Salt, photoresist composition, and pattern formation method

Abstract

The present invention provides a salt, a photoresist composition, and a pattern formation method. [Solution] A salt containing a cation represented by the following formula (1) or (2): TIFF2026114994000060.tif27166 (In the formula, Ar 1 ~Ar 5 At least one of them is equation (A): TIFF2026114994000061.tif39166 be).

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority and benefits under U.S. Provisional Patent Application No. 63 / 738,955, filed with the U.S. Patent and Trademark Office on 26 December 2024, which is incorporated herein by reference in its entirety.

[0002] The present invention relates to a salt, a photoresist composition, and a pattern forming method. The present invention is particularly suitable for lithography applications in the semiconductor manufacturing industry. [Background technology]

[0003] Photoresist materials are photosensitive compositions typically used to transfer images onto one or more underlying layers, such as metal, semiconductor, or dielectric layers, placed on a semiconductor substrate. High-resolution photoresists and photolithography processing tools have been and continue to be developed to increase the integration density of semiconductor devices and enable the formation of structures with dimensions in the nanometer range.

[0004] Chemically amplified resists (CARs) remain a cornerstone technology in high-resolution lithography. Innovations over the past 20 years in this platform have enabled industry to print highly uniform features at the nanometer scale. This, in turn, allows resists to meet the increasingly demanding requirements for high-performance semiconductors driven by modern technological advancements.

[0005] There is a continuous need for photoresist compositions and patterning methods using such photoresist compositions that improve multiple aspects of lithography performance (e.g., photospeed or sensitivity (S), line width roughness (LWR), line edge roughness (LER), local limiting dimensional uniformity (LCDU), and resolution (R)). [Prior art documents] [Patent Documents]

[0006]

Patent Document 1

Patent Document 2

Non-Patent Document

[0007]

Non-Patent Document 1

Summary of the Invention

Means for Solving the Problems

[0008] One aspect provides a salt containing a cation represented by formula (1) or (2):

Chemical Formula

[0009] Another embodiment provides a photoresist composition comprising the salt and solvent described herein.

[0010] Another embodiment provides a pattern forming method comprising: coating a layer of photoresist composition onto a substrate to obtain a photoresist composition layer; pattern-exposing the photoresist composition layer to activating radiation to obtain an exposed photoresist composition layer; and developing the exposed photoresist composition layer to obtain a pattern. [Modes for carrying out the invention]

[0011] Here, exemplary embodiments are referenced in detail, and examples thereof are illustrated in this description. In this regard, these exemplary embodiments may take different forms and should not be construed as being limited to the descriptions expressed herein. Accordingly, exemplary embodiments are described below by reference to the figures in order to illustrate aspects of this description. As used herein, the terms “and / or” encompass any and all combinations of one or more of the related enumerated items. Expressions such as “at least one of” qualify the entire list of elements, when preceding a list of elements, and do not qualify the individual elements of the list.

[0012] As used herein, the terms “a,” “an,” and “the” do not imply a limitation of quantity and should be interpreted as encompassing both singular and plural forms unless otherwise specifically stated herein or clearly contradicted by the context. “Or” means “and / or” unless otherwise specified. The modifying phrase “about” used in relation to quantity includes the expressed value and has meaning determined by the context (e.g., the degree of error associated with the measurement of a particular quantity). All scopes disclosed herein include endpoints, which are independently combinable with one another. The suffix “(s)” includes both singular and plural forms of the term it modifies and is intended to include at least one of those terms. “Optional” or “optionally” means that the event or situation described thereafter may or may not occur, and that the description includes both the cases in which the event occurs and the cases in which the event does not occur. The terms “first,” “second,” etc., used herein do not imply 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 an intervening element may exist between them. In contrast, when an element is said to be “directly on” another element, no intervening element is present. It should be understood that the components, elements, limitations, and / or features described in the embodiments may be combined in any preferred manner in various embodiments.

[0013] Unless otherwise specified, all terms used herein (including technical and scientific terms) have the same meaning as those generally understood by those skilled in the art to which the invention pertains. Terms such as those defined in commonly used dictionaries should be interpreted as having the same meaning as those defined in the relevant art and in relation to this disclosure, and it will be further understood that unless explicitly defined herein, they should not be interpreted in an ideal or overly formal sense.

[0014] As used herein, "chemical beam" or "radiation" means, for example, the emission spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet (EUV) light, X-rays, particle beams such as electron beams and ion beams. Furthermore, in this invention, "light" means chemical beam or radiation. A krypton fluoride laser (KrF laser) is a specific type of excimer laser that may be called an exciplex laser. "Excimer" is an abbreviation for "excitation dimer," while "exciplex" is an abbreviation for "excitation complex." An excimer laser uses a mixture of a noble gas (argon, krypton, or xenon) and a halogen gas (fluorine or chlorine) and emits coherent stimulating radiation (laser light) in the ultraviolet range under suitable conditions of electrical stimulation and high pressure. Furthermore, unless otherwise specified, "exposure" in this specification includes not only exposure using far ultraviolet light such as mercury lamps and excimer lasers, X-rays, and extreme ultraviolet (EUV) light, but also writing using particle beams such as electron beams and ion beams.

[0015] As used herein, the terms “hydrocarbon” means an organic compound having at least one carbon atom and at least one hydrogen atom; “alkyl” means a linear or branched saturated hydrocarbon group having the specified number of carbon atoms and a valency of 1; “alkylene” means an alkyl group having a valency of 2; “hydroxyalkyl” means an alkyl group substituted with at least one hydroxyl group (-OH); “alkoxy” means “alkyl-O-”; “carboxyl” and “carbone” "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; "cycloalkylene" refers to a cycloalkyl group having a valency of 2; "alkenyl" refers to a monovalent hydrocarbon group having at least one carbon-carbon double bond, either straight-chain or branched-chain; "alkenoxy" refers to "alkenyl-O-"; "alkenylene" refers to an alkenyl group having a valency of 2; "cycloalkenyl" refers to a group having at least one carbon- "A" refers to a non-aromatic cyclic divalent hydrocarbon group having at least three carbon atoms and a 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 aromatic ring system that satisfies Huckel's rule (4n + 2π electrons) and contains carbon atoms in the ring; the term "heteroaromatic group" refers to an aromatic group that contains one or more heteroatoms (e.g., 1 to 4 heteroatoms) selected from N, O, and S instead of carbon atoms in the ring; "A" "Riel" refers to a monovalent monocyclic or polycyclic aromatic ring system in which all ring members are carbon, and may include a group having an aromatic ring fused to at least one cycloalkyl or heterocycloalkyl ring; "Arylene" refers to an aryl group having a valence of 2; "Alkylaryl" refers to an aryl group substituted with an alkyl group; "Arylalkyl" refers to an alkyl group substituted with an aryl group; "Aryloxy" refers to "aryl-O-"; and "Arylthio" refers to "aryl-S-".

[0016] The prefix "hetero" means that a compound or group contains at least one ring member that is a heteroatom (e.g., 1, 2, 3, or 4 or more heteroatoms) instead of a carbon atom, and each heteroatom can be independently N, O, S, Si, or P. "Heteroatom-containing group" refers to a substituent containing at least one heteroatom, "heteroalkyl" refers to an alkyl group having at least one heteroatom instead of carbon, and "heterocycloalkyl" refers to a cycloalkyl group having 1 to 4 heteroatoms as ring members instead of carbon. The terms "heterocycloalkylene" refers to a heterocycloalkyl group having a valence of 2, and "heteroaryl" refers to an aromatic 4-8 member monocyclic, 8-12 member bicyclic, or 11-14 member tricyclic group having 1-4 heteroatoms (in the case of a monocyclic), 1-6 heteroatoms (in the case of a bicyclic), or 1-9 heteroatoms (in the case of a tricyclic) (for example, in the case of a monocyclic, bicyclic, or tricyclic, respectively, carbon atoms and 1-3, 1-6, or 1-9 heteroatoms of N, O, or S). Examples of heteroaryl groups include pyridyl, furyl (furyl or furanyl), imidazolyl, benzimidazolyl, pyrimidinyl, thiophenyl or thienyl, quinolinyl, indolyl, thiazolyl, etc., and "heteroarylene" refers to a heteroaryl group having a valence of 2.

[0017] 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 or more fluoro, chloro, bromo, or iodo substituents instead of a hydrogen atom. A combination of halo groups (e.g., bromo and fluoro) or a fluoro group alone may exist. For example, the term "haloalkyl" refers to an alkyl group substituted with one or more halogens. As used herein, "substituted C 1~8 "Haloalkyl" refers to C substituted with at least one halogen. 1~8Refers to an alkyl group, which is further substituted with one or more other substituents that are not halogen. It should be understood that since a halogen atom does not replace a carbon atom, substitution of a group with a halogen atom is not considered a heteroatom-containing group.

[0018] Each of the foregoing substituents may be optionally substituted, unless otherwise expressly defined. The term "optionally substituted" refers to being either substituted or unsubstituted. "Substituted" means that at least one hydrogen atom of a chemical structure or group is replaced with another terminal substituent, typically monovalent, provided that it does not exceed the normal valence of the designated atom. When the substituent is oxo (i.e., O), two geminal hydrogen atoms on a carbon atom are replaced with a terminal oxo group. It is further pointed out that the oxo group is bonded to carbon via a double bond to form a carbonyl (C=O), and the carbonyl group is represented herein as -C(O)-. Combinations of substituents or variables are permitted. Exemplary substituents that may be present at a "substituted" position include, but are not limited to, nitro (-NO2), cyano (-CN), hydroxyl (-OH), oxo (O), amino (-NH2), mono- or di-(C 1~6 )alkylamino, alkanoyl (e.g., a C 2~6 alkanoyl group), formyl (-C(O)H), carboxylic acid or its alkali metal salt or ammonium salt; ester (including acrylate, methacrylate, lactone), e.g., C 2~6 alkyl ester (-C(O)O-alkyl or -OC(O)-alkyl) and C 7~13 aryl ester (-C(O)O-aryl or -OC(O)-aryl); amide (-C(O)NR2, where R is hydrogen or C 1~6 alkyl), carboxamide (-CH2C(O)NR2, where R is hydrogen or C 1~6 alkyl), halogen, thiol (-SH), C 1~6 alkylthio (-S-alkyl), thiocyanato (-SCN), C 1~6 alkyl, C 2~6 alkenyl, C 2~6 alkynyl, C1~6 Haloalkyl, C 1~9 Alkoxy, C 1~6 Haloalkoxy, C 3~12 Cycloalkyl, C 5~18 Cycloalkenyl, C 2~18 Heterocycloalkenyl, a C having at least one aromatic ring 6~12 Aryls (e.g., phenyl, biphenyl, naphthyl, etc., where each ring is substituted or unsubstituted aromatic), C having 1 to 3 independent or fused rings and 6 to 18 ring carbon atoms. 7~19 Arylalkyls, arylalkoxys having 1-3 independent or fused rings and 6-18 ring carbon atoms, C 7~12 Alkylaryl, C 3~12 Heterocycloalkyl, C 3~12 Heteroaryl, C 1~6 Alkylsulfonyl (-S(O)2-alkyl), C 6~12 Examples include arylsulfonyl (-S(O)2-aryl) or tosyl (CH3C6H4SO2-). When a group is substituted, the number of carbon atoms indicated is the total number of carbon atoms in the group, excluding the carbon atoms of any substituents. For example, the group -CH2CH2CN is a cyanosubstituted C2 alkyl group.

[0019] In this specification, unless otherwise defined, "divalent linking group" refers to -O-, -S-, -Te-, -Se-, -C(O)-, -N(R ’ )-, C(O)N(R ’ )-, -S(O)-, -S(O)2-, -C(S)-, -C(Te)-, -C(Se)-, substitution or non-substitution C 1~30 Alkylene, substituted, or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 This refers to a divalent group containing one or more heteroarylenes or combinations thereof, where each R ’ These are, independently, hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl or substituted or unsubstituted C 3~30 It is a heteroaryl compound. Typically, the divalent linking group is -O-, -S-, -C(O)-, -N(R')-, -S(O)-, -S(O)2-, substituted or unsubstituted C 1~30 Alkylene, substituted, or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 It comprises one or more heteroarylenes or combinations thereof, where R' is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl or substituted or unsubstituted C 3~30 It is a heteroaryl compound. More typically, the divalent linking groups are -O-, -S-, -C(O)-, -C(O)O-, -N(R ’ )-, -C(O)N(R')-, substitution or non-substitution C 1~10 Alkylene, substituted, or unsubstituted C 3~10 Cycloalkylene, substituted or unsubstituted C 3~10 Heterocycloalkylene, substituted or unsubstituted C 6~10 Arylene, substituted or unsubstituted C 3~10 The compound comprises at least one heteroarylene or a combination thereof, where R is hydrogen, substituted or unsubstituted C 1~10 Alkyl, substituted, or unsubstituted C 1~10 Heteroalkyl, substituted, or unsubstituted C 6~10 Aryl or substituted or unsubstituted C 3~10 It is a heteroaryl compound.

[0020] As used herein, “acid-unstable group” refers to a group whose bonds are optionally and typically cleaved by the action of an acid during heat treatment, resulting in the formation of a polar group such as a carboxylic acid group or an alcohol group. In some cases, the acid-unstable group may be formed on a polymer, and optionally and typically, the portion bound to the cleaved bond is detached from the polymer. In other systems, the nonpolymer compound may contain an acid-unstable group that can be cleaved by the action of an acid, resulting in the formation of a polar group such as a carboxylic acid group or an alcohol group on the cleaved portion of the nonpolymer compound. Such acids are typically photo-generated acids in which bond cleavage occurs during post-exposure baking (PEB). However, embodiments are not limited thereto, and for example, such acids may be thermally generated. Preferred acid-unstable groups include, for example, tertiary alkyl ester groups, secondary or tertiary ester groups having an aryl group, secondary or tertiary ester groups having a combination of an alkyl group and an aryl group, tertiary alkoxy groups, acetal groups, or ketal groups. In this technical field, acid-unstable groups are generally referred to as "acid-cleavable groups," "acid-cleavable protecting groups," "acid-unstable protecting groups," "acid-leaving groups," "acid-degradable groups," and "acid-sensitive groups."

[0021] Improving feature uniformity (LER, LWR, and LCDU) remains one of the major challenges in photolithography. CAR materials typically consist of multiple components, such as polymers, photoacid generators (PAGs), photodegradable deactivators (PDQs), and other additives. Differences in the affinity of each component to the surrounding matrix can lead to non-uniform distribution within the film. In addition, the dispersibility of the polymer itself can also cause non-uniformity, as its physical properties can vary dramatically depending on its chain length and composition. Therefore, film uniformity remains a crucial property for improving feature uniformity in high-resolution lithography.

[0022] The inventors have discovered a molecular photoresist platform for providing a homogeneous photoresist. This platform eliminates the need for a separate polymer that can be switched by acid by incorporating this function into the photoacid generator (PAG) itself. In the molecular photoresist described herein, the acid-generating component and the solubility-switching component are part of the same molecule. By reducing the number of added components and eliminating polymer-induced dispersibility, the inventors have provided a photoresist composition that is essentially more homogeneous compared to photoresist compositions containing separate, independent polymers that can be switched by acid.

[0023] A salt containing a cation represented by formula (1) or (2) is provided: [ka]

[0024] In equations (1) and (2), Ar 1 ~Ar 5 These are, independently, substitutional or non-substitutional C. 6~30 Aryl or substituted or unsubstituted C 3~30 It is a heteroaryl, but the Ar in equation (1) 1 ~Ar 3 At least one of the following, and Ar of formula (2) 4 ~Ar 5 At least one of them is of formula (A) as defined below. In other words, Ar of formula (1) 1 ~Ar 3 At least one of the following and Ar of formula (2) 4 ~Ar 5 At least one of these is substituted for formula (A) as defined herein.

[0025] C 6~30 Aryl group and C 3~30 Each heteroaryl group may be monocyclic or polycyclic. 3~30When an aryl group is polycyclic, it should be understood that the number of carbon atoms is sufficient to make the group chemically feasible. For example, "monocyclic or polycyclic C 6~30 "Aryl" refers to a monocyclic C6 aryl group or a polycyclic C6 group. 10~30 It can also refer to an "aryl group." Similarly, it can refer to a "monocyclic or polycyclic carbon." 3~30 If a heteroaryl is polycyclic, the number of carbon atoms is sufficient to make the group chemically feasible. For example, "monocyclic or polycyclic C 3~30 "Heteroaryl" is a "monocyclic C 3~6 Heteroaryl or polycyclic C 5~30 It can sometimes refer to "heteroaryl." 1 ~Ar 5 Examples of groups include, but are not limited to, benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenylene, chrysene, phenalene, benz[a]anthracene, dibenz[a,h]anthracene, or benzo[a]pyrene, each of which may be substituted or unsubstituted. Typically, Ar 1 ~Ar 5 benzene is benzene, which may be substituted or unsubstituted, but the Ar of formula (1) 1 ~Ar 3 At least one of the following and Ar of formula (2) 4 ~Ar 5 At least one of them is of formula (A) as defined below.

[0026] In equation (1), Ar 1 ~Ar 3 Each of these groups, whether independent or via a single bond or divalent linking group, can form another Ar group. 1 ~Ar 3 They may be connected to form a ring. For example, Ar 1 ~Ar 3 Two or more of these may be linked to each other via single bonds or divalent linking groups to form a ring. In some embodiments, Ar 1 and Ar 2 They may be connected to each other via single bonds.

[0027] In equation (2), Ar 4 ~Ar 5 Each of these groups, whether independent or via a single bond or divalent linking group, can form another Ar group. 4 ~Ar 5 They may be connected to form a ring. For example, Ar 4 and Ar 5 These may be linked to each other via single bonds or divalent linking groups to form a ring.

[0028] In equations (1) and (2), the Ar in equation (1) 1 ~Ar 3 At least one of the following and Ar of formula (2) 4 ~Ar 5 At least one of them is equation (A): [ka] It belongs to them.

[0029] In equation (A), each ring A 1 C 6~30 Aryl or C 3~30 It is a heteroaryl compound. 6~30 Aryl group and C 3~30 The heteroaryl groups are each Ar 1 ~Ar 5 As mentioned above, ring A may be monocyclic or polycyclic. 1 Examples of the group include, but are not limited to, benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenylene, chrysene, phenalene, benz[a]anthracene, dibenz[a,h]anthracene, or benzo[a]pyrene, each of which may be substituted or unsubstituted. Typically, ring A 1 It is benzene.

[0030] In equation (A), each R 1 These are independently non-hydrogen substituents. For example, each R 1These are independently deuterium, halogen, substituted or unsubstituted C 1~30 Alkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 3~30 Cycloalkenes, substituted or unsubstituted C 3~30 Heterocycloalkyl, 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 6~30 Aryloxy, substituted, or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 4~30 Alkyl heteroaryl, substituted or unsubstituted C 4~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 It may be a heteroaryloxy.

[0031] In equation (A), each R 1 It may optionally further include one or more divalent linking groups as part of its structure. Each of the one or more divalent linking groups may be substituted or unsubstituted. Exemplary divalent linking groups include -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R ’ )-, -C(O)N(R')-, substitution or non-substitution C 1~30 Alkylene, substituted, or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 You can choose from heteroarylenes or combinations thereof, R ’ C is hydrogen, substituted or unsubstituted. 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 It may be a heteroaryl compound.

[0032] In some embodiments, R1 It may further contain polymerizable groups. For example, R 1 This refers to polymerizable groups containing ethylenically unsaturated double bonds, such as substituted or unsubstituted C. 2~20 This may include alkenyls or substituted or unsubstituted norbornyls, preferably (meth)acrylates or C2 alkenyls.

[0033] In some embodiments, one or more R 1 Each of these groups may independently, as part of their structure, further include acid-unstable groups, lactone-containing groups, base-solubilizing groups, or combinations thereof.

[0034] In equation (A), each X is independently either a single bond or a substituted or unsubstituted C. 1~10 Alkylene, substituted, or unsubstituted C 3~10 Cycloalkylene, substituted or unsubstituted C 3~10 Heterocycloalkylene, substituted or unsubstituted C 6~10 Arylene, substituted or unsubstituted C 3~10 Heteroarylene, O, S, S(O), C(O), C(O)O, OC(O), C(O)N(R) 2 ), or NR 2 One or more of the following, R 2 C is hydrogen, deuterium, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, substituted, or unsubstituted C 3~20 Heterocycloalkyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 3~30 Heteroaryl, or Ar a In one or more embodiments, each X is independently O, S, or NR. 2 And R 2 C is hydrogen, deuterium, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, substituted, or unsubstituted C 3~20 Heterocycloalkyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 3~30 Heteroaryl, or Ara That is. R 2 Ar a If so, this is represented by equation (A) Ar a In addition to the base, a second or additional Ar a It should be understood that this represents a base. Typically, each X is independently either O or S.

[0035] In equation (A), n1 is an integer between 1 and 4. Typically, n1 is either 1 or 2.

[0036] In equation (A), each x1 is an independent integer between 0 and 10. For example, each x1 can be independently 0, 1, or 2.

[0037] In equation (A), w1 is an integer between 1 and 4.

[0038] In equation (A), w² is an integer between 0 and 4. Typically, w² is 0.

[0039] In equation (A), * indicates a bonding site to an adjacent atom.

[0040] In equation (A), each Ar a These are independently of equation (B) or (C): [ka] It is the basis of.

[0041] In equations (B) and (C), ring A 2 C 6~30 Aryl or C 3~30 It is a heteroaryl compound. 6~30 Aryl group and C 3~30 The heteroaryl groups are each Ar 1 ~Ar 5 As mentioned above, ring A may be monocyclic or polycyclic. 2Examples of the group include, but are not limited to, benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenylene, chrysene, phenalene, benz[a]anthracene, dibenz[a,h]anthracene, or benzo[a]pyrene, each of which may be substituted or unsubstituted. Typically, ring A 2 It is benzene.

[0042] In equations (B) and (C), L 1 and L 2 Each of these is independently either a single bond, or a substituted or unsubstituted C. 1~10 Alkylene, substituted, or unsubstituted C 3~20 Cycloalkylene, substituted or unsubstituted C 6~30 Arylene group, substituted or unsubstituted C 3~30 A divalent linking group selected from heteroarylenes or combinations thereof. Typically, L 1 and L 2 These are each independent single bonds.

[0043] In equations (B) and (C), each R 3 These are independently non-hydrogen substituents. For example, each R 3 These are independently deuterium, halogen, substituted or unsubstituted C 1~30 Alkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 3~30 Cycloalkenes, substituted or unsubstituted C 3~30 Heterocycloalkyl, 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 6~30 Aryloxy, substituted, or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 4~30 Alkyl heteroaryl, substituted or unsubstituted C 4~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 It may be a heteroaryloxy.

[0044] In equations (B) and (C), each R 3 It may optionally further include one or more divalent linking groups as part of its structure. Each of the one or more divalent linking groups may be substituted or unsubstituted. Exemplary divalent linkers are -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -S(O)2-, -N(R ’ )-, -C(O)N(R')-, substitution or non-substitution C 1~30 Alkylene, substituted, or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 You can choose from heteroarylenes or combinations thereof, R ’ C is hydrogen, substituted or unsubstituted. 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 It may be a heteroaryl compound.

[0045] In some embodiments, R 3 It may further contain polymerizable groups. For example, R 3 This refers to polymerizable groups containing ethylenically unsaturated double bonds, such as substituted or unsubstituted C2~ 20 This may include alkenyls or substituted or unsubstituted norbornyls, preferably (meth)acrylates or C2 alkenyls.

[0046] In some embodiments, one or more R 3 Each of these may independently further include, as part of their structure, lactone-containing groups, hydroxyaryl groups, base-solubilizing groups, or combinations thereof.

[0047] In equations (B) and (C), x² is an independent integer between 0 and 10. For example, each x² can be independently 0, 1, or 2.

[0048] In equation (B), R 4 ~R 6 These are, independently, hydrogen, substituted or unsubstituted C. 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, substituted, or unsubstituted C 3~20 Heterocycloalkyl, substituted, or unsubstituted C 2~20 Alkenyl, substituted, or unsubstituted C 3~20 Cycloalkenyl, substituted or unsubstituted C2-C 20 Alkinyl, substituted, or unsubstituted C 3~20 Heterocycloalkenyl, substituted or unsubstituted C 6~20 Aryl, or substituted or unsubstituted C 3~20 It is a heteroaryl, but R 4 ~R 6 One or fewer of these can be hydrogen, R 4 ~R 6 If one of them is hydrogen, then R 4 ~R 6 At least one of the others is a substitution or non-substitution C 6~20 Aryl or substituted or unsubstituted C 3~20 It is required that it be a heteroaryl compound. Preferably, R 4 ~R 6 These are, independently, substitutional or non-substitutional C. 1~6 Alkyl, substituted, or unsubstituted C 3~10 Cycloalkyl, or substituted or unsubstituted C 6~20 It is aryl. 4 ~R 6 Each of these may optionally further include a divalent linking group as part of their structure.

[0049] For example, R 4 ~R 6 One or more of the following are independent of the formula -CH2C(O)CH (3-n) Y n or -CH2C(O)OCH (3-n) Y n It can be a base, and each Y is independently a substituted or unsubstituted C 3~10It is a heterocycloalkyl group where n is 1 or 2. For example, each Y independently represents the formula -O(C a1 )(C a2 ) Substituted or unsubstituted C containing an O- group 3~10 It can be a heterocycloalkyl, where C a1 and C a2 Each is independently hydrogen or a substituted or unsubstituted alkyl, and C a1 and C a2 They optionally form a ring together.

[0050] In equation (B), R 4 ~R 6 Any two of these may optionally form a ring together, which may further contain a divalent linking group as part of its structure, and this ring may be substituted or unsubstituted.

[0051] In equation (C), R 7 and R 8 These are, independently, hydrogen, substituted or unsubstituted C. 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, substituted, or unsubstituted C 3~20 Heterocycloalkyl, substituted, or unsubstituted C 6~20 Aryl, or substituted or unsubstituted C 3~20 It is a heteroaryl compound. Preferably, R 7 and R 8 These are, independently, hydrogen, substituted or unsubstituted C. 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 3~20 It may be a heterocycloalkyl. 7 and R 8 Each of these may optionally further include a divalent linking group as part of their structure.

[0052] In equation (C), R 9 is a substitution or non-substitution C 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C3~20 It is heterocycloalkyl.

[0053] In equation (C), R 7 ~R 9 Any two of these may optionally form a ring together, which may further contain a divalent linking group as part of its structure, and this ring group may be substituted or unsubstituted.

[0054] In some embodiments, R 4 ~R 9 Each of these may optionally contain, as part of their structure, one or more divalent linking groups selected from -O-, -C(O)-, -C(O)-O-, -S-, -S(O)2-, and N(R')-S(O)2-, where R' is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 3~20 It may be a heterocycloalkyl.

[0055] In equation (B), n² is an integer between 1 and 4. Typically, n² is either 1 or 2.

[0056] In equation (C), n3 is an integer between 1 and 4. Typically, n3 is either 1 or 2.

[0057] In formulas (B) and (C), * indicates a bonding site to an adjacent atom.

[0058] In some embodiments, the acid-unstable group may be a tertiary alkyl ester. For example, the tertiary alkyl ester group is R 4 ~R 6 None of these can be hydrogen atoms, but rather those of formula (B).

[0059] In some embodiments, w2 is 0, and the structure of equation (A) is equation (A'): [ka] It is represented as follows.

[0060] In equation (A'), ring A 1 , R 1 , X, Ar a x1 and n1 are as defined for equation (A), respectively.

[0061] Equation (B) -C(O)OC(R 4 )(R 5 )(R 6 Examples of such examples include, but are not limited to, the following: [ka] [ka] In the formula, *' represents L 1 It is a binding site to R ’ and R ’’ These are, independently, substitutional or non-substitutional C. 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, substituted, or unsubstituted C 3~20 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 3~20 It is a heteroaryl compound.

[0062] Formula (C) contains the expression -C(O)OC(R 7 )(R 8 )-O-(R 9 Examples of such examples include, but are not limited to, the following: [ka] (In the formula, * represents L 2 (Represents the binding site to).

[0063] Non-limiting examples of cations represented by formula (1) include the following: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0064] Non-limiting examples of cations represented by formula (2) include the following: [ka] [ka] [ka] [ka] [ka]

[0065] In some embodiments, the salt may further contain an anion. Any suitable anion can be used. For example, in some embodiments, the salt may further contain an anion selected from halides, hexafluorophosphates, or anionic groups, such as sulfonates, sulfonamides, sulfonimidates, methides, borates, or carboxylates. The anionic group should be understood to include an organic group bonded to the described anionic site. An exemplary organic group may contain one or more heteroatoms. 1~100 or C 1~60 Examples of organic groups include -O-, -S-, -Te-, -Se-, -C(O)-, C(O)O-, and -N(R ’ )-,-C(O)N(R ’ )-, -S(O)-, -S(O)2-, -C(S)-, -C(Te)-, -C(Se)-, substitution or non-substitution C 1~30 Alkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 3~30 Heterocycloalkyl, substituted, or unsubstituted C6~30 Aryl, substituted, or unsubstituted C 3~30 One or more heteroaryls, or combinations thereof, can be listed, each R ’ These are, independently, hydrogen, deuterium, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 It is a heteroaryl compound.

[0066] Examples of anionic groups having a sulfonate group include one or more of the following: [ka]

[0067] Examples of non-sulfonated anionic groups include one or more of the following: [ka]

[0068] Examples of anionic groups having a carboxylate group include one or more of the following: [ka]

[0069] In some embodiments, the anionic group may further comprise a polymerizable group. Examples of polymerizable groups include, but are not limited to, vinyl and (meth)acrylic.

[0070] In some embodiments, the salt is polymeric. For example, the salt may be a polymer derived by polymerizing the polymerizable groups contained in the anionic groups of the salt.

[0071] The salts of this disclosure can be prepared by methods known in the art and by methods illustrated in the examples disclosed further in detail later.

[0072] Photoresist compositions comprising the salts and solvents described herein are also provided. Furthermore, the salts of this disclosure can be prepared by those skilled in the art using (but not limited to) standard organic chemical transformation reactions such as acyl and alkyl substitution reactions, metal-catalyzed cross-coupling reactions, aromatic nucleophilic substitution reactions, Diels-Alder reactions, addition reactions, and radical reactions.

[0073] 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, iso-propanol, tert-butanol, 2-methyl-2-butanol, 4-methyl-2-pentanol and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone) (DAA); propylene glycol monomethyl ether (PGME); ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane and anisole; acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, These include ketones such as cyclohexanone (CHO); esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), hydroxyisobutyrate methyl ester (HBM), and acetate acetate; lactones such as gamma-butyrolactone (GBL) and epsilon-caprolactone; lactams such as N-methylpyrrolidone; nitriles such as acetonitrile and propionitrile; cyclic or acyclic carbonate esters such as propylene carbonate, dimethyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, and propylene carbonate; polar aprotic solvents such as dimethyl sulfoxide and dimethylformamide; water; and combinations thereof. Of these, preferred solvents are PGME, PGMEA, EL, GBL, HBM, CHO, DAA, and combinations thereof.

[0074] The total solvent content in a photoresist composition (i.e., the cumulative solvent content for all solvents) is typically 40–99% by weight, for example, 60–99% by weight or 85–99% by weight, based on the total solids content of the photoresist composition. The desired solvent content will depend, for example, on the desired thickness of the photoresist layer to be coated and the coating conditions.

[0075] In the photoresist composition of the present invention, the salt is typically present in the photoresist composition in an amount of 50 to 99.9% by weight, typically 50 to 99% by weight, and more typically 50 to 95% by weight, based on the total solids content of the photoresist composition. In yet another embodiment, the salt may be present in the photoresist composition in an amount of 80 to 99.9% by weight, or 85 to 99% by weight, or 90 to 99% by weight, based on the total solids content of the photoresist composition. It will be understood that the total solids content includes the salt and other non-solvent components.

[0076] In some embodiments, the photoresist composition may not contain a polymer containing an acid-unstable group. In other embodiments, the photoresist composition may or may not contain a polymer containing one or more of the following: a base-soluble or base-solubilizing group such as a hydroxyaryl group, a lactone-containing group, a sultone-containing group, a polar group, a crosslinking group, or a combination thereof.

[0077] The photoresist composition may further contain additional photoacid generators different from the salts of formulas (1) and (2). The additional PAG may be in ionic or nonionic form. The additional PAG may be in polymer or nonpolymer form. In polymer form, the additional PAG may exist as a moiety in repeating units of a polymer derived from polymerizable PAG monomers.

[0078] A suitable additional PAG compound is formula G + A - (In the formula, G + A is a photoactive cation, -The photoactive cation may be an anion capable of generating a photoacid. The photoactive cation is preferably selected from onium cations, preferably iodonium or sulfonium cations. Particularly suitable anions include those whose conjugate acid has a pKa of -15 to 5, or -15 to 0, or -14 to 0, or -13 to 0. The anions are typically organic anions having a sulfonate group or a non-sulfonate type group, such as carboxylates, sulfonamides, sulfonimidates, methides, arsenates, or borates.

[0079] Examples of onium salts include 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. Other useful additional PAG compounds are known in the field of chemically amplified photoresists and include, for example, nonionic sulfonyl compounds, e.g., 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonic acid esters, e.g., 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene and 1,2,3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives, e.g., bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl) Examples include honyl)diazomethane; glyoxime derivatives, such as bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime and bis-O-(n-butanesulfonyl)-α-dimethylglyoxime; sulfonic acid ester derivatives of N-hydroxyimide compounds, such as N-hydroxysuccinidomethanesulfonic acid and N-hydroxysuccinidomitetrifluoromethanesulfonic acid; 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. Additional suitable PAGs are further described in (Patent Document 1) and (Patent Document 2).

[0080] Typically, when a photoresist composition contains additional PAGs, the additional PAGs are present in the photoresist composition in an amount of 0.1 to 55% by weight, more typically 1 to 25% by weight, based on the total solids content of the photoresist composition. When used in polymer form, the additional PAGs are typically present in the polymer in an amount of 1 to 25 mol%, typically 1 to 8 mol%, or 2 to 6 mol%, based on the total repeating units in the polymer.

[0081] In some embodiments, the photoresist composition may further include a substance containing one or more base-unstable groups ("base-unstable substance"). As referred to herein, a base-unstable group is a functional group that can undergo a cleavage reaction in the presence of an aqueous alkaline developer after the exposure step and the post-exposure baking step to provide polar groups such as hydroxyl, carboxylic acid, sulfonic acid, etc. The base-unstable group will not react significantly (e.g., not undergo a bond cleavage reaction) before the development step of the photoresist composition containing the base-unstable group. Therefore, for example, the base-unstable group will be substantially inert during the pre-exposure soft bake step, the exposure step, and the post-exposure bake step. "Substantially inert" means that 5% or less, typically 1% or less of the base-unstable group (or site) decomposes, cleaves, or reacts during the pre-exposure soft bake, exposure, and post-exposure bake steps. The base-unstable group reacts under typical photoresist development conditions using an aqueous alkaline photoresist developer, such as an aqueous solution of 0.26 N (N) tetramethylammonium hydroxide (TMAH). For example, a 0.26N aqueous solution of TMAH can be used for single-paddle development or dynamic development, and the 0.26N TMAH developer is distributed to the imaged photoresist layer for an appropriate time, such as 10 to 120 seconds (s). Exemplary base-unstable groups are ester groups, typically fluorinated ester groups. When coated onto a substrate, base-unstable substances may separate from other solid components of the photoresist composition and appear on the upper surface of the formed photoresist layer.

[0082] In some embodiments, the base-unstable material may be a polymeric material, also referred to herein as a base-unstable polymer, and the base-unstable polymer may comprise one or more repeating units containing one or more base-unstable groups. For example, the base-unstable polymer may comprise repeating units containing two or more identical or different base-unstable groups. A preferred base-unstable polymer comprises at least one repeating unit containing two or more base-unstable groups, for example, a repeating unit containing two or three base-unstable groups.

[0083] Base-unstable polymers can be prepared using any suitable method in the art, including those described herein for the first and second polymers. For example, base-unstable polymers can be obtained by polymerization of each monomer under any suitable conditions, such as heating at an effective temperature, irradiation with chemical rays at an effective wavelength, or a combination thereof. In addition or alternatively, one or more base-unstable groups can be grafted onto the polymer backbone using a suitable method.

[0084] In some embodiments, the base-unstable substance is a single molecule comprising one or more base-unstable ester groups, preferably one or more fluorinated ester groups. The base-unstable substance, being a single molecule, typically has a molecular weight in the range of 50 to 1,500 Da. W It has.

[0085] If present, the base-unstable substance is typically present in the photoresist composition in an amount of 0.01 to 10% by weight or 2 to 7% by weight, typically 1 to 5% by weight, based on the total solids content of the photoresist composition.

[0086] The photoresist composition may further contain one or more additional, optional additives. For example, optional additives may include actinic dyes and contrast agents, anti-striation agents, plasticizers, speed accelerators, sensitizers, photodegradable deactivators (PDQs, also known as photodegradable bases), basic deactivators, thermal acid generators, surfactants, etc., or combinations thereof. When present, the optional additives are typically present in the photoresist composition in an amount of 0.01 to 10% by weight, based on the total solids of the photoresist composition.

[0087] PDQ generates a weak acid upon irradiation. The acid generated from the photodegradable deactivator is not strong enough to react rapidly with the acid-labile groups present in the resist matrix. Exemplary photodegradable deactivators include, for example, photodegradable cations, preferably, for example, C 1~20 carboxylic acids or C 1~20 useful also for preparing strong acid generator compounds paired with anions of weak acids (pKa > -2), 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, etc. Exemplary sulfonic acids include p-toluenesulfonic acid, camphorsulfonic acid, etc. In a preferred embodiment, the photodegradable deactivator is a photodegradable organic zwitterionic compound such as diphenyliodonium-2-carboxylate.

[0088] The photodegradable deactivator may be in non-polymeric form or in polymer-bound form. In the case of polymer form, the photodegradable deactivator is present in the polymerization units on the first polymer or the second polymer. The polymerization units containing the photodegradable deactivator 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 repeating units of the polymer.

[0089] Exemplary PDQs include, but are not limited to, the following compounds and their derivatives:

Chemical formula

[0090] Exemplary basic deactivators include, for example, linear aliphatic amines such as tributylamine, trioctylamine, triisopropanolamine, 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; cyclic aliphatic amines such as 1-(tert-butoxycarbonyl)-4-hydroxypiperidine, tert-butyl 1-pyrrolidinecarboxylate, tert-butyl 2-ethyl-1H-imidazole-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)pivalamide, N,N-diethylacetamide, N 1 ,N 1 ,N 3 ,N 3 ,N-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; diazines such as optionally substituted pyrazine, piperazine and phenazine; diazoles such as optionally substituted pyrazole, thiadiazole and imidazole; and optionally substituted pyrrolidones such as 2-pyrrolidone and cyclohexylpyrrolidone.

[0091] The basic deactivator may be in a non-polymeric form or a polymer-bound form. If in a polymeric form, the deactivator may be present within the repeating units of the polymer. Repeating units containing the 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%, relative to the total repeating units of the polymer.

[0092] Exemplary surfactants include fluorinated and non-fluorinated surfactants, which may be ionic or nonionic, with nonionic surfactants being preferred. Exemplary fluorinated nonionic 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 containing fluorine-containing repeating units.

[0093] This invention describes a pattern formation method using the photoresist composition of the present invention. Suitable substrates to which the photoresist composition can be coated include electronic device substrates. Various electronic device substrates, such as semiconductor wafers, polycrystalline silicon substrates, packaging substrates such as multi-chip modules, flat panel display substrates, and substrates for light-emitting diodes (LEDs) such as organic light-emitting diodes (OLEDs), can be used in the present invention, 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 may 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 may be of any suitable size. Typical wafer substrate diameters are 200 to 300 millimeters (mm), but wafers with smaller and larger diameters can be preferably used. The substrate may include one or more layers or structures that optionally contain the effective or operable portion of the device to be formed.

[0094] Typically, one or more lithography layers, such as hard mask layers (e.g., spin-on carbon (SOC), amorphous carbon, or metallic hard mask layers), CVD layers (e.g., silicon nitride (SiN), silicon oxide (SiO), or silicon oxynitride (SiON) layers), organic or inorganic underlayers, or combinations thereof, are provided on the upper surface of the substrate before coating the photoresist composition. Such layers, together with the overcoated photoresist layer, form a lithography material stack.

[0095] Optionally, a layer of adhesion promoter may be applied to the substrate surface before 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 such as trimethoxyvinylsilane, triethoxyvinylsilane, and hexamethyldisilazane, or aminosilane coupling agents such as gamma-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those sold under the names AP®3000, AP®8000, and AP®9000S, available from DuPont Electronic Materials International (Marlborough, Massachusetts).

[0096] The photoresist composition can be coated onto a substrate by any preferred method, such as spin coating, spray coating, dip coating, doctor blading, etc. For example, the application of a photoresist layer can be achieved by spin coating the photoresist in a solvent using a coating track, in which case the photoresist is distributed onto a rotating wafer. During distribution, the wafer is rotated for 15 to 120 seconds at a speed typically of 4,000 revolutions per minute (rpm) or less, for example, 200 to 3,000 rpm, for example, 1,000 to 2,500 rpm, to obtain a layer of the photoresist composition on the substrate. It will be well understood by those skilled in the art that the thickness of the coated layer can be adjusted by changing the spin speed and / or the total solid content of the composition. The photoresist composition layer formed from the composition of the present invention typically has a dry layer thickness of 1 nanometer (nm) to 120 micrometers (μm), preferably more than 5 nm to 110 μm, more preferably 6 to 100 μm. In some embodiments, the photoresist composition layer formed from the composition may have a dry layer thickness of 10 nm to 25 μm, or 3 to 20 μm.

[0097] Photoresist compositions are typically then soft-baked to minimize the solvent content in the layer, thereby forming a non-stick coating and improving the adhesion of the layer to the substrate. Soft baking is performed, for example, on a hot plate or in an oven, with a hot plate being typical. The soft-bake temperature and time will depend, for example, on the photoresist composition and thickness. Soft-bake temperatures are typically 80–170°C, more typically 90–150°C. Soft-bake times are typically 10 seconds–20 minutes, more typically 1 minute–10 minutes, and even more typically 1 minute–2 minutes. The heating time can be easily determined by those skilled in the art based on the composition's components.

[0098] The photoresist layer is then pattern-exposed to activating radiation to create a difference in solubility between exposed and unexposed areas. References herein to exposure of a photoresist composition to activating radiation indicate that the radiation can form a latent image in the photoresist composition. Exposure is typically performed through a patterned photomask having optically transparent and optically opaque regions, corresponding to the exposed and unexposed areas of the resist layer, respectively. Such exposure may instead be performed without a photomask using direct drawing methods, typically used for e-beam lithography. Activating radiation typically has wavelengths less than 400 nm, less than 300 nm, or less than 200 nm, with 248 nm (KrF), 193 nm (ArF), 13.5 nm (EUV) wavelengths, or electron beam lithography being preferred. This method is utilized in immersion or dry (non-immersion) lithography techniques. Exposure energy depends on the exposure tool and the components of the photoresist composition, typically ranging from 1 to 200 millijoules (mJ / cm²) per square centimeter. 2 ), preferably 10 to 100 mJ / cm² 2 More preferably 20-50 mJ / cm² 2 That is the case.

[0099] After exposure of the photoresist layer, post-exposure baking (PEB) of the exposed photoresist layer may be performed. PEB can be performed, for example, on a hot plate or in an oven, with a hot plate being typical. The conditions for PEB will depend, for example, on the photoresist composition and layer thickness. PEB is typically performed at a temperature of 70-150°C, preferably 75-120°C, for a time of 30-120 seconds. A latent image is formed in the photoresist, defined by polarity switching regions (exposed regions) and non-switching regions (unexposed regions).

[0100] The exposed photoresist layer is then developed with a developer suitable for selectively removing the soluble regions of the layer, while the remaining insoluble regions form the resulting photoresist pattern relief image. In a positive development (PTD) process, the exposed regions of the photoresist layer are removed during development, leaving the unexposed regions. Conversely, in a negative development (NTD) process, the exposed regions of the photoresist layer remain, and the unexposed regions are removed during development. The application of the developer can be achieved by any preferred method as described above for applying the photoresist composition, with spin coating being a typical example. The development time is an effective time for removing the soluble regions of the photoresist, typically 5 to 60 seconds. Development is typically carried out at room temperature.

[0101] Suitable developers for the PTD process include aqueous base developers, such as tetramethylammonium hydroxide (TMAH), preferably 0.26 N (N) TMAH, quaternary ammonium hydroxide solutions such as tetraethylammonium hydroxide and tetrabutylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. Suitable developers for the NTD process are organic solvent systems, meaning 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.

[0102] A coated substrate may be formed from the photoresist composition of the present invention. Such a coated substrate comprises (a) a substrate having one or more layers patterned on its surface; and (b) a layer of the photoresist composition on one or more patterned layers.

[0103] A photoresist pattern can be used, for example, as an etching mask, thereby enabling the transfer of the pattern to one or more consecutive underlying layers by known etching techniques, typically by dry etching such as reactive ion etching. A photoresist pattern can be used, for example, for pattern transfer to an underlying hard mask layer, and it can subsequently be 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 during pattern transfer, it can be removed from the substrate by 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.

[0104] The present invention is further illustrated by the following non-limiting embodiments. [Examples]

[0105] All reactions were carried out under ambient conditions. All chemicals were used directly from suppliers. Nuclear magnetic resonance (NMR) spectra of all compounds were obtained using a 500 MHz spectrometer unless otherwise specified. Chemical shifts are reported as δ (parts per million, ppm) values ​​relative to the internal heavy chloroform residual signal. Multiplicity is indicated by s (singlet), d (doublet), t (triplet), m (multiplet), dd (doublet of doublets), dt (doublet of triplets), tt (triplet of triplets), and br (broad singlet).

[0106] Synthesis Examples Synthesis of compound Ci [ka] Hydroxyisophthalic acid (30.0 grams (g), 165 millimoles (mmol)) was dissolved in N,N-dimethylformamide (330 milliliters (mL)) to form a solution. Carbonyl diimidazole (57.8 g, 356 mmol) was added little by little to the solution to form a reaction mixture. The reaction mixture was heated at 40 °C for 2 hours. Then, 1,8-diazabicyclo(5.4.0)undec-7-ene (54.2 g, 356 mmol) was added to the reaction mixture, followed by the addition of 1-ethylcyclopentanol (56.4 g, 712 mmol). The resulting reaction mixture was heated at 55 °C for 48 hours. Then, the reaction mixture was cooled to room temperature, and water (700 mL) was added thereto. The solution was adjusted to pH 8 with glacial acetic acid and then extracted with heptane (700 mL). The organic layer was separated and then washed with water (3 × 700 mL) and saturated aqueous sodium hydrogen carbonate solution (700 mL). Thereafter, the organic layer was separated, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The obtained oil was dried under vacuum to obtain 55.4 g of a viscous transparent oil. Compound C-i is a mixture of about 74.1% by weight with 1-ethylcyclopentanol (yield 67%). 1 H NMR (500 MHz, acetone-d6) δ 9.06 (br, 1H), 8.08 (s, 1H), 7.65 (s, 2H), 2.30 (m, 4H), 2.14 (q, 4H), 1.83 - 1.48 (m, 12H), 0.92 (t, 6H).

[0107] Synthesis of Compound C-iii

Chemical Structure

[0108] Synthesis of Example 1 (C-1) [ka] Compound C-iii (5.01 g, 3.63 mmol) in dichloromethane was diluted with dichloromethane (20 mL) to form a solution. Then, compound C-iv (3.32 g, 5.36 mmol) was added to the solution, followed by the addition of water (50 mL) to form a reaction mixture. The reaction mixture was stirred for 1 hour. The layers were separated, and the organic layer was washed with water (3 × 50 mL). The organic layer was then dried on filter paper and concentrated under reduced pressure. Heptane (200 mL) was added to the resulting residue, and the mixture was heated at 80°C for 1 hour. The mixture was allowed to cool to approximately 45°C, and the mixture was decanted to leave an oily substance. This residue was dissolved in acetone (20 mL), to which heptane (200 mL) was added, and the resulting mixture was then heated at 80°C for 30 minutes. The solution was then decanted. The heptane / acetone precipitation step was then repeated three more times. The obtained substance was vacuum-dried to yield 4.00 g of pure compound C-1 (yield 56%). 1 H NMR(500MHz,acetone-d6)δ 11.55(brs,1H),8.43(t,3H),8.30(d,1H),8.24(d,1H),8.04(d,6H),7.92(d,6H),7.48(d,6 H),4.72(t,2H),2.92(m,2H),2.28(m,12H),2.14(q,12H),1.83-1.68(m,36H),0.92(t,18H).

[0109] Synthesis of Example 2 (C-2) [ka] Diiodosalicylic acid (2.12 g, 5.44 mmol) was dissolved in a solution of lithium hydroxide (0.122 g, 5.08 mmol) in water (50 mL) to form a reaction mixture. Compound C-iii (5.01 g, 3.63 mmol) was dissolved in dichloromethane (50 mL) and mixed with the reaction mixture. The resulting mixture was stirred for 1 hour. The layers were separated, and the organic layer was washed with saturated sodium bicarbonate solution (50 mL) and water (3 × 50 mL). The organic layer was then concentrated under reduced pressure. Heptane (300 mL) was added to the resulting residue, and the resulting mixture was heated at 80°C for 1 hour. A solid was formed, which was filtered while the solution was still hot. The solid was dissolved again in acetone (80 mL), and heptane (500 mL) was added. The solution was concentrated under reduced pressure until a solid precipitated, and then the solution was heated at 80°C for 1 hour. The solid was filtered while the solution was still hot, and then the solid was rinsed with heptane. The product was dried on filter paper to obtain 2.52 g of compound C-2 as a white solid (39%). 1 H NMR(500MHz,acetone-d6)δ 8.43(t,3H),8.06(d,1H),8.03(d,6H),7.92(d,6H),7.81(d,1H),7.48 (d,6H),2.28(m,12H),2.14(q,12H),1.84-1.67(m,36H),0.92(t,18H).

[0110] Synthesis of Example 3 (C-3) [ka] Compound C-iii (5.01 g, 3.63 mmol) in dichloromethane was diluted with dichloromethane (50 mL). Compound Cv (4.64 g, 10.9 mmol) was added, followed by water (50 mL). The reaction was stirred for 30 minutes. The layers were separated, and the organic layer was washed with water (50 mL x 5). The organic layer was dried on filter paper and concentrated under reduced pressure. The residue was dissolved in acetone and precipitated using heptane. The solid precipitate was isolated by decantation of the solvent and vacuum-dried to obtain 3.0 g of compound C-3 as a white solid (46%). 1H NMR(500MHz,acetone-d6)δ 8.43(t,3H),8.03(d,6H),7.92(d,6H),7.47(d,6H),4.32(t,2H),2.70(m,2H),2.35-2.10(m,26H),1.89-1.62(m,46H),0.92(t,18H).

[0111] Synthesis of compound C-vi [ka] In a three-necked flask equipped with a condenser, thermocouple, and stirrer, compound 4-hydroxybenzoate tert-butyl (19.6 g, 101 mmol) and compound Ci (8.00 g, 20.1 mmol) were dissolved in N,N-dimethylformamide (250 mL). Cesium carbonate (32.8 g, 101 mmol) was added, and the reaction mixture was heated at 55°C for 2 hours. After the reaction mixture was allowed to cool to room temperature, it was partitioned into dichloromethane (350 mL) and water (350 mL). The organic layer was washed with water (3 × 300 mL) and dried over sodium sulfate. The solution was filtered and concentrated under reduced pressure. The residue was recrystallized with a mixture of dichloromethane and methyl tert-butyl ether to obtain 13.8 g of C-vi as a white solid (yield 75%). 1 H NMR (500MHz, acetone-d6) δ 8.09(d,6H),8.05(d,6H),7.80(d,2H),7.42(d,6H),7.25(d,6H),6.92(d,2H),1.58(s,27H),1.54(s,9H).

[0112] Synthesis of Example 4 (C-4) [ka] Compound C-vi (13.8 g, 13.3 mmol) and compound C-iv (8.28 g, 13.3 mmol) were partitioned into dichloromethane (100 mL) and water (100 mL) and stirred for 1 hour. The layers were separated, and the organic layer was washed with water (3 × 100 mL). The organic layer was dried on filter paper and concentrated under reduced pressure. The residue was dissolved in tert-butyl methyl ether (100 mL), and heptane (600 mL) was added while stirring vigorously. The precipitated oil was isolated by decantation of the heptane layer. The residue was again dissolved in acetone (100 mL), and heptane (600 mL) was added while stirring vigorously. The formed oil was isolated by decantation of the supernatant. The residue was again dissolved in MTBE (150 mL), and residual salts were removed by washing with water (3 × 100 mL). The organic layer was dried on filter paper and concentrated under reduced pressure. The residue was dissolved in acetone (100 mL), and heptane (600 mL) was added. The precipitated oil was isolated by decantation of the liquid and rinsed with heptane. The product was vacuum-dried to obtain 14.0 g of compound C-4 as a white solid (yield 69%). 1 H NMR(500MHz,DMSO-d6)δ 11.16(s,1H),8.30(s,1H),8.10-7.94(m,7H),7.87(d,6H),7.41(d,6H),7.26(d,6H),4.56(t,2H),2.77(m,2H),1.55(s,27H).

[0113] Synthesis of compound C-ix [ka] Compound Ci (4.07 g, 10.2 mmol) and compound C-viii (15.0 g, 35.8 mmol) were dissolved in N,N-dimethylformamide (100 mL). Cesium carbonate (10.0 g, 30.7 mmol) was added, and the reaction was heated at 45°C for 16 hours. The reaction was cooled to room temperature and poured into saturated sodium iodide aqueous solution (200 mL). The precipitated solid was filtered and thoroughly rinsed with water. The solid was dissolved again in dichloromethane (200 mL) and washed with saturated sodium iodide solution (3 × 200 mL) and water (3 × 200 mL). The organic layer was dried on filter paper and concentrated under reduced pressure. The resulting residue was triturated with tert-butyl methyl ether (MTBE) (200 mL), and the solvent was discarded. The residue was dissolved in acetone (100 mL) and precipitated from tert-butyl methyl ether (600 mL). The formed solid was isolated by decantation of the solvent. This precipitation procedure was repeated, and the resulting solid was vacuum-dried to obtain 11.3 g of compound C-ix as a white solid (67%). 1 H NMR (500MHz, acetone-d6) δ 8.52(t,3H),8.07(d,6H),7.95(d,6H),7.54-7.45(m,12H),7.42(d,6H),7.34(t,12H),7.26(d,6H),1.92(s,36H).

[0114] Synthesis of Example 5 (C-5) [ka] Compound C-ix (11.3 g, 6.89 mmol) and compound C-iv (4.27 g, 6.89 mmol) were partitioned into dichloromethane (100 mL) and water (100 mL). The reaction mixture was then stirred at room temperature for 30 minutes. The layers were separated, and the organic layer was washed with water (3 × 100 mL). The organic layer was dried on filter paper and concentrated under reduced pressure. The resulting residue was dissolved in a mixture of acetone (20 mL) and tert-butyl methyl ether (100 mL), and the product was precipitated using heptane (700 mL). The precipitated solid was isolated by decantation of the supernatant and dried under vacuum to obtain 9.5 g of compound P-5 as a white solid (66%). 1 H NMR(500MHz,acetone-d6)δ 11.52(s,1H),8.52(s,3H),8.27(d,1H),8.21(d,1H),7.99(d,6H),7.94(s,6H),7.48(d ,12H),7.43(d,6H),7.34(t,12H),7.26(t,6H),4.69(t,2H),2.90(m,2H),1.92(s,36H).

[0115] Synthesis of C-xi [ka] Compound Ci (8.96 g, 22.6 mmol) and compound Cx (31.4 g, 69.1 mmol) were dissolved in DMF (220 mL). Cesium carbonate (22.1 g, 67.9 mmol) was added, and the reaction was heated at 45°C for 32 hours. The reaction was cooled to room temperature and poured into saturated sodium chloride aqueous solution (1200 mL). The solid precipitate was filtered, thoroughly rinsed with saturated brine, and then rinsed with water. The solid was dissolved again in DCM (200 mL) and passed through filter paper. The solution was concentrated under reduced pressure. The resulting residue was recrystallized in an acetone / heptane / MTBE mixture and vacuum dried to obtain 28.5 g of C-xi (60%). 1 H NMR(500MHz,DMSO-d6)δ 8.32(t,3H),7.95-7.73(m,12H),7.45(m,12H),7.38(d,6H),7.13(t,12H),1.82(s,37H). 19F NMR(470MHz,DMSO-d6)δ -118.19(m)

[0116] Synthesis of C-xii [ka] Compound Ci (3.96 g, 9.96 mmol) and compound Cx (35.0 g, 77.0 mmol) were dissolved in DMF (230 mL). Cesium carbonate (22.8 g, 70.0 mmol) was added, and the reaction was heated at 45°C for 32 hours. The reaction was cooled to room temperature and poured into a saturated aqueous solution of sodium iodide (700 mL). The solid precipitate was filtered and thoroughly rinsed with water. The solid was dissolved again in DCM (400 mL) and passed through filter paper. The solution was concentrated under reduced pressure. The resulting residue was dissolved in acetone (120 mL) and added to a mixture of MTBE (600 mL) and heptane (600 mL) being vigorously stirred. The precipitated solid was filtered and vacuum-dried to obtain 35.7 g of C-xii (88%). 1 H NMR(500MHz,DMSO-d6)δ 8.32(t,3H),7.95-7.73(m,12H),7.45(m,12H),7.38(d,6H),7.13(t,12H),1.82(s,37H). 19 F NMR(470MHz,DMSO-d6)δ -118.19(m)

[0117] Synthesis of compound C-6 [ka] Compound C-xi (5.00 g, 3.02 mmol) and compound C-iv (1.91 g, 3.08 mmol) were partitioned into dichloromethane (50 mL) and water (50 mL). The layers were separated, and the organic layer was washed with water (100 mL x 5). The organic layer was passed through filter paper, and the solution was concentrated under reduced pressure. The residue was precipitated from a mixture of acetone and heptane. The resulting solid was filtered and vacuum-dried to obtain 5.68 g of compound C-6 (85%). 1H NMR(500MHz,DMSO-d6)δ 11.14(s,1H),8.34(q,3H),8.27(d,1H),8.01(d,1H),7.94-7.77(m,12H),7.54- 7.35(m,18H),7.22-7.04(m,12H),4.55(t,2H),2.89-2.65(m,2H),1.83(s,36H). 19 F NMR(470MHz,DMSO-d6)δ -113.51(m,2F),-118.15(m,6F),-120.76(m,2F).

[0118] Synthesis of compound C-7 [ka] Compound C-xii (8.00 g, 5.58 mmol) and 3,5-diiodosalicylic acid (2.68 g, 6.87 mmol) were partitioned into DCM (70 mL) and saturated sodium bicarbonate aqueous solution (70 mL). The reaction was stirred for 1 hour. The layers were separated, and the organic layer was washed with saturated sodium bicarbonate aqueous solution (70 mL x 2) and water (70 mL x 4). The organic layer was passed through filter paper and concentrated under reduced pressure. The residue was purified by precipitation from an acetone / heptane / MTBE mixture and vacuum-dried to obtain 5.94 g of compound C-7 (65%). 1 H NMR(500MHz,DMSO-d6)δ 8.33(t,3H),7.93-7.74(m,14H),7.53-7.31(m,18H),7.12(t,12H),1.82(s,37H).

[0119] C-XIV synthesis [ka] Compound Ci (7.65 g, 19.3 mmol) and compound C-xiii (40.0 g, 59.7 mmol) were dissolved in DMF (160 mL). Cesium carbonate (18.8 g, 57.8 mmol) was added, and the reaction was heated at 45°C for 48 hours. The reaction was then cooled to room temperature and poured into saturated sodium chloride aqueous solution (800 mL). The precipitated solid was filtered, thoroughly rinsed with saturated saline solution, and then rinsed with water. The solid was dissolved again in ethyl acetate (500 mL) and passed through filter paper. The solution was precipitated with MTBE, filtered, and vacuum dried to obtain 32.4 g of compound C-xiv (77%). 1 H NMR(500MHz,DMSO-d6)δ 8.33(t,3H),7.96-7.78(m,12H),7.78-7.61(m,13H),7.45-7.33(m,6H),7.27-7.12(m,13H),1.80(s,38H).

[0120] Synthesis of compound C-8 [ka] Compound C-xiv (10.0 g, 4.34 mmol) and compound C-iv (2.75 g, 4.43 mmol) were partitioned into water (100 mL) and dichloromethane (100 mL). The mixture was then vigorously stirred for 16 hours. The layers were separated, and the organic layer was washed with water (100 mL x 5). The organic layer was passed through filter paper and concentrated under reduced pressure. The residue was precipitated from a mixture of acetone, MTBE, and heptane. The resulting solid was filtered and vacuum-dried to obtain 8.06 g of compound C-8 (65%). 1 H NMR(500MHz,DMSO-d6)δ 11.15(s,1H),8.33(t,3H),8.26(d,1H),8.00(d,1H),7.92-7.80(m,12H),7.6 7(d,12H),7.39(d,6H),7.22(d,12H),4.55(s,2H),2.75(s,2H),1.80(s,37H).

[0121] Synthesis of compound C-9 [ka] Compound C-xiv (10.0 g, 4.34 mmol) and 3,5-diiodosalicylic acid (2.03 g, 5.21 mmol) were partitioned into DCM (100 mL) and saturated sodium bicarbonate aqueous solution (100 mL). The reaction was stirred for 1 hour. The layers were separated, and the organic layer was washed with saturated sodium bicarbonate aqueous solution (100 mL x 2) and water (100 mL x 5). The organic layer was passed through filter paper and concentrated under reduced pressure. The residue was purified by precipitation from an acetone / MTBE mixture and vacuum-dried to obtain 7.40 g of compound P-9 (64%). 1 H NMR(500MHz,DMSO-d6)δ 8.33(t,3H),7.97-7.76(m,14H),7.67(d,12H),7.39(d,6H),7.22(d,12H),1.80(s,36H).

[0122] Photoresist composition and evaluation The photoresist compositions were prepared by dissolving the solid components in a solvent using the materials and quantities shown in Table 1. The quantities are expressed as weight percent based on 100% of the total weight of the solids. The total solid content of the photoresist composition was 2.2% by weight. The solvent system contained propylene glycol monomethyl ether acetate (PGMEA) (50% by weight) and methyl 2-hydroxyisobutyrate (HBM) (50% by weight). Each mixture was shaken using a mechanical shaker and then filtered through a PTFE disc filter with a pore size of 0.2 microns.

[0123] Photolithography was performed using the CLEAN TRACK ACT8 (TEL, Tokyo Electron Co.) wafer track. A 200 nm wafer for photolithography testing was coated with AR®3 BARC (DuPont Electronics & Industrial) and soft-baked at 205°C for 60 seconds to obtain a 60 nm film. Next, a photoresist composition was coated onto the AR®3 BARC stack and soft-baked at 110°C for 60 seconds to obtain a photoresist film layer with a thickness of approximately 60 nm.

[0124] Using a mask with selected features, the wafer was exposed to 248 nm radiation with a Canon FPA-5000 ES4 scanner (NA=0.8, outer sigma=0.85, inner sigma=0.57). After exposure, the wafer was baked at 90°C for 60 seconds, developed with MF(trademark) CD26 TMAH developer (DuPont Electronics & Industrial) for 60 seconds, rinsed with DI water, and dried. The limiting dimension (CD) linewidth of the formed pattern was measured using a Hitachi S-9380 CD-SEM. The LWR value was determined by top-down SEM. Sizing energy (E) size The line width roughness (LWR) and line width roughness were determined based on CD measurements. The pseudo-Z factor is reported below. This was determined according to Equation 1: Pseudo Z-factor = (E size ×LWR 2 ) / 100 formula 1 (In the formula, E size This is millijoules per square centimeter (mJ / cm²). 2 The values ​​are reported in units of ) and LWR is reported in nanometers (nm), and the pseudo-Z factor is mJ × 10⁻⁶. -11 (Reported in units of 100). The pseudo-Z factor (Z'-factor) is a modified measure of photoresist performance based on the Z factor, which is an indicator of known parameters of RLS (Resolution, Line Edge Roughness, Sensitivity) photoresist performance (see, for example, Non-Patent Literature 1). The pseudo-Z factor was calculated at a constant resolution (CD size of 180 nm).

[0125] [Table 1]

[0126] [ka] Polymer P-1 is a copolymer derived from monomers M1 and M2 (50.3 / 49.7 mol / mol), and this polymer has a molecular weight of 4.9 kDa. w It has.

[0127] Photoresist compositions PR-2 to PR-7, which contain PAG components C-1 to C-5 having acid-unstable groups and do not contain polymer components, have lower LWR and pseudo-Z factor compared to PR-1, which contains a polymer with acid-unstable groups and PAG components.

[0128] EUV evaluation The photoresist compositions were prepared by dissolving the solid components in a solvent using the materials and quantities shown in Table 2. The quantities are expressed as weight percent based on 100% of the total weight of the solids. The total solid content of the photoresist composition was 2.2% by weight. The solvent system contained PGMEA (50% by weight) and propylene glycol monomethyl ether (PGME) (50% by weight). Each mixture was shaken using a mechanical shaker and then filtered through a PTFE disc filter with a pore size of 0.2 microns.

[0129] EUV exposure was performed on a 300 mm wafer, and photoresist compositions PR1 and PR8 were spin-coated onto a stack of 60 nm organic BARC and 20 nm SiARC to achieve a film thickness of 45 nm. This was followed by coating at 110°C for 60 seconds and baking. EUV exposure was performed using an ASML NXE3400B (NA=0.33) scanner with a hole pattern mask having a 45 nm pitch and a 24 nm hole CD. The exposed wafer was exposed at 100°C for 60 seconds and baked, developed in 0.26 N TMAH solution for 60 seconds, rinsed with DI water, and spin-dried to form the hole pattern. Hole CD measurement was performed using a Hitachi CG5000CD-SEM. Exposure amount vs. size (E size The exposure margin was determined from the exposure amount versus CD exposure margin plot. This is the exposure amount that provides a hole pattern of size 24 nm, and is in millijoules (mJ / cm²) per square centimeter. 2The report is in units of ). The local limiting dimensional uniformity (LCDU) of a single image was calculated as the standard deviation (σ) of the Hall CD measurement multiplied by 3. The reported LCDU was the average of the 3σ values ​​for 20 distinct images at different locations on the wafer. The pseudo-Z factor is reported in Table 2 below. This was determined according to Equation 2. The results are reported in Table 2. Pseudo Z-factor = (E size ×LCDU 2 ) / 100 formula 2

[0130] [Table 2]

[0131] Photoresist composition PR-8, which contains PAG components C-6 and C-7 having acid-unstable groups and does not contain polymer components, had a faster photospeed and a lower pseudo-Z factor compared to PR-1, which contains a polymer with acid-unstable groups and PAG components. Photoresist composition PR-9, which contains PAG components C-9 and C-8 having acid-unstable groups and does not contain polymer components, had a faster photospeed and a lower pseudo-Z factor compared to PR-1, which contains a polymer with acid-unstable groups and PAG components.

[0132] While this disclosure has been described in relation to what is currently considered to be a practical and exemplary embodiment, it should be understood that the present invention is not limited to the disclosed embodiments, but rather is intended to encompass various modifications and equivalent arrangements that fall within the spirit and scope of the appended claims.

Claims

1. Salts containing cations represented by formula (1) or (2): 【Chemistry 1】 (In equations (1) and (2), Ar １ ~Ar ５ These are, independently, substitutional or non-substitutional C. ６～３０ Aryl, or substituted or unsubstituted C ３～３０ It is a heteroaryl, Ar １ ~Ar ３ Each of these groups, whether independent or via a single bond or divalent linking group, can form another Ar group. １ ~Ar ３ They may be connected to form a ring, R ４ ~R ５ Each of them may be independent or linked to another group Ar via a single bond or a divalent linking group ４ ~Ar ５ to form a ring, Ar in equation (1) １ ~Ar ３ At least one of the and Ar of formula (2) ４ ~Ar ５ At least one of them is equation (A): 【Chemistry 2】 It is, In equation (A), Each ring A １ Independently, C ６～３０ Aryl or C ３～３０ It is a heteroaryl, Each R １ These are independently non-hydrogen substituents, Each R １ It may optionally further include one or more divalent linking groups as part of its structure. Each X is independently either a single bond or a substituted or unsubstituted C. １～１０ Alkylene, substituted, or unsubstituted C ３～１０ Cycloalkylene, substituted or unsubstituted C ３～１０ Heterocycloalkylene, substituted or unsubstituted C ６～１０ Arylene, substituted or unsubstituted C ３～１０ Heteroarylene, O, S, S(O), C(O), C(O)O, OC(O), C(O)N(R) ２ ), or NR ２ One or more of the following: R ２ C is hydrogen, deuterium, substituted or unsubstituted C １～２０ Alkyl, substituted, or unsubstituted C ３～２０ Cycloalkyl, substituted, or unsubstituted C ３～２０ Heterocycloalkyl, substituted, or unsubstituted C ６～３０ Aryl, substituted, or unsubstituted C ３～３０ Heteroaryl, or Ar ａ And, n1 is an integer between 1 and 4. Each x1 is independently between 0 and 10. w1 is an integer between 1 and 4. w2 is an integer between 0 and 4. * indicates a bonding site to an adjacent atom. Each Ar ａ is independently a base of formula (B) or (C): 【Transformation 3】 And, In equations (B) and (C), Ring A ２ is C ６～３０ Aryl or C ３～３０ It is a heteroaryl, L １ and L ２ Each of these is independently either a single bond, or a substituted or unsubstituted C. １～１０ Alkylene, substituted, or unsubstituted C ３～２０ Cycloalkylene, substituted or unsubstituted C ６～３０ Arylene group, substituted or unsubstituted C ３～３０ A divalent linking group selected from heteroarylenes or combinations thereof, R ３ It is a non-hydrogen substituent, Each R ３ It may optionally further include one or more divalent linking groups as part of its structure. x² is an integer between 0 and 10. R ４ ~R ６ These are, independently, hydrogen, substituted or unsubstituted C. １～２０ Alkyl, substituted, or unsubstituted C ３～２０ Cycloalkyl, substituted, or unsubstituted C ３～２０ Heterocycloalkyl, substituted, or unsubstituted C ２～２０ Alkenyl, substituted, or unsubstituted C ３～２０ Cycloalkenyl, substituted or unsubstituted C ２ ~C ２０ Alkynyl, substituted, or unsubstituted C ３～２０ Heterocycloalkenyl, substituted or unsubstituted C ６～２０ Aryl, or substituted or unsubstituted C ３～２０ It is a heteroaryl, but R ４ ~R ６ One or fewer of these can be hydrogen, R ４ ~R ６ If one of them is hydrogen, then R ４ ~R ６ At least one of the others is a substitution or non-substitution C ６～２０ Aryl, substituted, or unsubstituted C ３～２０ The condition is that it is a heteroaryl, R ４ ~R ６ Each of these may optionally further include one or more divalent linking groups as part of its structure. R ４ ~R ６ Any two of these may optionally form a ring together, which may further contain a divalent linking group as part of its structure, and the ring may be substituted or unsubstituted. R ７ and R ８ These are, independently, hydrogen, substituted or unsubstituted C. １～２０ Alkyl, substituted, or unsubstituted C ３～２０ Cycloalkyl, substituted, or unsubstituted C ３～２０ Heterocycloalkyl, substituted, or unsubstituted C ６～２０ Aryl, or substituted or unsubstituted C ３～２０ It is a heteroaryl, R ９ is a substitution or non-substitution C １～２０ Alkyl, substituted, or unsubstituted C ３～２０ Cycloalkyl, or substituted or unsubstituted C ３～２０ It is a heterocycloalkyl, R ７ ~R ９ Each of these may optionally further include one or more divalent linking groups as part of its structure. R ７ ~R ９ Any two of these may optionally form a ring together, which may further include a divalent linking group as part of its structure, and the ring group may be substituted or unsubstituted. n² is an integer between 1 and 4. n3 is an integer between 1 and 4. (* indicates a bonding site to an adjacent atom).

2. Each X independently becomes O, S, or NR ２ The salt according to claim 1.

3. L １ and L ２ The salt according to claim 1 or 2, wherein the bond is a single bond.

4. Ar ａ The salt according to any one of claims 1 to 3, wherein Ar is a group of formula (B) containing a tertiary ester group.

5. The salt according to any one of claims 1 to 4, wherein n2 and n3 are each independently 1 or 2.

6. A salt according to any one of claims 1 to 5, further comprising a halide, a hexafluorophosphate, or an anion selected from an anionic group, wherein the anionic group comprises a sulfonate, a sulfonamide, a sulfonimidate, a methide, a borate, or a carboxylate.

7. The salt according to claim 6, wherein the anionic group further comprises a polymerizable group.

8. The salt according to any one of claims 1 to 7, wherein the salt is polymeric.

9. The salt according to any one of claims 1 to 8, wherein the cation further comprises a hydroxyaryl group.

10. A photoresist composition, A salt according to any one of claims 1 to 8, solvent and A photoresist composition containing [a specific compound / component].

11. The photoresist composition according to claim 10, wherein the salt is present in the photoresist composition in an amount exceeding 50% by weight, based on the total solid content of the photoresist composition.

12. The photoresist composition according to claim 10 or 11, further comprising a photoacid generator, wherein the salt and the photoacid generator are different from each other.

13. A method for forming a pattern, A photoresist composition layer is obtained by coating a layer of the photoresist composition according to any one of claims 10 to 12 onto a substrate; Obtaining an exposed photoresist composition layer by pattern-like exposure of the photoresist composition layer with activating radiation; and Develop the exposed photoresist composition layer to obtain the pattern; A method that includes this.

Images