Photoresist composition and pattern forming method

Abstract

To provide photoresist compositions and pattern formation methods.SOLUTION: A photoresist composition comprises a first polymer comprising a first repeating unit comprising a hydroxy-aryl group and a second repeating unit comprising an acid-labile group, wherein the first polymer does not comprise a lactone group; a second polymer comprising a first repeating unit comprising a hydroxy-aryl group, a second repeating unit comprising an acid-labile group, and a third repeating unit comprising a lactone group; a photoacid generator; and a solvent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to photoresist compositions that contain a photoactive component and a blend of two different polymers, and to patterning methods using such photoresist compositions. The present invention finds particular applicability in lithography applications in the semiconductor manufacturing industry. [Background technology]

[0002] Photoresist materials are typically photosensitive compositions used to transfer images 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 enable the formation of structures with dimensions in the nanometer range, photoresists and photolithography processing tools with high-resolution capabilities have been developed.

[0003] Positive-tone chemically amplified photoresists are traditionally used for high-resolution processing. Such resists typically use a polymer with acid-labile groups and a photoacid generator. Patternwise exposure to activating radiation through a photomask causes the acid generator to form an acid, which, during post-exposure bake, causes cleavage of the acid-labile groups in the exposed areas of the polymer. This results in differential solubility characteristics of the exposed and unexposed areas of the resist in a developer. In a positive-tone development (PTD) process, the exposed areas of the photoresist layer become soluble in the developer and are removed from the substrate surface, while the unexposed areas, which are insoluble in the developer, remain after development, forming a positive image. The resulting relief image allows for selective processing of the substrate. See, for example, (Non-Patent Document 1) and (Non-Patent Document 2).

[0004] One approach to achieving nanometer-scale features in semiconductor devices is to use short wavelengths of light, e.g., 193 nanometers (nm) or shorter, during exposure of chemically amplified photoresists. To further improve lithographic performance, immersion lithography tools have been developed, effectively increasing the numerical aperture (NA) of the imaging device's lens, such as scanners with KrF (248 nm) or ArF (193 nm) light sources. This is achieved by using a relatively high refractive index fluid, typically water, between the lower surface of the imaging device and the upper surface of the semiconductor wafer. ArF immersion tools are currently pushing the limits of lithography up to the 16 nm and 14 nm nodes by using multiple (dual or higher order) patterning. However, compared to single-step direct imaging patterning, the use of multiple patterning is generally more costly due to increased material usage and the need for multiple processing steps. This provides motivation for the development of next-generation technologies such as extreme ultraviolet (EUV) lithography and electron beam lithography. However, as lithography resolution becomes ever higher, the line width roughness (LWR) and critical dimension uniformity (CDU) of the photoresist pattern become increasingly important in forming high fidelity patterns.

[0005] EUV and electron beam photoresist compositions and their uses have been described in the literature. For example, Patent Document 1 discloses an electron beam photoresist composition containing a single polymer or a blend of polymers having repeating units containing a hydroxy group attached to an aromatic ring. The resulting electron beam lithography image was a rough pattern with an LWR value of 16-19 nm for a 100 nm line / space 1 / 1 pattern and a CDU of 6-9 nm for a contact hole pattern with a 100 nm diameter contact hole.

[0006] Despite advances in resist technology, there remains a need for photoresist compositions that address one or more of the problems associated with the prior art. In particular, there is a continuing need for photoresist compositions with good sensitivity, including photoresist compositions that can achieve low LWR for line / space patterns and low CDU for contact hole patterns. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] US Patent Application Publication No. 2019 / 0243244 [Patent Document 2] U.S. Patent No. 8,431,325 [Patent Document 3] U.S. Patent No. 4,189,323 [Patent Document 4] US Patent Application Publication No. 2018 / 0284605 [Non-patent literature]

[0008] [Non-Patent Document 1] Uzodinma Okoroanyanwu,Chemistry and Lithography,SPIE Press and John Wiley and Sons,Inc.,2010 [Non-patent document 2] Chris Mack, Fundamental Principles of Optical Lithography, John Wiley and Sons, Inc., 2007 Summary of the Invention [Means for solving the problem]

[0009] Provided is a photoresist composition that includes: a first polymer that includes a first repeat unit that includes a hydroxyaryl group and a second repeat unit that includes an acid labile group, the first polymer not including a lactone group; a second polymer that includes a first repeat unit that includes a hydroxyaryl group, a second repeat unit that includes an acid labile group, and a third repeat unit that includes a lactone group; a photoacid generator; and a solvent.

[0010] Also provided is a patterning method that includes the steps of: (a) applying a layer of a photoresist composition described herein onto a substrate; (b) patternwise exposing the photoresist composition layer to activating radiation; and (c) developing the exposed photoresist composition layer to provide a resist relief image. DETAILED DESCRIPTION OF THE INVENTION

[0011] Reference will now be made in detail to the exemplary embodiments, examples of which are set forth herein. In this regard, the exemplary embodiments may have different forms and should not be construed as limited to the description set forth herein. Accordingly, the exemplary embodiments are described below by reference to the figures only to illustrate aspects of the present description. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items. Phrases such as "at least one," when preceding a list of elements, modify the entire list of elements and not individual elements of the list.

[0012] As used herein, the terms "a," "an," and "the" do not denote quantitative limitations and should be construed to include both the singular and the plural unless otherwise indicated herein or clearly contradicted by context. "Or" means "and / or" unless expressly stated otherwise. The modifier "about," used in connection with a quantity, is inclusive and has the meaning dictated by the context (e.g., including the degree of error associated with measurement of the particular quantity). All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independent and inclusive of each other. The suffix "(s)" is intended to include both the singular and the plural of the term it modifies, thereby including at least one of that term. "Optional" or "optionally" means that the described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where the event does not occur. The terms "first," "second," etc., as used herein, do not denote order, quantity, or importance, but rather are used to distinguish one element from another. When an element is said to be "on" another element, it may be in direct contact with the other element, or intervening elements may be present between them. In contrast, when an element is said to be "directly on" another element, there are no intervening elements present. It should be understood that the described components, elements, limitations, and / or features of the embodiments can be combined in any suitable manner in the various embodiments.

[0013] Unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted to have a meaning consistent with their meaning in the relevant technical field and in the context of this disclosure, and it will be further understood that they should not be interpreted in an idealized or overly formal sense unless expressly defined as such in this specification.

[0014] As used herein, the term "hydrocarbon group" means an organic compound having at least one carbon atom and at least one hydrogen atom, optionally substituted with one or more substituents, where indicated; "alkyl group" means a straight- or branched-chain saturated hydrocarbon having the specified number of carbon atoms and having a valence of one; "alkylene group" means an alkyl group having a valence of two; "hydroxyalkyl group" means an alkyl group substituted with at least one hydroxyl group (-OH); "alkoxy group" means "alkyl-O-"; "carboxylic acid group" means a group having the formula "-C(=O)-OH"; "cycloalkyl group" means a monovalent group having one or more saturated rings in which all ring members are carbon; "cycloalkylene group" means a cycloalkyl group having a valence of two; "alkenyl group" means a straight- or branched-chain monovalent hydrocarbon group having at least one carbon-carbon double bond; "alkenoxy group" means "alkenyl-O-"; "alkenylene group" means an alkene group having a valence of two. "cycloalkenyl group" means a non-aromatic cyclic divalent hydrocarbon group having at least three carbon atoms and at least one carbon-carbon double bond; "alkynyl group" means a monovalent hydrocarbon group having at least one carbon-carbon triple bond; the term "aromatic group" means a monocyclic or polycyclic ring system that satisfies Huckel's rule and has carbon in the ring and may optionally contain one or more heteroatoms selected from N, O, and S in place of the carbon in the ring; "aryl group" means a monovalent aromatic monocyclic or polycyclic ring system whose ring members are all carbon and may include groups having an aromatic ring fused to at least one cycloalkyl or heterocycloalkyl ring; "arylene group" means an aryl group having a valence of two; "alkylaryl group" means an aryl group substituted with an alkyl group; "arylalkyl group" means an alkyl group substituted with an aryl group; "aryloxy group" means "aryl-O-"; and "arylthio group" means "aryl-S-".

[0015] The prefix "hetero" means that the compound or group contains at least one member that is a heteroatom (e.g., 1, 2, 3, or more heteroatoms) in place of a carbon atom, where the heteroatoms are each independently N, O, S, Si, or P; a "heteroatom-containing group" means a substituent having at least one heteroatom; a "heteroalkyl group" means an alkyl group having 1 to 4 heteroatoms in place of carbon; a "heterocycloalkyl group" means a cycloalkyl group having 1 to 4 heteroatoms in place of carbon as ring members; a "heterocycloalkylene group" means a heterocycloalkyl group having a valence of 2; a "heteroaryl group" means an aryl group having 1 to 4 heteroatoms in place of carbon as ring members; and a "heteroarylene group" means a divalent heteroaryl group.

[0016] The term "halogen" refers to a monovalent substituent that is fluorine (fluoro), chlorine (chloro), bromine (bromo), or iodine (iodo). The prefix "halo" refers to a group that contains one of a fluoro, chloro, bromo, or iodo substituent in place of a hydrogen atom. Combinations of halo groups (e.g., bromo and fluoro) or only fluoro groups can be present.

[0017] "Fluorinated" shall be understood to mean having one or more fluorine atoms incorporated into the group. For example, C 1~18 When a fluoroalkyl group is indicated, the fluoroalkyl group may contain one or more fluorine atoms, such as a single fluorine atom, two fluorine atoms (such as, for example, a 1,1-difluoroethyl group), three fluorine atoms (such as, for example, a 2,2,2-trifluoroethyl group), or a fluorine atom at each free valence of carbon (e.g., as in perfluoro groups such as -CF3, -CF5, -CF7, or -CF9). A "substituted fluoroalkyl group" shall be understood to mean a fluoroalkyl group substituted by further substituents.

[0018] As used herein, "hydroxy-aryl group" and "hydroxy-substituted aryl group" refer to an aromatic group in which a hydroxy group is bonded directly to a carbon atom of the aromatic ring. "Hydroxy" shall be understood to mean having one or more hydroxy groups incorporated into the group. For example, C 6~12 Where a hydroxy-aryl group is indicated, the hydroxy-aryl group may contain one or more hydroxy groups, e.g., a single hydroxy group, two hydroxy groups, three or more hydroxy groups, etc. A "substituted hydroxy-aryl group" shall be understood to mean a hydroxy-aryl group substituted with a further substituent.

[0019] As used herein, "acid labile group" refers to a group formed on a polymer that undergoes bond cleavage, optionally and typically accompanied by thermal treatment, under the catalytic action of an acid, resulting in a polar group such as a carboxylic acid group or an alcohol group, and optionally and typically results in the moiety connected to the cleaved bond being cleaved from the polymer. Such acids are typically photogenerated acids, with bond cleavage occurring during baking after exposure. Suitable acid labile groups include, for example, tertiary alkyl ester groups, secondary or tertiary aryl ester groups, secondary or tertiary ester groups having a combination of alkyl and aryl groups, tertiary alkoxy groups, acetal groups, or ketal groups. Acid labile groups are also commonly referred to in the art as "acid-cleavable groups," "acid-cleavable protecting groups," "acid-labile protecting groups," "acid-leaving groups," "acid-decomposable groups," and "groups that are sensitive to acid."

[0020] "Substituted" means that at least one hydrogen atom on a group has been replaced with another group, provided that the normal valence of the designated atom is not exceeded. When the substituent is oxo (i.e., =0), two hydrogens on the carbon atom are replaced. Combinations of substituents or variables are permissible. Exemplary groups that may be present in a "substituted" position are nitro (-NO), cyano (-CN), hydroxy (-OH), oxo (=0), amino (-NH), mono- or di-(C 1~6) alkylamino, alkanoyl (acyl, etc. C 2~6 alkanoyl group, etc.), formyl (-C(=O)H), carboxylic acid or their alkali metal or ammonium salts;C 2~6 Alkyl esters (-C(=O)O-alkyl or -OC(=O)-alkyl) and C 7~13 Esters (including acrylates, methacrylates, and lactones) such as aryl esters (-C(=O)O-aryl or -OC(=O)-aryl); amides (-C(=O)NR2 (where R is hydrogen or C 1~6 alkyl), carboxamide (-CHC(=O)NR (R is hydrogen or C 1~6 Alkyl), halogen, thiol (-SH), C 1~6 Alkylthio (-S-alkyl), thiocyano (-SCN), C 1~6 Alkyl, C 2~6 Alkenyl, C 2~6 Alkynyl, C 1~6 Haloalkyl, C 1~9 Alkoxy, C 1~6 Haloalkoxy, C 3~12 Cycloalkyl, C 5~18 Cycloalkenyl, C having at least one aromatic ring (e.g., phenyl, biphenyl, naphthyl, etc., each ring being substituted or unsubstituted aromatic). 6~12 Aryl, C having 1 to 3 separated or fused rings and 6 to 18 ring carbon atoms 7~19 arylalkyl, arylalkoxy having 1 to 3 separated or fused rings and 6 to 18 ring carbon atoms, C 7~12 Alkylaryl, C 1~12 Heterocycloalkyl, C 2~12 Heteroaryl, C 1~6 Alkylsulfonyl (-S(=O)2-alkyl), C 6~12 Examples of alkyl groups include, but are not limited to, arylsulfonyl (-S(=O)-aryl), or tosyl (CHCHSO-). If a group is substituted, the indicated number of carbon atoms is the total number of carbon atoms in the group, excluding carbon atoms of any substituents. For example, the group -CHCHCN is a C alkyl group substituted with a cyano group.

[0021] The present invention relates to a photoresist composition that contains a first polymer, a second polymer, a photoacid generator, a solvent, and may contain additional optional components. The inventors have surprisingly found that certain photoresist compositions of the present invention can achieve significantly improved lithographic properties, such as better contrast of resolved patterns, higher resolution, and reduced roughness.

[0022] The first polymer comprises a first repeat unit comprising a hydroxy-aryl group and a second repeat unit comprising an acid labile group cleavable by acid generated by photoexposure under post-exposure bake conditions, and the first polymer does not comprise a lactone group.

[0023] The first repeat unit of the first polymer may be derived from one or more monomers of formula (1). [ka]

[0024] In formula (1), R a is hydrogen, fluorine, cyano, substituted or unsubstituted C 1~10 Alkyl or substituted or unsubstituted C 1~10 Preferably, R a is hydrogen, fluorine, or substituted or unsubstituted C 1~5 R is alkyl, typically methyl. b is hydrogen, L 1 -C(O)- or Ar 1 is a single bond that forms a ring together with R. b is hydrogen.

[0025] In formula (1), L 1 is a single bond or a substituted or unsubstituted C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 1~30 Heterocycloalkylene, substituted or unsubstituted C 6~30Arylene, substituted or unsubstituted C 2~30 Heteroarylene, -O-, -C(O)-, -N(R 2a is a divalent linking group containing one or more of -S-, -S(O)-, or -S(O)-; R 2a is hydrogen, C 1~6 Alkyl, or R b is a single bond that forms a ring with R 2a R b When R is a single bond that forms a ring together with b L 1 and L are —C(O)—, which together form a ring. 1 represents a single bond, -C(O)-O-, -O-(C 1~12 hydrocarbylene)-, -C(O)-O-(C 1~12 hydrocarbylene)-, -C(O)-O-(C 1~12 hydrocarbylene)-O-, or a combination thereof.

[0026] R 2a But R b is a single bond that forms a ring together with R b But, L 1 When R is -C(O)- which forms a ring together with b and L 1 The ring formed by R 2a and R b For example, L 1 , R a and R b The structural unit comprising may be of the following structure: [ka] (In the formula, Ar 1 is as defined in equation (1).

[0027] In formula (1), Ar 1 is optionally substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C 1~30 Heteroalkyl, substituted or unsubstituted C 3~30Cycloalkyl, substituted or unsubstituted C 1~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, substituted or unsubstituted C 6~30 Aryl, substituted or unsubstituted C 7~30 Aryl alkyl, substituted or unsubstituted C 7~30 Alkylaryl, substituted or unsubstituted C 2~30 Heteroaryl, substituted or unsubstituted C 3~30 Heteroarylalkyl, C 3~30 Alkylheteroaryl, -OR 21 , or -NR 22 R 23 hydroxy-substituted C optionally further substituted with one or more of 6~60 Aryl group, hydroxy-substituted C 4~60 heteroaryl groups, or combinations thereof, where R 21 ~R 23 are each independently a substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C 3~30 Cycloalkyl, substituted or unsubstituted C 1~30 Heterocycloalkyl, substituted or unsubstituted C 6~30 Aryl, substituted or unsubstituted C 7~30 Aryl alkyl, substituted or unsubstituted C 7~30 Alkylaryl, substituted or unsubstituted C 4~30 Heteroaryl, substituted or unsubstituted C 5~30 Heteroarylalkyl or substituted or unsubstituted C 5~30 alkylheteroaryl. Ar 1 It may be preferred that Ar contains a single hydroxyl group or multiple hydroxyl groups (e.g., Ar 1 each independently represents a hydroxy-substituted C optionally further substituted with a hydroxyl group; 6~60 Aryl group, hydroxy-substituted C 4~60 heteroaryl groups or combinations thereof).

[0028] Non-limiting examples of monomers of formula (1) include: [ka]

[0029] The first repeat unit and all repeat units of the first polymer combined that include a hydroxyaryl group are typically present in the first polymer in an amount of 20 to 80 mole percent (mol %), more typically 25 to 70 mol %, and even more typically 30 to 60 mol %, based on the total repeat units present in the first polymer.

[0030] The second repeat unit of the first polymer can be derived from one or more monomers of formula (2a), (2b), (2c), (2d), or (2e). [ka]

[0031] In formulas (2a) and (2b), R c and R d are each independently hydrogen, fluorine, cyano, substituted or unsubstituted C 1~10 Alkyl, or substituted or unsubstituted C 1~10 Preferably, R C is hydrogen, fluorine, or substituted or unsubstituted C 1~5 It is alkyl, typically methyl.

[0032] In formula (2a), L 2 is a linking group. For example, L 2 can be a divalent linking group containing at least one carbon atom, at least one heteroatom, or a combination thereof. For example, L 2 may contain 1 to 10 carbon atoms and at least one heteroatom. 2 is -OCH2-, -OCH2CH2O- or -N(R 41 )-(where R 41is hydrogen or C 1~6 alkyl).

[0033] In formulas (2a) and (2b), R 1 ~R 6 are each independently hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, substituted or unsubstituted C 1~20 Heterocycloalkyl, substituted or unsubstituted C 2~20 Alkenyl, substituted or unsubstituted C 3~20 Cycloalkenyl, substituted or unsubstituted C 3~20 Heterocycloalkenyl, substituted or unsubstituted C 6~20 Aryl, or substituted or unsubstituted C 2~20 Heteroaryl, but R 1 ~R 3 Only one of R can be hydrogen, and 4 ~R 6 Only one of R can be hydrogen and 1 ~R 3 If one of R is hydrogen, then the other R 1 ~R 3 One or both of the C 6~20 Aryl or substituted or unsubstituted C 4~20 heteroaryl, and R 4 ~R 6 If one of R is hydrogen, then the other R 4 ~R 6 One or both of which may be substituted or unsubstituted C 6~20 Aryl or substituted or unsubstituted C 4~20 Heteroaryl. Preferably, R 1 ~R 6 are each independently a substituted or unsubstituted C 1~6 Alkyl or substituted or unsubstituted C 3~10 It is cycloalkyl.

[0034] In formula (2a), R 1 ~R 3any two of optionally together form a ring, and R 1 ~R 3 Each of the optionally includes as part of its structure -O-, -C(O)-, -N(R 42 )-, -S-, or -S(O)-, where R 42 is hydrogen, straight or branched C 1~20 Alkyl, monocyclic or polycyclic C 3~20 Cycloalkyl or monocyclic or polycyclic C 1~20 In formula (2b), R 4 ~R 6 any two of optionally together form a ring, and R 4 ~R 6 Each of the optionally includes as part of its structure -O-, -C(O)-, -N(R 43 )-, -S-, or -S(O)-, where R 43 is hydrogen, straight or branched C 1~20 Alkyl, monocyclic or polycyclic C 3~20 Cycloalkyl or monocyclic or polycyclic C 1~20 Heterocycloalkyl. For example, R 1 ~R 6 any one or more of the formula -CHC(=O)CH (3-n) Y n wherein each Y is independently a substituted or unsubstituted C 1~30 heterocycloalkyl, and n is 1 or 2. For example, each Y is independently a group of the formula —O(C a1 )(C a2 )O- group. 1~30 heterocycloalkyl, where C a1 and C a2 are each independently hydrogen or a substituted or unsubstituted C 1~10 alkyl, C a1 and C a2 are optionally taken together to form a ring.

[0035] In formulas (2c) and 2(e), R 7 ~R 8 are each independently hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, substituted or unsubstituted C 1~20 Heterocycloalkyl, substituted or unsubstituted C 6~20 Aryl, or substituted or unsubstituted C 2~20 heteroaryl, and R 9 is a substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 1~30 is heterocycloalkyl. , R 7 or R 8 One of them is R 9 and form a heterocycle together. Preferably, R 7 and R 8 are each independently hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 1~20 It may be a heterocycloalkyl.

[0036] In equation (2d), R 10 ~R 12 are each independently hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, substituted or unsubstituted C 1~20 Heterocycloalkyl, substituted or unsubstituted C 6~20 Aryl, or substituted or unsubstituted C 2~20 may be heteroaryl, R 10 ~R 12 any two of which together optionally form a ring, and R 10 ~R 12 Each of the optionally includes as part of its structure -O-, -C(O)-, -N(R 44)-, -S-, or -S(O)-, wherein R 44 is hydrogen, linear or branched C 1~20 Alkyl, monocyclic or polycyclic C 3~20 Cycloalkyl, or monocyclic or polycyclic C 1~20 However, if the acid labile group is not an acetal group, R 10 ~R 12 and only one of R 10 ~R 12 If one of R is hydrogen, then the other R 10 ~R 12 One or both of the groups may be substituted or unsubstituted C 6~20 Aryl or substituted or unsubstituted C 4~20 It is heteroaryl.

[0037] In formulas (2d) and (2e), X a is a polymerizable group selected from vinyl and norbornyl, and L 3 is a single bond or a divalent group, provided that X a When is a vinyl group, L 3 is not a single bond. Preferably, L 3 is a substituted or unsubstituted C 6~30 Arylene or substituted or unsubstituted C 3~30 In formula (2d), n is 0 or 1. When n is 0, L 3 It is understood that the group is attached directly to the oxygen atom.

[0038] Non-limiting examples of monomer (2a) include: [ka]

[0039] Non-limiting examples of monomers of formula (2b) include: [ka] [ka] (In the formula, R d is as defined above, and R′ and R″ are each independently a straight-chain or branched C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, substituted or unsubstituted C 1~20 Heterocycloalkyl, linear or branched C 2~20 Alkenyl, monocyclic or polycyclic C 3~20 Cycloalkenyl, monocyclic or polycyclic C 3~20 Heterocycloalkenyl, monocyclic or polycyclic C 6~20 Aryl, or monocyclic or polycyclic C 4~20 (heteroaryl).

[0040] Non-limiting examples of monomers of formula (2c) include: [ka] (In the formula, R d is as defined above).

[0041] Non-limiting examples of monomer (2d) include: [ka]

[0042] Non-limiting examples of monomers (2e) include: [ka]

[0043] In yet another example, the second repeat unit of the first polymer may be derived from one or more monomers having a cyclic acetal or cyclic ketal group, for example, the formula: [ka] (In the formula, R d is as defined above).

[0044] In yet another example, the second repeat unit of the first polymer may be derived from one or more monomers having a tertiary alkoxy group, such as the following formula: [ka]

[0045] The second repeat unit of the first polymer, and all second repeat units of the first polymers combined, are typically present in the first polymer in an amount of from 20 to 80 mol %, more typically from 25 to 75 mol %, and even more typically from 30 to 70 mol %, based on the total repeat units in the first polymer.

[0046] For example, the first polymer may have the formula: [ka] [ka] (wherein a, b, and c represent the mole fraction of the corresponding repeating unit, and n is an integer of 10 to 1,000).

[0047] The photoresist composition further comprises a photoacid generator (PAG). Suitable PAGs are capable of generating an acid during post-exposure bake (PEB) that causes cleavage of acid-labile groups present on the polymer of the photoresist composition. The PAG can be included as a non-polymerizable PAG compound (described below), as a repeat unit of a polymer having a PAG moiety derived from a polymerizable PAG compound, or a combination thereof. For example, the first polymer can optionally include a repeat unit comprising a PAG, such as a repeat unit derived from one or more monomers of formula (3): [ka]

[0048] In equation (3), R h is hydrogen, fluorine, cyano, substituted or unsubstituted C 1~10 Alkyl or substituted or unsubstituted C 1~10 Preferably, R h is hydrogen, fluorine, or substituted or unsubstituted C 1~5 Q is an alkyl group, typically methyl. 2 represents a single bond, a heteroatom, a substituted or unsubstituted C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 1~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 4~30 Preferably, Q is a divalent linking group selected from one or more of: 2 may contain 1 to 10 carbon atoms and at least one heteroatom, and is more preferably —C(O)—O—.

[0049] In formula (3), A is a substituted or unsubstituted C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 1~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, or substituted or unsubstituted C 4~30 Preferably, A is one or more of an optionally substituted divalent C 1~30 It is a perfluoroalkylene group.

[0050] In equation (3), Z - is an anionic moiety containing a sulfonate, carboxylate, anion of a sulfonamide, anion of a sulfonimide, or a methide anion. + is an organic cation as described below.

[0051] Exemplary monomers of formula (3) include: [ka] (In the formula, G + is an organic cation). Organic cations include, for example, iodonium cations substituted with two alkyl groups, aryl groups, or a combination of alkyl and aryl groups, and sulfonium cations substituted with three alkyl groups, aryl groups, or a combination of alkyl and aryl groups. In some embodiments, G + is an iodonium cation substituted with two alkyl groups, aryl groups, or a combination of alkyl and aryl groups, or a sulfonium cation substituted with three alkyl groups, aryl groups, or a combination of alkyl and aryl groups. + may be one or more of a substituted sulfonium cation having formula (3A) or an iodonium cation having formula (3B): [ka] (In the formula, each R aa independently, C 1~20 Alkyl group, C 1~20 Fluoroalkyl group, C 3~20 Cycloalkyl groups, C 3~20 Fluorocycloalkyl groups, C 2~20 Alkenyl group, C 2~20 Fluoroalkenyl group, C 6~30 Aryl group, C 6~30 Fluoroaryl group, C 6~30 Iodoaryl group, C 4~30 Heteroaryl groups, C 7~20 Arylalkyl groups, C 7~20 Fluoroarylalkyl groups, C 5~30 Heteroarylalkyl group, or C 5~30 fluoroheteroarylalkyl groups, each of which may be substituted or unsubstituted; aa is another R aa groups or are connected via a single bond or a divalent linking group to form a ring). aaoptionally includes as part of its structure -O-, -C(O)-, -C(O)-O-, -C 1~12 Hydrocarbylene-, -O-(C 1~12 hydrocarbylene)-, -C(O)-O-(C 1~12 hydrocarbylene)- and -C(O)-O-(C 1~12 Each R may contain one or more groups selected from the group consisting of (hydrocarbylene)-O-. aa R may independently optionally include acid labile groups selected from, 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. aa Divalent linking groups suitable for linking groups include, for example, -O-, -S-, -Te-, -Se-, -C(O)-, -C(S)-, -C(Te)-, -C(Se)-, S(O)-, S(O)2-, or -N(R)-, where R is hydrogen, a straight or branched C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 3~20 It is heterocycloalkyl.

[0052] Exemplary sulfonium cations of formula (3A) include: [ka]

[0053] Exemplary iodonium cations of formula (3B) include: [ka]

[0054] The first polymer may include one or more repeat units that comprise a photoacid generator. When 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 even more typically 2 to 6 mol %, based on the total repeat units of the first polymer.

[0055] The first polymer may optionally include one or more additional repeat units different from the first repeat unit, the second repeat unit, and, if present, the repeat unit containing the photoacid generator. The additional repeat units may include, for example, one or more additional units for the purpose of adjusting the properties of the photoresist composition, such as etch rate and solubility. Exemplary additional units may include one or more of (meth)acrylate, vinyl ether, vinyl ketone, and vinyl ester. When one or more additional repeat units are present in the first polymer, the additional repeat units may be used in an amount of up to 70 mol %, typically 3 to 50 mol %, based on the total repeat units of the first polymer.

[0056] The weight average molecular weight (M w ) is typically 1,000 to 50,000 daltons (Da), preferably 2,000 to 30,000 Da, more preferably 3,000 to 20,000 Da, and even more preferably 3,000 to 10,000 Da. w The number average molecular weight (M n The polydispersity index (PDI) of the first polymer, which is the ratio of the molecular weight of the first polymer to the molecular weight of the second polymer, is typically 1.1 to 3, more specifically 1.1 to 2. The molecular weight is determined by gel permeation chromatography (GPC) using polystyrene standards.

[0057] The second polymer comprises a first repeat unit comprising a hydroxyaryl group, a second repeat unit comprising an acid labile group, and a third repeat unit comprising a lactone group.

[0058] The first repeat unit of the second polymer can be derived from one or more of the monomers of formula (1) disclosed for the first polymer. The first repeat unit of the second polymer can be the same or different from the first repeat unit of the first polymer.

[0059] The second repeat unit of the second polymer can be derived from one or more of the monomers of formula (2a), (2b), (2c), or (2d) disclosed for the first polymer. The second repeat unit of the second polymer can be the same or different from the second repeat unit of the first polymer.

[0060] The third repeat unit of the second polymer can be derived from one or more monomers of formula (4): [ka]

[0061] In equation (4), R f is hydrogen, fluorine, cyano, substituted or unsubstituted C 1~10 Alkyl or substituted or unsubstituted C 1~10 Preferably, R f is hydrogen, fluorine, or substituted or unsubstituted C 1~5 It is alkyl, typically methyl. 4 may be a single bond or a divalent linking group. For example, L 4 is a single bond or a 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 1~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, or substituted or unsubstituted C 4~30 and a divalent linking group comprising one or more of the following: heteroarylene, wherein L 4 is optionally selected from groups such as -O-, -C(O)-, -C(O)-O-, -S-, -S(O)2-, and -N(R 44 )—S(O)—, and R 44 is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 1~20R may be heterocycloalkyl. 14 is a monocyclic, polycyclic, or fused polycyclic C 4~20 Lactone-containing groups or monocyclic, polycyclic, or fused polycyclic C 4~20 It may be a sultone-containing group.

[0062] Non-limiting examples of monomers of formula (4) include: [ka] (In the formula, R f as disclosed herein).

[0063] The first repeat unit and all of the combined first repeat units of the second polymer containing a hydroxyaryl group are typically present in the second polymer in an amount of 30 to 70 mol %, more typically 35 to 65 mol %, and even more typically 40 to 60 mol %, based on the total repeat units in the second polymer. The second repeat unit and all of the combined second repeat units of the second polymer are typically present in an amount of 30 to 60 mol %, more typically 35 to 60 mol %, and even more typically 35 to 55 mol %, based on the total repeat units in the second polymer. The third repeat unit and all of the combined third repeat units of the second polymer are typically present in an amount of 2 to 40 mol %, more typically 5 to 25 mol %, and even more typically 8 to 20 mol %, based on the total repeat units in the second polymer. For example, the second polymer contains the first repeating unit in an amount of 30 to 70 mol%, more typically 35 to 65 mol%, and even more typically 40 to 60 mol%, the second repeating unit in an amount of 30 to 60 mol%, more typically 35 to 60 mol%, and even more typically 35 to 55 mol%, and the third repeating unit in an amount of 2 to 40 mol%, more typically 5 to 25 mol%, and even more typically 8 to 20 mol%, each based on the total repeating units in the second polymer.

[0064] The second polymer may optionally include one or more additional repeat units different from the first repeat unit, the second repeat unit, and the third repeat unit. For example, the second polymer may optionally include one or more additional repeat units as described above for the optional additional repeat units of the first polymer. When one or more additional units are present in the second polymer, they may be used in an amount of up to 70 mol %, typically 3 to 50 mol %, based on the total repeat units of the second polymer.

[0065] For example, the second polymer may optionally further comprise a repeat unit comprising a base-soluble group, typically a base-soluble group having a pKa of less than or equal to 12. For example, the repeat unit comprising a base-soluble group may be derived from one or more monomers of formula (5): [ka]

[0066] In equation (5), R g is hydrogen, fluorine, cyano, substituted or unsubstituted C 1~10 Alkyl or substituted or unsubstituted C 1~10 Preferably, R g is hydrogen, fluorine, or substituted or unsubstituted C 1~5 Q is an alkyl group, typically methyl. 1 is a substituted or unsubstituted C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 1~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 4~30 W may be one or more of: -C(O)-O-; heteroarylene; or -C(O)-O-; W is a base-solubilizing group, for example, -C(O)-OH; a fluorinated alcohol such as -C(CF)OH; an amide; an imide; or -NH-S(O)-Y 1 (where Y 1 is F or C 1~4In formula (5), a is an integer of 1 to 3.

[0067] Non-limiting examples of monomers of formula (5) include: [ka] (In the formula, R g and Y 1 is as above).

[0068] The second polymer may optionally include repeat units comprising a PAG derived from one or more monomers of formula (3), as disclosed above. The second polymer may include repeat units comprising a PAG in an amount typically between 1 and 10 mol %, more typically between 1 and 8 mol %, and even more typically between 2 and 6 mol %, based on the total repeat units of the second polymer.

[0069] Non-limiting examples of second polymers include: [ka] (wherein a, b, c and d each represent the mole fraction of the corresponding repeating unit).

[0070] The second polymer typically has an M of 1,000 to 50,000 Da, preferably 2,000 to 30,000 Da, more preferably 3,000 to 20,000 Da, and even more preferably 3,000 to 10,000 Da. w The PDI of the polymer is typically 1.1 to 3, more typically 1.1 to 2. The molecular weight is determined by GPC using polystyrene standards.

[0071] 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 combined or separately fed using a suitable solvent and initiator 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 heating at an effective temperature, irradiating with actinic radiation at an effective wavelength, or a combination thereof.

[0072] The photoresist composition typically comprises the first polymer and the second polymer in a weight ratio of 1:4 to 4:1, for example 1:4 to 4:1, or 1:3 to 3:1, or 1:2 to 2:1.

[0073] In the photoresist compositions of the invention, the first polymer and second polymer are typically present in the photoresist composition in an amount of from 10 to 99.9 weight percent, typically from 25 to 99 weight percent, and more typically from 50 to 95 weight percent, based on the total solids content of the photoresist composition, which will be understood to include the first and second polymers, the PAG, and other non-solvent components.

[0074] In some embodiments, the photoresist composition may further comprise a material containing one or more base-labile groups ("base-labile material"). As referred to herein, a base-labile group is a functional group that undergoes a cleavage reaction to provide a polar group, such as a hydroxyl, carboxylic acid, or sulfonic acid, in the presence of an aqueous alkaline developer after the exposure and post-exposure bake steps. The base-labile group does not react significantly (e.g., no bond-breaking reaction occurs) before the development step of the photoresist composition containing the base-labile group. Thus, for example, the base-labile group is substantially inert during the pre-exposure soft bake, exposure, and post-exposure bake steps. "Substantially inert" means that 5% or less, typically 1% or less, of the base-labile groups (or sites) decompose, cleave, or react during the pre-exposure soft bake, exposure, and post-exposure bake steps. The base-labile group is reactive under typical photoresist development conditions, for example, using an aqueous alkaline photoresist developer, such as a 0.26N (N) aqueous tetramethylammonium hydroxide (TMAH) solution. For example, a 0.26N aqueous solution of TMAH can be used to dispense the 0.26N TMAH developer onto the imaged photoresist layer over a suitable time, such as a single puddle or dynamic development, such as 10 to 120 seconds. An exemplary base-labile group is an ester group, typically a fluorinated ester group. Preferably, the base-labile material is substantially immiscible with the first and second polymers and other solid components of the photoresist composition and has a lower surface energy than the first and second polymers and other solid components of the photoresist composition. When coated onto a substrate, the base-labile material can thereby separate from the other solid components of the photoresist composition to the top surface of the formed photoresist layer.

[0075] In some embodiments, the base-labile material is a polymeric material, also referred to herein as a base-labile polymer, which can include one or more repeating units containing one or more base-labile groups. For example, the base-labile polymer can include repeating units containing two or more base-labile groups, which may be the same or different. Preferred base-labile polymers include at least one repeating unit containing two or more base-labile groups, for example, repeating units containing two or three base-labile groups.

[0076] The base labile polymer has the formula (E1) [ka] (In the formula, X b is a polymerizable group selected from vinyl and acrylic; L 5 is a substituted or unsubstituted straight-chain or branched C 1~20 Alkylene, substituted or unsubstituted C 3~20 Rf is a divalent linking group containing one or more of cycloalkylene, -C(O)-, or -C(O)O-; Rf is a substituted or unsubstituted C 1~20 The polymer may be a polymer comprising repeat units derived from one or more monomers of formula (E1) which are fluoroalkyl groups, with the proviso that the carbon atom bonded to the carbonyl (C=O) of formula (E1) is substituted with at least one fluorine atom.

[0077] Exemplary monomers of formula (E1) include: [ka]

[0078] The base-labile polymer may include repeat units containing more than one base-labile group. For example, the base-labile polymer may be a repeat unit of formula (E2): [ka] (In the formula, X b and Rf are as defined in formula (E1); L 6is a substituted or unsubstituted straight-chain or branched C 1~20 Alkylene, substituted or unsubstituted C 3~20 and n is an integer of 2 or greater, e.g., 2 or 3.

[0079] Exemplary monomers of formula (E2) include: [ka]

[0080] The base labile polymer may comprise repeat units comprising one or more base labile groups. For example, the base labile polymer may comprise one or more repeat units of formula (E3): [ka] (In the formula, X b is as defined in formula (E1); L 7 is a substituted or unsubstituted straight-chain or branched C 1~20 Alkylene, substituted or unsubstituted C 3~20 a divalent linking group containing one or more of cycloalkylene, —C(O)—, —, or —C(O)O—; L f is a substituted or unsubstituted C 1~20 A fluoroalkylene group, wherein the carbon atom bonded to the carbonyl (C=O) in formula (E1) is substituted with at least one fluorine atom; Rg is a substituted or unsubstituted straight-chain or branched C 1~20 Alkyl, or substituted or unsubstituted C 3~20 The repeat units may be derived from a monomer of the formula (I) wherein the repeat units are cycloalkyl.

[0081] Exemplary monomers of formula (E3) include: [ka]

[0082] In a further preferred embodiment of the present invention, the base-labile polymer can contain one or more base-labile groups and one or more acid-labile groups, such as one or more acid-labile ester moieties (e.g., t-butyl esters) or acid-labile acetal groups. For example, the base-labile polymer can contain a repeating unit containing a base-labile group and an acid-labile group, i.e., a repeating unit in which both the base-labile group and the acid-labile group are present on the same repeating unit. In another example, the base-labile polymer can contain a first repeating unit containing a base-labile group and a second repeating unit containing an acid-labile group. Preferred photoresists of the present invention can exhibit reduced defects associated with resist relief images formed from the photoresist compositions.

[0083] The base-labile polymer can be prepared using any suitable method in the art, including those described herein for the first and second polymers. For example, the base-labile polymer can be obtained by polymerization of the respective monomers under any suitable conditions, such as heating at an effective temperature, irradiating with actinic radiation at an effective wavelength, or a combination thereof. Additionally or alternatively, one or more base-labile groups can be grafted onto the backbone of the polymer using a suitable method.

[0084] The base-labile polymer typically has an M of 1,000 to 50,000 Da, preferably 2,000 to 30,000 Da, more preferably 3,000 to 20,000 Da, and even more preferably 3,000 to 10,000 Da. w The PDI of the polymer is typically 1.1 to 3, more typically 1.1 to 2.0. The molecular weight is determined by GPC using polystyrene standards.

[0085] In some embodiments, the base-labile material is a single molecule containing one or more base-labile ester groups, preferably one or more fluorinated ester groups. Single-molecule base-labile substances typically have a molecular weight in the range of 50 to 1,500 Da. Exemplary base-labile substances include: [ka]

[0086] In addition to or instead of the base-labile polymer, the photoresist composition can further include one or more polymers different from the first and second polymers described above. For example, the photoresist composition can include additional polymers as described above but different in composition, or polymers similar to those described above but lacking each of the essential repeating units. Additionally or alternatively, the one or more additional polymers can include those well known in the photoresist art, such as polyacrylates, polyvinyl ethers, polyesters, polynorbornenes, polyacetals, polyethylene glycols, polyamides, polyacrylamides, polyphenols, novolacs, styrenic polymers, polyvinyl alcohols, or combinations thereof.

[0087] The photoresist composition may further contain a photoacid generator (PAG). The PAG may be polymeric, for example, present within the polymerized repeat units of the first and / or second polymers described above, or may be present as part of another polymer. Additionally or alternatively, the PAG may be in a non-polymeric form. Suitable non-polymeric PAG compounds have the formula G + A - where G + is defined above in equation (3), and A -is a non-polymeric organic anion. Suitable non-polymeric PAG compounds are known in the chemically amplified photoresist art and include, for example, onium salts such as triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; di-t-butylphenyliodonium perfluorobutanesulfonate, and di-t-butylphenyliodonium camphorsulfonate. Nonionic sulfonate and sulfonyl compounds are also known to function as photoacid generators, such as nitrobenzyl derivatives, such as 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate, and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonic acid esters, such as 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives, such as bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl) Examples of suitable non-polymeric photoacid generators include diazomethane, glyoxime derivatives such as bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime and bis-O-(n-butanesulfonyl)-α-dimethylglyoxime, sulfonate derivatives of N-hydroxyimide compounds such as N-hydroxysuccinimide methanesulfonate and N-hydroxysuccinimide trifluoromethanesulfonate, and halogen-containing 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 non-polymeric photoacid generators are further described in Hashimoto et al. (Patent Document 2), column 37, lines 11-47, and columns 41-91.Other suitable sulfonate PAGs include sulfonated esters and sulfonyloxy ketones, nitrobenzyl esters, s-triazine derivatives, benzoin tosylate, t-butylphenyl α-(p-toluenesulfonyloxy)-acetate, and t-butyl α-(p-toluenesulfonyloxy)-acetate, as described in U.S. Patent No. 5,629,992 and U.S. Patent No. 5,629,992.

[0088] PAGs that are onium salts typically contain an anion that has a sulfonate or non-sulfonate group, such as a sulfonamidate group, a sulfonimidate group, a methide group, or a borate group.

[0089] Exemplary anions having a sulfonate group include: [ka]

[0090] Exemplary non-sulfonated anions include: [ka]

[0091] The photoresist composition may optionally contain multiple PAGs. The multiple PAGs may be polymeric or non-polymeric, or may include both polymeric and polymeric PAGs. Preferably, each of the multiple PAGs is non-polymeric. Preferably, when multiple PAGs are used, a first PAG has a sulfonate group on the anion, and a second PAG has an anion without a sulfonate group, such as a sulfonamidate group, sulfonimidate group, methide group, or borate group, as described above.

[0092] In one or more embodiments, the photoresist composition can include a first photoacid generator that includes a sulfonate group on the anion, and the photoresist composition can include a second photoacid generator that is non-polymeric, and the second photoacid generator can include an anion that does not include a sulfonate group.

[0093] Typically, the photoresist composition may include the non-polymeric photoacid generator in an amount of 1 to 65%, more typically 5 to 55%, and even more typically 8 to 30% by weight, based on the total solids content of the photoresist composition. In some embodiments, the photoresist composition may include two or more different non-polymeric photoacid generators in a combined amount of 1 to 65%, more typically 5 to 55%, and even more typically 8 to 30% by weight, based on the total solids content of the photoresist composition.

[0094] The photoresist composition further comprises a solvent for dissolving the components of the composition and facilitating its coating on a substrate. Preferably, the solvent is an organic solvent conventionally used in the manufacture of electronic devices. Suitable solvents include, for example, aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, and 1-chlorohexane; alcohols such as methanol, ethanol, 1-propanol, isopropanol, tert-butanol, 2-methyl-2-butanol, and 4-methyl-2-pentanol; ethers such as propylene glycol monomethyl ether (PGME), diethyl ether, tetrahydrofuran, 1,4-dioxane, and anisole; acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone. Examples of suitable solvents include ketones such as non-(CHO); esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), hydroxyisobutyrate methyl ester (HBM), and ethyl acetoacetate; lactones such as 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 are PGME, PGMEA, EL, GBL, HBM, CHO, and combinations thereof. The total solvent content (i.e., the cumulative solvent content of all solvents) in the photoresist composition is typically 40 to 99 wt %, more typically 70 to 99 wt %, and even more typically 85 to 99 wt %, based on the total weight of the photoresist composition. The desired solvent content depends, for example, on the desired thickness of the coated photoresist layer and the coating conditions.

[0095] The photoresist composition may further comprise one or more additional optional additives. For example, optional additives may include chemical dyes and contrast dyes, anti-striation agents, plasticizers, rate enhancers, sensitizers, photolytic quenchers (also known as photolytic bases), base quenchers, surfactants, and the like, or combinations thereof. When present, optional additives are typically present in the photoresist composition in an amount of 0.01 to 10 weight percent, based on the total solids content of the photoresist composition.

[0096] Photolytic deactivators generate a weak acid upon irradiation. The acid generated from the photolytic deactivator is not strong enough to react quickly with acid labile groups present in the resist matrix. Exemplary photolytic deactivators include, for example, photolytic cations, preferably C 1~20 Carboxylic acid or C 1~20 Also included are those useful for preparing strong acid generator compounds paired with anions of weak acids (pKa > -1), such as anions of sulfonic acids. Exemplary carboxylic acids include formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexanecarboxylic acid, benzoic acid, salicylic acid, and the like. Exemplary carboxylic acids include p-toluenesulfonic acid, camphorsulfonic acid, and the like. In a preferred embodiment, the photolytic quencher is a photolytic organic zwitterionic compound, such as diphenyliodonium-2-carboxylate.

[0097] The photodegradable deactivator may be in a non-polymer-bound form or a polymer-bound form. When in a polymer form, the photodegradable deactivator is present in polymerized units on the first polymer or the second polymer. The polymerized units containing the photodegradable deactivator 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 repeat units of the polymer.

[0098] Exemplary basic quenching agents include, for example, straight-chain aliphatic amines such as tributylamine, trioctylamine, triisopanolamine, tetrakis(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''-nitrilotriethanol; cycloaliphatic amines such as N,N-bis(2-hydroxyethyl)pivalamide, N,N-diethylacetamide, N-(2-hydroxyethyl)-4-hydroxypiperidine, tert-butyl 1-pyrrolidinecarboxylate, tert-butyl 2-ethyl-1H-imidazole-1-carboxylate, di-tert-butylpiperazine-1,4-dicarboxylate, and N-(2-acetoxyethyl)morpholine; aromatic amines such as pyridine, di-tert-butylpyridine, and pyridinium; N,N-bis(2-hydroxyethyl)pivalamide, N,N-diethylacetamide, N-(2-hydroxyethyl)-4-hydroxypiperidine, tert-butyl 1-pyrrolidinecarboxylate, tert-butyl 2-ethyl-1H-imidazole-1-carboxylate, di-tert-butylpiperazine-1,4-dicarboxylate, and N-(2-acetoxyethyl)morpholine; 1 ,N 1 ,N 3 ,N 3 linear and cyclic amides and derivatives thereof, such as tetrabutylmalonamide, 1-methylazepan-2-one, 1-allylazepan-2-one, and tert-butyl 1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylcarbamate; ammonium salts, such as quaternary ammonium salts of sulfonates, sulfamates, carboxylates, and phosphonates; imines, such as primary and secondary aldimines and ketimines; optionally substituted diazines, such as pyrazine, piperazine, and phenazine; optionally substituted diazoles, such as pyrazole, thiadiazole, and imidazole; and optionally substituted pyrrolidones, such as 2-pyrrolidone and cyclohexylpyrrolidine.

[0099] The basic quenching agent may be in a non-polymer-bound form or a polymer-bound form. When in a polymeric form, the quenching agent is present in polymerized units on the first polymer or the second polymer. The polymerized units containing the quenching agent are typically present in an amount of 0.1 to 30 mol %, preferably 1 to 10 mol %, more preferably 1 to 2 mol %, based on the total repeat units of the polymer.

[0100] Exemplary surfactants include fluorinated and non-fluorinated surfactants, and may be ionic or non-ionic, with non-ionic surfactants being preferred. Exemplary fluorinated non-ionic surfactants include perfluoro C4 surfactants such as FC-4430 and FC-4432 surfactants available from 3M Corporation; and fluorodiols such as POLYFOX PF-636, PF-6320, PF-656, and PF-6520 fluorosurfactants from Omnova. In one embodiment, the photoresist composition further comprises a surfactant polymer comprising a fluorine-containing repeating unit.

[0101] A pattern formation method using the photoresist composition of the present invention will now be described. Suitable substrates onto which the photoresist composition can be coated include electronic device substrates. A variety of electronic device substrates can be used in the present invention, including semiconductor wafers; polycrystalline silicon substrates; packaging substrates such as multichip modules; flat panel display substrates; and substrates for light-emitting diodes (LEDs) such as organic light-emitting diodes (OLEDs), with semiconductor wafers being typical. Such substrates are typically composed of one or more of silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. Suitable substrates can be in the form of wafers, such as those used in the manufacture of integrated circuits, optical sensors, flat panel displays, optical integrated 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 in accordance with the present invention. The substrate may optionally include one or more layers or structures that may contain the active or operable portions of the device being formed.

[0102] Typically, one or more lithography layers, such as a hard mask layer, for example, a spin-on carbon (SOC), amorphous carbon or metal hard mask layer, a CVD layer such as a silicon nitride (SiN) layer, a silicon oxide (SiO) layer or a silicon oxynitride (SiON) layer, an organic or inorganic underlayer, or a combination thereof, are provided on the upper layer of the substrate before coating with the photoresist composition of the present invention. Such layers, together with the overcoated photoresist layer, form a lithography material stack.

[0103] Optionally, a layer of adhesion promoter can be applied to the substrate surface before coating with the photoresist composition. If an adhesion promoter is desired, any suitable adhesion promoter for polymer films can be used, such as a silane, typically an organosilane such as trimethoxyvinylsilane, triethoxyvinylsilane, or hexamethyldisilazane, or an aminosilane coupling agent such as γ-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those sold under the names AP3000, AP8000, and AP9000S, available from DuPont Electronics & Imaging (Marlborough, Massachusetts).

[0104] The photoresist composition can be coated onto a substrate by any suitable method, including spin coating, spray coating, dip coating, doctor blading, and the like. For example, application of a photoresist layer can be achieved by spin-coating the photoresist in a solvent using a coating track, in which the photoresist is dispensed onto a rotating wafer. During dispensing, the wafer is typically spun at a speed of 4,000 revolutions per minute (rpm) or less, e.g., 200 to 3,000 rpm, e.g., 1,000 to 2,500 rpm, for 15 to 120 seconds, to obtain a layer of photoresist composition on the substrate. Those skilled in the art will understand that the thickness of the coated layer can be adjusted by varying the spin 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 200 nanometers (nm), preferably 15 to 100 nm, and more preferably 20 to 60 nm.

[0105] The photoresist composition is typically then soft-baked to minimize the solvent content in the layer, thereby forming a tack-free coating and improving adhesion of the layer to the substrate. Soft-baking can be performed, for example, on a hot plate or in an oven, with a hot plate being typical. The soft-baking temperature and time depend, for example, on the specific photoresist composition and thickness. The soft-baking temperature is typically 90 to 170°C, more typically 110 to 150°C. The soft-baking time is typically 10 seconds to 20 minutes, more typically 1 minute to 10 minutes, and even more typically 1 minute to 5 minutes. The heating time can be easily determined by one skilled in the art based on the components of the composition.

[0106] The photoresist layer is then patternwise exposed to activating radiation to create a solubility differential between the exposed and unexposed regions. References herein to exposing a photoresist composition to radiation activating the composition indicate that the radiation is capable of forming a latent image in the photoresist composition. Exposure is typically carried out through a patterned photomask having optically transparent and optically opaque regions corresponding to the exposed and unexposed regions of the resist layer, respectively. Alternatively, such exposure can be carried out without a photomask in a direct-write process, typically used in electron beam lithography. The activating radiation typically has a wavelength of less than 400 nm, less than 300 nm, or less than 200 nm, with wavelengths of 248 nm (KrF), 13.5 nm (EUV), or electron beam lithography being preferred. This method is also applicable to immersion or dry (non-immersion) lithography techniques. Exposure energy is typically between 1 and 200 millijoules per square centimeter (mJ / cm). 2 ), preferably 10 to 100 mJ / cm 2 , more preferably 20 to 50 mJ / cm 2 but also depends on the exposure tool and photoresist composition.

[0107] After the photoresist layer is exposed, a post-exposure bake (PEB) of the exposed photoresist layer is performed. PEB can be performed, for example, on a hot plate or in an oven, with a hot plate being typical. PEB conditions will depend, for example, on the specific photoresist composition and layer thickness. PEB is typically performed at a temperature of 80-150°C for 30-120 seconds. A latent image defined by polarity switching (exposed regions) and non-polarity switching (unexposed regions) is formed in the photoresist.

[0108] The exposed photoresist layer is then developed in an appropriate developer to selectively remove the areas of the layer that are soluble in the developer, while the remaining insoluble areas form a resulting photoresist pattern relief image. In a positive-tone development (PTD) process, the exposed areas of the photoresist layer are removed during development, leaving the unexposed areas. Conversely, in a negative-tone development (NTD) process, the exposed areas of the photoresist layer remain, while the unexposed areas are removed during development. Application of the developer can be by any suitable method, as described above for applying the photoresist composition; spin coating is typical. The development time is effective to remove the soluble areas of the photoresist, typically 5 to 60 seconds. Development is typically performed at room temperature.

[0109] Suitable developers for the PTD process include aqueous base developers, such as quaternary ammonium hydroxide solutions such as tetramethylammonium hydroxide (TMAH), preferably 0.26N (N), tetraethylammonium hydroxide, tetrabutylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. Suitable developers for the NTD process are organic solvent-based. This means that the cumulative content of organic solvents in the developer is 50% by weight or more, typically 95% by weight or more, 98% by weight or more, or 100% by weight, 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. The developer is typically 2-heptanone or n-butyl acetate.

[0110] Coated substrates can be formed from the photoresist compositions of the invention, including (a) a substrate having one or more layers to be patterned on its surface, and (b) a layer of a photoresist composition over the one or more layers to be patterned.

[0111] The photoresist pattern can be used, for example, as an etching mask, allowing the pattern to be transferred to one or more subsequently underlying layers by known etching techniques, typically dry etching such as reactive ion etching. The photoresist pattern can be used, for example, to transfer the pattern to an underlying hard mask layer, which is then used as an etching mask for pattern transfer to one or more layers below the hard mask layer. If the photoresist pattern is not consumed in the pattern transfer, it can be removed from the substrate by known techniques, such as oxygen plasma ashing. When used in one or more such pattern formation processes, the photoresist composition can be used to manufacture semiconductor devices such as memory devices, processor chips (CPUs), graphics chips, optoelectronic chips, LEDs, OLEDs, and other electronic devices.

[0112] The present invention is further illustrated by the following examples. [Example]

[0113] The chemical structures of the polymers used in the examples and comparative examples are shown below. The preparation of polymers P2 and P3 is disclosed in Patent Document 4. Polymers P1 to P4 were prepared using methods commonly used in the art. [ka]

[0114] The chemical structures of the photoacid generators A1 to A4 and the deactivators Q1 to Q3 used in the examples are shown below. [ka]

[0115] Example 1: Contrast Curve Measurement. Contrast curves at 248 nm were generated using a Canon ES2 scanner. The solvent for all compositions used in this example was a 50 / 50 w / w blend of propylene glycol monomethyl ether acetate and methyl 2-hydroxyisobutyrate. The total solids content of each composition was 1.55 wt%. The resulting mixtures were shaken on a mechanical shaker and then filtered through a 0.2 micrometer pore size PTFE disk filter. Each photoresist composition was spin-coated onto a 200 mm silicon wafer overcoated with a BARC stack (60 nm thick AR3 antireflective material laminated over 80 nm thick AR40A antireflective material, DuPont Electronics & Imaging) on ​​a TEL Clean Track ACT 8 wafer track and soft-baked at 110°C for 90 seconds to achieve a target photoresist layer thickness of approximately 40 nm. The resists were then scanned with 248 nm radiation at 5-50 mJ / cm. 2 The wafers were exposed to increasing doses from 0°C to 100°C, post-exposure baked (PEB) at 110°C for 60 seconds, developed in TMAH developer (MF-CD26, DuPont Electronics & Imaging) for 60 seconds, rinsed with deionized water, and dried. The thickness of each exposed area was measured and plotted against the dose. The dose-to-clear (E0) was calculated as the point at which the residual film thickness was less than 10% of the original coating thickness. An additional contrast curve for each wafer was generated by plotting the normalized photoresist layer thickness in the exposed area against the logarithm of the dose. The contrast (γ) was determined from the normalized contrast curve as the slope between 80% and 20% photoresist film thickness. The unexposed film thickness loss (UFTL) was calculated by measuring the film thickness at 10 points on an unexposed photoresist film spin-coated onto a cured BARC layer on a 200 mm silicon wafer and calculating the difference between the film thickness of the coated film and the average thickness of the 10 points after rinsing with 0.26 N TMAH.

[0116] Example 1A: Using the contrast curve method described above, the contrast (γ) was measured for Comparative Compositions 1-4 containing polymer P1, Comparative Compositions 2-5 containing polymer P2, and Comparative Composition 6 containing polymer P3. Inventive Composition 7 contained a blend of polymers P1 and P2, and Inventive Composition 8 contained a blend of polymers P1 and P5. Table 1 shows the compositions (amounts are in weight percent of the composition), E0, and contrast (γ) at 248 nm.

[0117] [Table 1]

[0118] As shown in Table 1, the contrast (γ) of inventive compositions 7 and 8 is significantly higher than the comparative composition, and therefore the inventive compositions are higher contrast resists.

[0119] Example 1B: Using the contrast curve method described above, the contrast was measured for Comparative Composition 10 containing polymer P1, Comparative Composition 11 containing polymer P2, and Inventive Compositions 13-15 containing blends of polymers P1 and P2. Table 2 shows the compositions (amounts are in weight percent of the composition), E0, and γ at 248 nm.

[0120] [Table 2]

[0121] As shown in Table 2, the γ of inventive compositions 13, 14, and 15 is significantly higher than the γ of comparative compositions 10-11, and therefore the inventive compositions are higher contrast resists.

[0122] Example 1C: Using the contrast curve method described above, the contrast of comparative composition 16, which included polymer P1, and comparative composition 17, which included polymer P2, was measured. Inventive composition 18 included a blend of polymers P1 and P2. Table 3 shows the composition (amounts are in weight percent of the composition), E0, and UFTL.

[0123] [Table 3]

[0124] As shown in Table 3, the UFTL of inventive composition 18 is lower than that of comparative compositions 16-17, indicating that inventive composition 18 has better developer resistance in unexposed areas, which correlates with improved lithographic properties.

[0125] Example 1D: Using the contrast curve method described above, the contrast was measured for Comparative Composition 19 comprising polymer P1, Comparative Composition 20 comprising polymer P2, Comparative Composition 21 comprising polymer P3, Inventive Composition 22 comprising a blend of polymers P1 and P4, and Inventive Composition 23 comprising a blend of polymers P1 and P5. Table 4 shows the compositions (amounts are in weight percent of the composition), E0, and UFTL.

[0126] [Table 4]

[0127] As shown in Table 4, the UFTL of inventive compositions 22 and 23 was significantly lower than that of comparative compositions 19, 20, and 21, indicating that inventive compositions 22 and 23 have better developer resistance in unexposed areas, which correlates with improved lithographic properties.

[0128] Example 2: Electron Beam High-Density Line-Space Patterning. Coating resist compositions having the compositions shown in Tables 6-8 were prepared by combining the listed ingredients in a 50 / 50 (w / w) mixture of propylene glycol monomethyl ether acetate and methyl 2-hydroxyisobutyrate. The total solids content of each composition was 1.55 wt%. Each resist composition was spin-coated onto a cured organic bottom reflective coating (BARC) layer on a 200 mm silicon wafer and baked at 110°C for 90 seconds (forming a 40 nm thick photoresist film).

[0129] Lithographic patterning was performed using an electron beam (E-beam) lithography tool (model JEOL JBX9500FS) to print high-density line-space (L / S) patterns with a 1:1 ratio at different pitch sizes. After exposure, a post-exposure bake was performed at 100°C for 60 seconds, followed by a 60-second development step using 0.26N TMAH solution. Scanning electron microscopy (SEM) was performed to collect images and analyze the printed patterns. The critical dimensions (CDs) of the line-space patterns in nanometers (nm) were analyzed. At this time, the sizing energy "E size " is the unit of microcoulombs per square centimeter (μC / cm 2 ), which represents the irradiation energy required to resolve a 1:1 line-space pattern with a specific half-pitch. The line width roughness (LWR), expressed in nanometers, was determined by obtaining a 3-sigma value from the distribution of a total of 100 random points of line width measurements, followed by removing the measurement noise (MetroLER software).

[0130] Example 2A: Using the high density line-space patterning and analysis method described above, the lithographic properties of comparative composition 24 containing polymer P1, comparative composition 25 containing polymer P2, and inventive composition 26 containing a blend of polymers P1 and P2 were evaluated. Table 6 shows the compositions (amounts are in weight percent of the composition), E size The results of LWR for a 1:1 L / S pattern with a half pitch (HP) of 35 nm are shown.

[0131] [Table 5]

[0132] As shown in Table 6, inventive composition 26 achieved a lower LWR compared to comparative compositions 24 and 25.

[0133] Example 2B: Using the high density line-space patterning and analysis method described above, the lithographic properties of comparative composition 27 containing polymer P1, comparative composition 28 containing polymer P2, and inventive composition 29 containing a blend of polymers P1 and P2 were evaluated. Table 7 shows the compositions (amounts are in weight percent of the composition), E size , and LWR results for a 1:1 L / S pattern with a HP of 35 nm are shown.

[0134] [Table 6]

[0135] As shown in Table 7, inventive composition 29 achieved a lower LWR compared to comparative compositions 27 and 28. In addition, inventive composition 6 exhibits a significant light speed advantage over comparative composition 4.

[0136] Example 2C: Using the high density line-space patterning and analysis methods described above, the lithographic performance of comparative compositions 30 and 31, each containing polymers P1 and P2, and compositions 32-34 of the present invention, each containing a blend of polymers P1 and P2, was evaluated. Table 8 shows the composition (amounts are in weight percent of the composition), E size , and LWR results for a 1:1 L / S pattern with a HP of 35 nm are shown.

[0137] [Table 7]

[0138] As shown in Table 8, inventive compositions 32, 33, and 34 achieved lower LWR compared to comparative compositions 30 and 31.

[0139] Example 3: Electron Beam Grid Contact Hole (CH) Patterning. Coating resist compositions were prepared using the compositions shown in Tables 10 and 11 in a 50 / 50 (w / w) mixture of PGMEA and methyl 2-hydroxyisobutyrate. The total solids content of each composition was 1.55 wt%. Each resist composition was spin-coated onto a cured organic bottom antireflective coating (BARC) layer on a 200 mm silicon wafer and baked at 110°C for 90 seconds to form a 40 nm thick photoresist film. Each resist composition was spin-coated onto a silicon wafer with an organic antireflective coating and soft-baked at 110°C for 90 seconds.

[0140] Lithographic patterning was performed using an electron beam (E-beam) lithography tool (model JEOL JBX9500FS) to print grid contact hole (CH) patterns with varying pitches. After exposure, a post-exposure bake was performed at 100°C for 60 seconds, followed by a 60-second development step using 0.26N TMAH solution. Scanning electron microscopy was used to collect images and analyze the printed patterns. The critical dimensions (CD) of the contact hole patterns were analyzed and expressed in nm. The sizing energy, E siz e" is the unit of microcoulombs per square centimeter (μC / cm 2 ) and the critical dimension uniformity (CDU) expressed in nm was determined by measuring the CD of 35 contact holes using a Fractilia MetroLER metrology tool in noise filter mode.

[0141] Example 3A: Using the CH patterning and analysis methods described above, the lithographic performance of comparative compositions 35 and 36, comprising polymers P1 and P2, respectively, and composition 37 of the present invention, comprising a blend of polymers P1 and P3, was evaluated. Table 9 shows the composition (amounts are in weight percent of the composition), E size, and the CDU results for CH patterns with a HP of 35 nm are shown.

[0142] [Table 8]

[0143] As shown in Table 9, inventive composition 37 achieved lower CDU compared to comparative compositions 35 and 36.

[0144] Example 3B: Photoresist compositions were prepared by dissolving the solid components in a solvent using the materials and ratios shown in Table 10 to achieve a total solids content of 1.55%. Each wafer was spin-coated with the respective photoresist composition and soft-baked at 110°C for 90 seconds to obtain a 40 nm thick photoresist layer. The photoresist-coated substrates were exposed to electron beam radiation using a JEOL Ltd. JBX-9500FS electron beam lithography system to print a 1:1 contact hole pattern with a 35 nm diameter and 70 nm pitch. The resist was post-exposure baked at 90°C for 60 seconds, developed in MF™-CD26 TMAH developer (DuPont Electronics & Imaging) for 45 seconds, rinsed with deionized water, and dried. Scanning electron microscopy was used to collect images and analyze the printed patterns. CD measurements of the contact hole patterns were performed based on the SEM images using Fractilia MetroLER metrology software. Sizing energy (E size The sizing energy and CD uniformity (3σ) (CDU) were determined based on the measurements. The sizing energy is the irradiation energy required to resolve a target contact hole pattern with a diameter of 35 nm. The CDU was determined based on the CD of 35 contact holes. Table 10 shows the composition (amounts are in weight percent based on the total solids in a 1:1 mixture of solvents S1 and S2), E size (μC / cm 2 ) and CDU (nm). S1 is propylene glycol monomethyl ether acetate and S2 is methyl 2-hydroxyisobutyrate.

[0145] [Table 9]

[0146] As shown in Table 10, compositions 38-41 of the present invention achieve significantly lower CDU in the range of 1.1 to 1.6, which is desirable for electronic devices.

[0147] While the present disclosure has been described in conjunction with what are presently considered to be practical exemplary embodiments, it is to 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 first polymer consisting solely of a first repeat unit comprising a hydroxyaryl group and a second repeat unit comprising an acid labile group, the first polymer not comprising a lactone group; a second polymer consisting solely of first repeat units comprising hydroxyaryl groups, second repeat units comprising acid labile groups, and third repeat units comprising lactone groups; a photoacid generator; and solvent; A photoresist composition comprising: The second repeat unit of the first polymer is represented by formula (2a) or (2b): 【Chemistry 1】 (In the formula (2a) or (2b), R ｃ and R ｄ are each independently hydrogen, fluorine, cyano, substituted or unsubstituted C １～１０ Alkyl, or substituted or unsubstituted C １～１０ is fluoroalkyl; R １ ~R ６ are each independently hydrogen, substituted or unsubstituted C １～２０ Alkyl, substituted or unsubstituted C ３～２０ Cycloalkyl, substituted or unsubstituted C １～２０ Heterocycloalkyl, substituted or unsubstituted C ２～２０ Alkenyl, substituted or unsubstituted C ３～２０ Cycloalkenyl, substituted or unsubstituted C ３～２０ Heterocycloalkenyl, substituted or unsubstituted C ６～２０ Aryl, or substituted or unsubstituted C ２～２０ heteroaryl, provided that R １ ~R ３ Only one of R ４ ~R ６ can be hydrogen, provided that only one of R １ ~R ３ If one of R is hydrogen, then the other R １ ~R ３ One or both of the C ６～２０ Aryl or substituted or unsubstituted C ４～２０ heteroaryl, and R ４ ~R ６ If one of R is hydrogen, then the other R ４ ~R ６ One or both of which are substituted or unsubstituted C ６～２０ Aryl or substituted or unsubstituted C ４～２０ is heteroaryl; R １ ~R ３ any two of optionally together form a ring, and R １ ~R ３ Each of the optionally includes as part of its structure -O-, -C(O)-, -N(R ４２ )-, -S-, or -S(O) ２ -, where R ４２ is hydrogen, linear or branched C １～２０ Alkyl, monocyclic or polycyclic C ３～２０ Cycloalkyl or monocyclic or polycyclic C １～２０ may be heterocycloalkyl; R ４ ~R ６ any two of optionally together form a ring, and R ４ ~R ６ Each of the optionally includes as part of its structure -O-, -C(O)-, -N(R ４３ )-, -S-, or -S(O) ２ -, where R ４３ is hydrogen, linear or branched C １～２０ Alkyl, monocyclic or polycyclic C ３～２０ Cycloalkyl or monocyclic or polycyclic C １～２０ is heterocycloalkyl; L ２ is a divalent linking group) and The first repeating unit of the second polymer is 【Chemistry 2】 is selected from The second repeat unit of the second polymer has the formula (2b'): 【Transformation 3】 (In the formula, R d is hydrogen, fluorine, cyano, substituted or unsubstituted C １～１０ Alkyl, or substituted or unsubstituted C １～１０ is fluoroalkyl; R ４ ~R ６ are each independently hydrogen, substituted or unsubstituted C １～２０ Alkyl, substituted or unsubstituted C ３～２０ Cycloalkyl, substituted or unsubstituted C １～２０ Heterocycloalkyl, substituted or unsubstituted C ２～２０ Alkenyl, substituted or unsubstituted C ３～２０ Cycloalkenyl, substituted or unsubstituted C ３～２０ Heterocycloalkenyl, substituted or unsubstituted C ６～２０ Aryl, or substituted or unsubstituted C ２～２０ heteroaryl, provided that R ４ ~R ６ can be hydrogen, provided that only one of R ４ ~R ６ If one of R is hydrogen, then the other R ４ ~R ６ One or both of which are substituted or unsubstituted C ６～２０ Aryl or substituted or unsubstituted C ４～２０ is heteroaryl; R ４ ~R ６ any two of optionally together form a ring, and R ４ ~R ６ Each of the optionally includes as part of its structure -O-, -C(O)-, -N(R ４３ )-, -S-, or -S(O) ２ -, where R ４３ is hydrogen, linear or branched C １～２０ Alkyl, monocyclic or polycyclic C ３～２０ Cycloalkyl or monocyclic or polycyclic C １～２０ heterocycloalkyl) wherein the second repeat unit of the second polymer is derived from one or more monomers of 【Chemistry 4】 Not and A photoresist composition wherein the second polymer comprises the second repeat unit in an amount of 30 to 60 mole % based on the total repeat units in the second polymer.

2. The first repeating unit of the first polymer is represented by formula (1'): 【Transformation 5】 (In the formula, R ａ is hydrogen, halogen, cyano, substituted or unsubstituted C １～１０ Alkyl, or substituted or unsubstituted C １～１０ is fluoroalkyl; R ｂ is hydrogen, L １ -C(O)-, which forms a ring together with Ar １ is a single bond that forms a ring together with L １ is a single bond or -N(R ２ａ )- is a divalent linking group optionally containing R ２ａ is hydrogen, C １～６ alkyl, or R ｂ is a single bond that forms a ring together with However, R ２ａ is R ｂ When R is the single bond that forms a ring with ｂ Is, L １ and —C(O)—, which forms a ring with Ar １ each optionally 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 １～３０ Heterocycloalkyl, substituted or unsubstituted C ２～３０ Alkenyl, substituted or unsubstituted C ２～３０ Alkynyl, substituted or unsubstituted C ６～３０ Aryl, substituted or unsubstituted C ７～３０ Aryl alkyl, substituted or unsubstituted C ７～３０ Alkylaryl, substituted or unsubstituted C ４～６０ Heteroaryl, substituted or unsubstituted C ５～６０ Heteroarylalkyl, substituted or unsubstituted C ５～６０ alkylheteroaryl, —OR ２１ , or -NR ２２ R ２３ hydroxy-substituted C further substituted with one or more of ６～６０ Aryl group, hydroxy-substituted C ４～６０ heteroaryl groups, or combinations thereof, where R ２１ ~R ２３ are each independently a substituted or unsubstituted C １～３０ Alkyl, substituted or unsubstituted C ３～３０ Cycloalkyl, substituted or unsubstituted C １～２０ Heterocycloalkyl, substituted or unsubstituted C ６～３０ Aryl, substituted or unsubstituted C ７～３０ Aryl alkyl, substituted or unsubstituted C ７～３０ Alkylaryl, substituted or unsubstituted C ４～３０ Heteroaryl, substituted or unsubstituted C ５～３０ Heteroarylalkyl or substituted or unsubstituted C ５～３０ alkylheteroaryl) 2. The photoresist composition of claim 1, wherein the repeating unit is:

3. The third repeating unit of the second polymer is represented by formula (4): 【Transformation 6】 (In the formula, R ｆ is hydrogen, fluorine, cyano, substituted or unsubstituted C １～１０ Alkyl, or substituted or unsubstituted C １～１０ is fluoroalkyl; L ４ is a single bond or a divalent linking group; R １４ is a monocyclic, polycyclic, or fused polycyclic C ４～２０ lactone-containing group or a monocyclic, polycyclic, or fused polycyclic C ４～２０ sultone-containing group) 3. The photoresist composition of claim 1, wherein the photoresist composition is derived from one or more monomers of the formula:

4. 4. The photoresist composition according to claim 1, wherein the photoacid generator is a non-polymerizable type.

5. the photoacid generator comprises a sulfonate group on the anion; The photoresist composition of any one of claims 1 to 4, further comprising a non-polymerizable second photoacid generator, wherein the second photoacid generator comprises an anion that does not have a sulfonate group.

6. The photoresist composition of any one of claims 1 to 5, further comprising a photolytic deactivator.

7. The photoresist composition of any one of claims 1 to 6, further comprising a base labile material comprising one or more base labile groups, wherein the base labile material is different from the first polymer and the second polymer.

8. The photoresist composition of any one of claims 1 to 7, wherein the weight ratio of the first polymer to the second polymer is from 1:4 to 4:

1.

9. A pattern formation method, comprising: (a) applying a layer of a photoresist composition of any one of claims 1 to 8 to a substrate; (b) patternwise exposing the photoresist composition layer to activating radiation; and (c) developing the exposed photoresist composition layer to provide a resist relief image; A pattern forming method comprising:

10. The first repeating unit of the first polymer is 【Transformation 7】 The photoresist composition of claim 1 selected from:

Images