted C 1-10 Fluoroalkyl. Preferably, R h It is hydrogen, fluorine, or a substituted or unsubstituted C1-5 alkyl group, typically methyl. Q 2 It is a single bond or a divalent linker selected from one or more of the following: heteroatom, 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 divalent C 1-30 Hybrid aryl groups, or combinations thereof. For example, Q 2 It may include 1 to 10 carbon atoms and at least one heteroatom, more preferably -C(O)-O-.

[0093] In equation (5), A is one or more of the following: 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 1-30 Hybrid aryl. Preferably, A is an optionally substituted divalent C. 1-30 Perfluoroalkylene. Z- is the anionic moiety containing sulfonate, carboxylate, sulfonamide, sulfonamide, or methyl anion. G + It is an organic cation as described below.

[0094] Exemplary monomers having formula (5) include the following:

[0095]

[0096] Among them G + It is an organic cation. Organic cations include, for example, iodonium cations substituted with two alkyl, aryl, or combinations of alkyl and aryl groups; and sulfonium cations substituted with three alkyl, aryl, or combinations of alkyl and aryl groups. In some embodiments, G + It is an iodonium cation substituted with two alkyl, aryl, or a combination of alkyl and aryl groups; or a sulfonium cation substituted with three alkyl, aryl, or a combination of alkyl and aryl groups. In some embodiments, G + It can be one or more of a substituted sulfonium cation having formula (5A) or an iodonium cation having formula (5B):

[0097]

[0098] Among them, each R aa C is independent 1-20 Alkyl, C 1-20 fluoroalkyl, C 3-20 cycloalkyl, C 3-20 Fluorocycloalkyl, C 2-20 alkenyl, C 2-20 Fluoroolefin, C 6-30 Aryl, C 6-30 Fluoroaryl, C 6-30 Iodoaryl, C 1-30 heteroaryl, C 7-20 Arylalkyl, C 7-20 Fluoroarylalkyl, C 2-30 heteroarylalkyl, or C 2-30 Fluoroarylalkyl groups, each of which is substituted or unsubstituted, wherein each R aa It is either independent or connected to another group Raa via a single bond or a divalent linker to form a ring. Each R aa Optionally, it may include one or more groups selected from the following as part of its structure: -O-, -C(O)-, -C(O)-O-, -C 1-12 -, -O-(C) 1-12 (-, -C(O)-O-(C) 1-12 (Hydroalkyl)- and -C(O)-O-(C 1-12 (Hydroxy)-O-. Each R aa Independently, it may optionally contain an acid-indestructible group selected from, for example, of the following: tertiary alkyl ester group, secondary or tertiary aryl ester group, secondary or tertiary ester group having a combination of alkyl and aryl groups, tertiary alkoxy group, acetal group, or ketal group. Suitable divalent linking groups for attaching the Raa group include, for example, -O-, -S-, -Te-, -Se-, -C(O)-, -C(S)-, -C(Te), S(O)-, S(O)2-, -N(R)- or -C(Se-), substituted or unsubstituted C1-5 Alkylenes and combinations thereof, wherein R is hydrogen, C is carbon, and C is hydrogen. 1-20 Alkyl, C 1-20 Heteroalkyl, C 6-30 Aryl or C 1-30 Heteroaryl groups, wherein each of the groups other than hydrogen can be substituted or unsubstituted.

[0099] Exemplary sulfonium cations having formula (5A) include the following:

[0100]

[0101]

[0102] Exemplary iodonium cations having formula (5B) include the following:

[0103]

[0104] PAGs that are onium salts typically contain organic anions with sulfonate groups or non-sulfonate groups, such as sulfonamide groups, sulfonimidate groups, methyl groups, or borate groups.

[0105] Exemplary organic anions having a sulfonate group include the following:

[0106]

[0107] Exemplary nonsulfonated anions include the following:

[0108]

[0109]

[0110] The photoresist composition may optionally contain a variety of PAGs. The PAGs may be polymeric, non-polymeric, or may include both polymeric and non-polymeric PAGs. Preferably, each of the PAGs is non-polymeric.

[0111] In one or more aspects, the photoresist composition may include a first photoacid generator comprising a sulfonate group on an anion, and the photoresist composition may include a non-polymerized second photoacid generator, wherein the second photoacid generator may include an anion without a sulfonate group.

[0112] Typically, when a photoresist composition contains one or more nonpolymerized photoacid generators, these photoacid generators are present in the photoresist composition in a combined amount of 1 to 65 wt%, more typically 5 to 55 wt%, and still more typically 8 to 30 wt%, based on the total solids of the photoresist composition.

[0113] The first polymer may include one or more repeating units comprising a photoacid generator. If used in the first polymer, such units are typically present in an amount of 1 to 15 mol%, more typically 1 to 10 mol%, and still more typically 2 to 6 mol% based on the total repeating units in the first polymer.

[0114] The second polymer may optionally include repeating units containing PAG derived from one or more monomers having formula (5), as disclosed above. The second polymer may include one or more repeating units containing PAG based on a typical amount of 1 to 10 mol%, more typically 1 to 8 mol%, and still more typically 2 to 6 mol% of the total repeating units in the second polymer.

[0115] 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, 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); propylene glycol monomethyl ether (PGME); ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and anisole; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 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 pyruvate; 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, propylene carbonate, diphenyl carbonate, and propylene carbonate; polar aprotic solvents such as dimethyl sulfoxide and dimethylformamide; water; and combinations thereof. Among these, preferred solvents are PGME, PGMEA, EL, GBL, HBM, CHO, and combinations thereof. The total solvent content in the photoresist composition (i.e., the cumulative solvent content of all solvents) is typically 40 to 99 wt%, for example 70 to 99 wt%, or 85 to 99 wt%, based on the total solids of the photoresist composition. The desired solvent content will depend on, for example, the desired thickness of the photoresist layer and the coating conditions.

[0116] The photoresist composition typically comprises a first polymer and a second polymer in a weight ratio of 1:1 to 1,000:1, for example 1:1 to 100:1, or 1:1 to 20:1, or 1:1 to 10:1.

[0117] In the photoresist composition of the present invention, the first polymer and the second polymer are typically present together in the photoresist composition in amounts ranging from 10 to 99.9 wt%, typically 25 to 99 wt%, and more typically 50 to 95 wt% based on the total solids of the photoresist composition. It will be understood that the total solids include the first and second polymers, PAG, and other non-solvent components.

[0118] Based on the total solids of the photoresist composition, the photoresist composition typically comprises 0.1 wt% to 20 wt% of a second polymer. For example, the photoresist composition preferably comprises 0.1 wt% to 10 wt% of a second polymer or 0.1 wt% to 5 wt% of a second polymer, each based on the total solids of the photoresist composition.

[0119] In some aspects, the photoresist composition may further comprise a material containing one or more base-indestructible groups (“base-indestructible material”). As mentioned herein, a base-indestructible group is a functional group that can undergo a cleavage reaction in the presence of an aqueous base developer after the exposure and post-exposure baking steps to provide a polar group (such as hydroxyl, carboxylic acid, sulfonic acid, etc.). The base-indestructible group will not react significantly prior to the development step of the photoresist composition containing the base-indestructible group (e.g., will not undergo bond-breaking reactions). Thus, for example, the base-indestructible group will be substantially inert during the pre-exposure soft bake step, the exposure step, and the post-exposure baking step. “Substantially inert” means that ≤5%, typically ≤1%, of the base-indestructible group (or portion) will decompose, cleave, or react during the pre-exposure soft bake, exposure, and post-exposure baking steps. The base-indestructible group is reactive under typical photoresist development conditions using, for example, an aqueous base photoresist developer (such as an aqueous solution of 0.26 standard (N) tetramethylammonium hydroxide (TMAH)). For example, a 0.26N aqueous solution of TMAH can be used for single-immersion development or dynamic development, where, for example, 0.26N of TMAH developer is dispensed onto the imaged photoresist layer for a suitable duration (e.g., 10 to 120 seconds). Exemplary base-insecure groups are ester groups, typically fluorinated ester groups. Preferably, the base-insecure material is substantially immiscible with the first and second polymers of the photoresist composition and other solid components and has a lower surface energy than them. Thus, when coated onto a substrate, the base-insecure material can separate from the other solid components of the photoresist composition and reach the top surface of the formed photoresist layer.

[0120] In some respects, an alkali-insecure material is a polymeric material that may comprise one or more repeating units containing one or more alkali-insecure groups (also referred to herein as an alkali-insecure polymer). For example, an alkali-insecure polymer may comprise repeating units containing two or more identical or different alkali-insecure groups. Preferred alkali-insecure polymers comprise at least one repeating unit containing two or more alkali-insecure groups, such as repeating units containing two or three alkali-insecure groups.

[0121] Alkali-unstable polymers can be polymers comprising repeating units derived from one or more monomers having the formula (E1):

[0122]

[0123] Where X b It is a polymerizable group selected from vinyl and acrylic acid, L 5 It is a divalent linker containing one or more of the following: substituted or unsubstituted straight-chain or branched C-chains. 1-20 Alkylene, substituted or unsubstituted C 3-20 Cycloalkylene, -C(O)- or -C(O)O-; and Rk is a substituted or unsubstituted C 1-20 Fluoroalkyl, provided that the carbon atom bonded to the carbonyl group (C=O) in formula (E1) is replaced by at least one fluorine atom.

[0124] Exemplary monomers having formula (E1) include the following:

[0125]

[0126] Alkali-insecure polymers may include repeating units comprising two or more alkali-insecure groups. For example, alkali-insecure polymers may include repeating units derived from one or more monomers having the formula (E2):

[0127]

[0128] Where Xb and Rk are defined as in equation (E1); L 6 It is a multivalent linker containing one or more of the following: substituted or unsubstituted straight-chain or branched C 1-20 Alkylene, substituted or unsubstituted C 3-20 Cycloalkylene, -C(O)- or -C(O)O-; and n represents an integer of 2 or greater, such as 2 or 3.

[0129] Exemplary monomers having formula (E2) include the following:

[0130]

[0131] Base-instable polymers may comprise repeating units including one or more base-instable groups. For example, a base-instable polymer may comprise repeating units derived from one or more monomers having the formula (E3):

[0132]

[0133] Where X b It is as defined in equation (E1); L 7 It is a divalent linker containing one or more of the following: substituted or unsubstituted straight-chain or branched C-chains. 1-20 Alkylene, substituted or unsubstituted C 3-20 Cycloalkylene, -C(O)- or -C(O)O-; L f Is it substituted or unsubstituted C? 1-20 A fluoroalkyl group wherein the carbon atom bonded to the carbonyl group (C=O) in formula (E1) is substituted with at least one fluorine atom; and Rm is a substituted or unsubstituted straight-chain or branched C-group. 1-20 Alkyl, or substituted or unsubstituted C 3-20 Cycloalkyl.

[0134] Exemplary monomers having formula (E3) include the following:

[0135]

[0136] In another preferred aspect of the invention, the alkali-insecure polymer may comprise one or more alkali-insecure groups and one or more acid-insecure groups, such as one or more acid-insecure ester moieties (e.g., tert-butyl ester) or acid-insecure acetal groups. For example, the alkali-insecure polymer may comprise repeating units including both alkali-insecure and acid-insecure groups, i.e., where both alkali-insecure and acid-insecure groups are present on the same repeating unit. In another example, the alkali-insecure polymer may comprise a first repeating unit containing alkali-insecure groups and a second repeating unit containing acid-insecure groups. Preferred photoresists of the present invention can exhibit reduced defects associated with resist relief images formed from photoresist compositions.

[0137] Base-instable polymers can be prepared using any suitable method in the art, including those described herein with respect to the first and second polymers. For example, base-instable polymers can be obtained by polymerization of the respective monomers under any suitable conditions, such as by heating at an effective temperature, irradiation with photochemical radiation at an effective wavelength, or a combination thereof. Furthermore or alternatively, suitable methods can be used to graft one or more base-instable groups onto the polymer backbone.

[0138] In some respects, alkali-instable materials are single molecules comprising one or more alkali-instable ester groups, preferably one or more fluorinated ester groups. Alkali-instable materials that are single molecules typically have an M value in the range of 50 to 1,500 Da. W Exemplary alkali-instable materials include the following:

[0139] In addition, or alternatively, besides the alkali-instable polymer, the photoresist composition may further include one or more polymers other than and different from the first and second polymers described above. For example, the photoresist composition may contain additional polymers as described above but with different compositions, or polymers similar to those described above but not containing each of the required repeating units. Furthermore, or alternatively, the one or more additional polymers may include those well-known in the field of photoresists, such as those selected from: polyacrylates, polyvinyl ethers, polyesters, polynorbornene, polyacetals, polyethylene glycol, polyamides, polyacrylamide, polyphenols, phenolic varnishes, styrene polymers, polyvinyl alcohol, or combinations thereof.

[0140] The photoresist composition may further include one or more additional optional additives. For example, optional additives may include photochemical dyes and contrast dyes, anti-stripping agents, plasticizers, accelerators, sensitizers, photodegradable quenchers (PDQ) (and also referred to as photodegradable bases), alkaline quenchers, hot acid generators, surfactants, etc., or combinations thereof. If present, optional additives are typically present in the photoresist composition in an amount of 0.01 to 10 wt% based on the total solids of the photoresist composition.

[0141] Photodegradable quenchers produce weak acids upon irradiation. The acids produced by photodegradable quenchers are not strong enough to react rapidly with acid-indegradable groups present in the resist matrix. Exemplary photodegradable quenchers include, for example, photodegradable cations, and are preferably also used to prepare strong acid-generating compounds, reacting with the anions of weak acids (pKa > -1) (e.g., C). 1-20 Carboxylic acid or C 1-20 Those sulfonic acids that are paired with the anion of the sulfonic acid. Exemplary carboxylic acids include formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexanecarboxylic acid, benzoic acid, salicylic acid, etc. Exemplary carboxylic acids include p-toluenesulfonic acid, camphorsulfonic acid, etc. In a preferred embodiment, the photodegradable quencher is a photodegradable organic zwitterionic compound, such as diphenyliodonium-2-carboxylic acid ester.

[0142] Photodegradable quenchers can be in non-polymeric or polymerically bonded forms. When in polymeric form, the photodegradable quencher is present in polymeric units on a first or second polymer. Polymeric units containing the photodegradable quencher are typically present in amounts of 0.1 to 30 mol%, typically 1 to 10 mol%, and more typically 1 to 2 mol%, based on the total repeating units in the polymer.

[0143] Exemplary alkaline 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-butoxycarbonyl)-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, di-tert-butylpyridine, and pyridinium; linear and cyclic amides and their derivatives such as N,N-bis(2-hydroxyethyl)palmitamide, N,N-diethylacetamide, N1,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.

[0144] Alkaline quenchers can be in non-polymeric or polymeric forms. When in polymeric form, the quencher is present in polymeric units on a first or second polymer. Polymeric units containing the quencher are typically present in amounts of 0.1 to 30 mol%, typically 1 to 10 mol%, and more typically 1 to 2 mol%, based on the total repeating units in the polymer.

[0145] 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 this aspect, the photoresist composition further comprises a surfactant polymer containing fluorinated repeating units.

[0146] 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 silicon, polycrystalline silicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanide, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. Suitable substrates can be in the form of wafers, such as those used for manufacturing integrated circuits, optical sensors, flat panel displays, integrated optical circuits, and LEDs. Such substrates can be of any suitable size. Typical wafer substrate diameters are 200 to 300 millimeters (mm), although wafers with smaller and larger diameters can be suitably used according to the present invention. The substrate may include one or more layers or structures that may optionally include active or operable portions of the formed device.

[0147] 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.

[0148] 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 from DuPont Electronics & Imaging (Marlborough, Massachusetts) under the names AP 3000, AP 8000, and AP 9000S.

[0149] 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 the photoresist in a solvent using a coating track, wherein the photoresist is dispensed onto a rotating wafer. During dispensing, the wafer is typically rotated at a speed up to 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 solids content of the composition. Photoresist layers formed from the compositions of the present invention typically have a dry layer thickness of 10 to 500 nanometers (nm), preferably 15 to 200 nm, and more preferably 20 to 120 nm.

[0150] 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 still more typically 1 minute to 2 minutes. Those skilled in the art can readily determine the heating time based on the composition's components.

[0151] Next, the photoresist layer is patterned and exposed to activating radiation to create a solubility difference between exposed and unexposed areas. The exposure of the photoresist composition to radiation that activates the composition, as described herein, indicates that radiation can form a latent image within the photoresist composition. Exposure is typically performed using a patterned photomask with optically transparent and optically opaque regions corresponding to the areas of the photoresist layer to be exposed and the areas of the photoresist layer to be unexposed, respectively. Alternatively, this exposure can be performed without a photomask in a direct-write method, typically used in electron beam lithography. The activating radiation typically has wavelengths less than 400 nm, less than 300 nm, or less than 200 nm, preferably 248 nm (KrF), 13.5 nm (EUV), or electron beam lithography. These methods are used in immersion or dry (non-immersion) lithography techniques. The 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 It depends on the exposed tool and the composition of the photoresist composition.

[0152] 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 from 80°C to 150°C for 30 to 120 seconds. A latent image is formed in the photoresist, defined by polarity-converted regions (exposed regions) and non-polarity-converted regions (unexposed regions).

[0153] 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.

[0154] 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.

[0155] 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.

[0156] Photoresist patterns can be used, for example, as an etching mask to transfer the pattern to one or more sequentially arranged underlying layers using known etching techniques, typically dry etching (such as reactive ion etching). Photoresist patterns can also be used, for example, to transfer a pattern to an underlying hard mask layer, which in turn serves as an etching 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 (such as 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.

[0157] The invention is further illustrated by the following examples.

[0158] Example

[0159] Synthesis of Monomer 1: Methacrylamide (10.0 g, 1.0 equivalent) and dimethylaminopyridine (1.45 g, 0.1 equivalent) were dissolved in 250 mL of dichloromethane. Di-tert-butyl dicarbonate (53.9 g, 2.1 equivalent) was slowly added, and the reaction was stirred at room temperature for 16 hours. The reaction mixture was then washed with saturated sodium bicarbonate, water, and brine, and then dried over magnesium sulfate. The solvent was removed under reduced pressure to yield monomer 1.

[0160]

[0161] Synthesis of Monomer 2: N-hydroxy-5-norbornene-2,3-dicarboxylic acid imide (15.8 g, 1.0 equivalent) and triethylamine (13.2 g, 1.5 equivalent) were dissolved in 200 mL of dichloromethane. The reaction mixture was cooled to 0 °C and methacryloyl chloride (10.0 g, 1.1 equivalent) was slowly added to it. The reaction mixture was stirred at 23 °C–25 °C for 16 hours. The reaction mixture was then washed with saturated sodium bicarbonate, water, and brine, and then dried over magnesium sulfate. The solvent was removed under reduced pressure to yield monomer 2.

[0162]

[0163] Synthesis of monomers 13A, 13B, 13C, and 13D: Monomer 13A was prepared as shown in Scheme 1.

[0164] Option 1

[0165]

[0166] Where R = CH3, n = 2, (B o c)2O is ditert-butyl dicarbonate, and DMAP is 4-dimethylaminopyridine.

[0167] Similarly, monomers 13B (R=CH3, n=1), 13C (R=H, n=2), and 13D (R=H, n=1) are prepared as shown in Scheme 1, wherein (Boc)2O and DMAP are as defined above.

[0168] Synthesis of 5-hydroxypentanamide: Tetrahydro-2H-pyran-2-one (80.0 g, 799.04 mmol) in ethanol (200 mL, 2.5 vol) was charged into a 2-L autoclave. The contents of the autoclave were cooled to below -30 °C, and liquid ammonia (400 mL, 5 vol) was added. The autoclave was sealed, and the reaction mixture was heated to 90 °C–100 °C at 500–575 psi for 24 h. The reaction mixture was then cooled to room temperature, and the resulting solid was filtered from the mixture. The wet filter cake of the resulting solid was washed with ethyl acetate (300 mL, 3.75 vol) and dried under vacuum to yield 5-hydroxypentanamide (64.0 g, 68%) as a white solid. 1 H NMR δ (ppm): 7.20 (bs, 1H), 6.67 (bs, 1H), 4.36 (t, J=8.0Hz, 1H); 3.39 (t, J=12Hz, 2H), 1.53-1.47 (m, 2H), and 1.46-1.39 (m, 2H); FT-IR: 3400.56cm -1 (-OH, strong), 1643.3 cm-1 (-C=O, amide), and 3183.57cm -1 (-NH, amide); UPLC-ELSD: 99.84% purity (at 1.49 RT); MS: m / z = 118.13 [M+H] + .

[0169]

[0170] Synthesis of 5-amino-5-oxopentyl methacrylate: 5-hydroxypentanamide (5.0 g, 42.68 mmol) in 100 mL of dry dichloromethane was added to a 250 mL three-necked round-bottom flask equipped with a magnetic stir bar, internal thermometer, and nitrogen bubbler at room temperature. N,N-dimethyl-4-aminopyridine (521 mg, 4.27 mmol) and triethylamine (11.9 mL, 85.36 mmol) were added, and the resulting suspension was stirred for 15 min. Methacryl chloride (5 mL, 51.21 mmol) was then added dropwise, and the resulting mixture was stirred at room temperature for 16 h. The reaction mixture was diluted with 100 mL of dichloromethane and washed with 100 mL of chilled water and 50 mL of brine. The organic layer was separated, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude material was ground with 10% dichloromethane in hexane to produce 5-amino-5-oxopentyl methacrylate (6.0 g, 75%), a pale yellow solid. 1 H NMR δ (ppm): 7.25 (bs, 1H), 6.71 (bs, 1H), 6.02-6.01 (m, 1H), 5.67-5.66 (m, 1H); 4.13-4.07 (m, 2H), 1.88 (s, 3H), 1.64-1.57 (m, 4H); FT-IR: 2955.0cm -1 (-C = CH, stretching), 1649.17cm -1 (-C=O, amide), 1717.64cm -1 (-C=O, ester) and 3193.21cm -1 (-NH, amide); LCMS-ELSD: 92.7% purity (at 1.40 RT); MS: m / z = 186.23 [M+H] + .

[0171]

[0172] Synthesis of 2-methylprop-2-enoic acid [5-[bis(tert-butoxycarbonyl)amino]-5-oxo-pentyl] ester (monomer 13A): 5-amino-5-oxopentyl methacrylate (200 mg, 1.08 mmol), N,N-dimethyl-4-aminopyridine (26.5 mg, 0.21 mmol), and acetonitrile (4 mL) were added to a 25 mL three-necked round-bottom flask equipped with a magnetic stir bar and a nitrogen bubbler at room temperature. (Boc)₂O (0.99 mL, 4.32 mmol) was added, and the resulting mixture was stirred at room temperature for 16 h, diluted with ethyl acetate (4 mL), and washed with water (2 mL) and brine (2 mL). The organic layer was separated, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude material was purified by rapid silica gel (100-200 mesh) column chromatography using an elution gradient of 0-3 vol% ethyl acetate in hexane to produce 13.50 mg, 12% 2-methylprop-2-enoic acid [5-[bis(tert-butoxycarbonyl)amino]-5-oxo-pentyl] ester, which was a pale yellow liquid. 1 H NMR δ (ppm): 6.02 (t, J=1.6Hz, 1H), 5.67 (t, J=3.2Hz, 1H), 4.11 (t, J=12Hz, 2H), 2.82 (t, J=14Hz, 2H), 1.88 (s, 3H), 1.66-1.61 (m, 4H), 1.60 (s, 18H); FT-IR: 2982.9cm -1 (-C = CH, stretching), 1711.8cm -1 (-C=O, amide), 1787.0 cm -1 (-CC=O, ester); UPLC-ELSD: 99.55% purity (at 2.85 RT). No ionization was observed in LCMS or GCMS. The structure of monomer 13A was confirmed by 2D NMR.

[0173]

[0174] Synthesis of monomer 17: Preparation of the two-arm monomer 17 as shown in Scheme 2:

[0175] Option 2

[0176]

[0177] Polymer Synthesis: Exemplary polymer A2 was prepared as follows. A monomer feed solution was prepared using 23.4 g of propylene glycol monomethyl ether acetate (PGMEA), 10.0 g of monomer 1, and 1.6 g of monomer 4. An initiator feed solution was prepared separately using 8.3 g of PGMEA and 0.84 g of V-601. In a reactor, 9.4 g of PGMEA was heated to 80 °C, and the monomer feed solution was then added dropwise over 240 min, followed by the dropwise addition of the initiator feed solution over 90 min. After 4 hours, the reaction mixture was cooled to room temperature at 1 °C / min, and the polymer was then precipitated by direct addition to 1 L of 9 / 1 methanol / water (v / v). The polymer was collected by filtration and dried under vacuum to produce polymer A2.

[0178] Each polymer in Table 1 was prepared using a similar procedure and with the corresponding monomer feed solution. Based on the total moles of repeating units of the polymer, the amounts in Table 1 are the mole percentage (mol%) of repeating units derived from each specified monomer.

[0179] Table 1

[0180] Polymer First monomer Second monomer Third monomer Fourth monomer A1 1(100％) A2 1(80％) 4(20％) A3 2(100％) A4 2(80％) 5(20％) A5 13A(100％) A6 13A(90％) 4(10％) Bl 4(40％) 7(30％) 9(20％) 10(10％) B2 6(40％) 7(40％) 8(20％)

[0181] The structures of monomers 1 to 10 and 13A are as follows:

[0182]

[0183] The structures of photoactive compounds C1 and C2, and quencher compounds D1 and D2 are shown below.

[0184]

[0185]

[0186] Photoresist formulations. The photoresist compositions (R1-R6) are prepared by dissolving the solid components in solvents using the materials and amounts listed in Table 2. The resulting mixtures, prepared in batches of 14-30 g, are shaken on a mechanical shaker for 3 to 24 hours and then filtered through a PTFE disc filter with a pore size of 0.2 μm. The amounts of polymer 1, polymer 2, PAG, quencher, and solvent are reported as wt% of the total weight of the photoresist composition containing the solvent.

[0187] Table 2.

[0188]

[0189] Immersion patterning. Immersion lithography was performed using a TEL Lithius 300mm wafer track and an ASML 1900i immersion scanner with dipole illumination of 1.3NA, 0.86 / 0.61 inner / outer σ, and 35Y polarization. Wafers used for lithography testing were coated with AR40A. TM The bottom anti-reflective coating (BARC) (DuPont Electronics & Imaging) is cured at 205°C for 60 seconds to produce... Membrane. Then in AR40A TM AR104BARC deposited on the layer TM (DuPont Electronics & Imaging) coating and cured at 175°C for 60 seconds to produce the top of the double BARC stack. The film was then coated with a photoresist composition onto the double BARC stack and baked at 90°C for 60 seconds to produce a film. Photoresist film. The wafer was exposed using a focal exposure matrix with 1:1 line / space (L / S) patterns at 55nm / 110nm and 43nm / 86nm pitches, and subjected to PEB at 100°C for 60 seconds. After PEB, the wafer was developed in 0.26N TMAH solution for 12 seconds, rinsed with deionized water, and spin-dried. Scanning electron microscopy (SEM) was performed to acquire images, and the printed patterns were analyzed using a Hitachi CG4000CD-SEM.

[0190] The photoresist compositions R1-R6 of the present invention are expected to achieve good patterning ability and lower defect rate.

[0191] 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 comprising a first repeating unit, wherein the first repeating unit comprises an acid-labile group; and The second polymer comprises repeating units derived from one or more monomers having formula (4a); Photoacid generator; and Solvent, (4a) in, In equation (4a), R a It is a hydrogen, fluorine, cyano, substituted or unsubstituted C group. 1-10 Alkyl, or substituted or unsubstituted C 1-10 fluoroalkyl, L is a single bond or a multivalent linker. Z 1 and Z 2 They are the same, where Z 1 and Z 2 Selected from single bonds, -O-, divalent linking groups containing groups having the formula -C(O)-, or divalent linking groups containing groups having the formula -C(O)-O-; and R 1 and R 2 Each is a substituted or unsubstituted C independently. 1-30 alkyl.

2. The photoresist composition as claimed in claim 1, wherein, L is a multivalent linking group that further includes other groups having the following formula: ， Z 1 Z 2 R 1 and R 2 The definition is the same as in claim 1.

3. The photoresist composition as described in claim 1, wherein, The first repeating unit of the first polymer is derived from one or more monomers having formula (1a), (1b), (1c), (1d), or (1e): (1a) (1b) (1c) (1d) (1e) in, R a It is a hydrogen, fluorine, cyano, substituted or unsubstituted C group. 1-10 Alkyl, or substituted or unsubstituted C 1-10 fluoroalkyl; R 7 To R 12 Each is independently a hydrogen, straight-chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 Cycloalkyl, monocyclic or polycyclic C 2-20 Heterocyclic alkyl, straight-chain or branched C 2-20 alkenyl, monocyclic or polycyclic C 3-20 Cycloalkenyl, monocyclic or polycyclic C 3-20 Heterocyclic alkenyl, monocyclic or polycyclic C 6-20 aryl, or monocyclic or polycyclic C 1-20 A heteroaryl group, each of which is substituted or unsubstituted; The premise is R 7 To R 9 Only one of them can be hydrogen and R 10 To R 12 Only one of them can be hydrogen; R 7 To R 9 Any two of them can optionally form a ring together, and R 7 To R 9 Each of these may optionally further include, as part of its structure, a selection from -O-, -C(O)-, -C(O)-O-, -S-, -S(O)2-, and -N(R-). 19 One or more groups of )-S(O)2-, wherein R 19 It is hydrogen, straight-chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 Cycloalkyl, or monocyclic or polycyclic C 2-20 Heterocyclic alkyl groups; R 10 To R 12 Any two of them can optionally form a ring together, and R 10 To R 12 Each of these may optionally further include, as part of its structure, a selection from -O-, -C(O)-, -C(O)-O-, -S-, -S(O)2-, and -N(R-). 20 One or more groups of )-S(O)2-, wherein R 20 It is hydrogen, straight-chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 Cycloalkyl, or monocyclic or polycyclic C 2-20 Heterocyclic alkyl groups; L 1 It is a divalent linking group containing at least one carbon atom, at least one heteroatom, or a combination thereof; R 13 To R 14 Each is independently a hydrogen, straight-chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 Cycloalkyl, monocyclic or polycyclic C 2-20 Heterocyclic alkyl, monocyclic or polycyclic C 6-20 Aryl, or monocyclic or polycyclic C 1-20 Heteroaryl groups, wherein each of the groups except hydrogen is substituted or unsubstituted. R 15 Is it a straight chain or a branched chain? 1-20 alkyl, monocyclic or polycyclic C 3-20 Cycloalkyl, or monocyclic or polycyclic C 2-20 Heterocyclic alkyl groups, each of which is substituted or unsubstituted, wherein R 13 or R 14 One of the optional R 15 Together they form a heterocyclic ring; R 16 To R 18 Each C is either a straight chain or a branched chain. 1-20 alkyl, monocyclic or polycyclic C 3-20 Cycloalkyl, monocyclic or polycyclic C 2-20 Heterocyclic alkyl, monocyclic or polycyclic C 6-20 Aryl, or monocyclic or polycyclic C 1-20 A heteroaryl group, each of which is substituted or unsubstituted; R 16 To R 18 Any two of them can optionally form a ring together, and R 16 To R 18 Each of these may optionally further include, as part of its structure, a component selected from -O-, -C(O)-, -C(O)-O-, -S-, -S(O)2-, and N(R). 21 One or more groups of )-S(O)2-, wherein R 21 It is hydrogen, straight-chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 Cycloalkyl, or monocyclic or polycyclic C 2-20 Heterocyclic alkyl groups; X a It is a polymerizable group selected from norborneol and vinyl groups; n is 0 or 1; and L 2 It is a single bond or a divalent linker, provided that X is a single bond or a divalent linker. a When it is vinyl, L 2 It's not a single key.

4. The photoresist composition of claim 1, wherein, The first polymer further comprises repeating units derived from one or more monomers having formula (2): (2) in, R b It is a hydrogen, fluorine, cyano, substituted or unsubstituted C group. 1-10 Alkyl, or substituted or unsubstituted C 1-10 fluoroalkyl; L 3 It is a single bond or a divalent linker containing 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 7-30 arylalkylene, or substituted or unsubstituted C 1-30 heteroaryl, or substituted or unsubstituted C 2-30 Heteroarylalkylene, wherein L 3 Optionally, it may further comprise -O-, -C(O)-, -C(O)-O-, -S-, -S(O)2- and -N(R)-. 23 One or more groups of )-S(O)2-, wherein R 23 It is hydrogen, straight-chain or branched C 1-20 alkyl, monocyclic or polycyclic C 3-20 Cycloalkyl, or monocyclic or polycyclic C 2-20 Heterocyclic alkyl groups; and R 22 It is a monocyclic, polycyclic, or fused polycyclic compound containing C. 4-20 Lactone groups, or monocyclic, polycyclic, or fused polycyclic compounds containing C 4-20 The group of sulfonyl lactone.

5. The photoresist composition according to any one of claims 1 to 4, wherein, The first polymer further comprises repeating units derived from one or more monomers having formula (3): (3) in, R c It is a hydrogen, fluorine, cyano, substituted or unsubstituted C group. 1-10 Alkyl, or substituted or unsubstituted C 1-10 fluoroalkyl; Q 1 It is one or more of the following: 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 1-30 Hybrid aryl, or -C(O)-O-; and W contains the following alkali-soluble groups: -C(O)-OH; -C(CF3)2OH; amide; imide; or -NH-S(O)2-Y. 1 , where Y 1 Is it F or C? 1-4 Perfluoroalkyl; and a is an integer from 1 to 3.

6. The photoresist composition according to any one of claims 1 to 4, wherein, L is a variable with the formula -C(O)-C 1-10 alkylene-O- groups; Z 1 and Z 2 Each is -O-; and R 1 and R 2 Each is a substituted or unsubstituted C independently. 1-30 alkyl.

7. The photoresist composition according to any one of claims 1 to 4, wherein, The photoacid generator is non-polymeric.

8. The photoresist composition according to any one of claims 1 to 4, further comprising: a photodegradable quencher, an alkaline quencher, or a combination thereof.

9. The photoresist composition according to any one of claims 1 to 4, wherein, The weight ratio of the first polymer to the second polymer is from 1:1 to 1,000:

1.

10. A method for forming a pattern, comprising: (a) Applying a layer of the photoresist composition as described in any one of claims 1 to 9 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.

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