Photoactive compounds, photoresist compositions comprising the same, and pattern forming methods

Abstract

A photoactive compound of formula (1a) or (1b): wherein R 1 is substituted or unsubstituted C 1‑30 alkyl, substituted or unsubstituted C 3‑30 cycloalkyl, substituted or unsubstituted C 3‑30 heterocycloalkyl, substituted or unsubstituted C 6‑30 aryl, or substituted or unsubstituted C 3‑30 heteroaryl; R 2 and R 3 are as provided herein; R 4 is substituted or unsubstituted C 1‑30 alkyl, substituted or unsubstituted C 3‑30 cycloalkyl, substituted or unsubstituted C 3‑30 heterocycloalkyl, substituted or unsubstituted C 6‑30 aryl, or substituted or unsubstituted C 3‑30 heteroaryl; and M + is an organic cation.

Description

Technical Field

[0001] This invention relates to photoactive compounds for use in photoresist compositions and to a method for patterning using such photoresist compositions. The invention has found applicability in photolithography applications within the semiconductor manufacturing industry. Background Technology

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

[0003] Chemically enhanced photoresists are commonly used for high-resolution processing. These resists typically employ a polymer with acid-indestabilized groups, a photoacid generator, and an acid quencher. Patterning exposure to activating radiation via a photomask causes the acid generator to form acid, which, during post-exposure baking, cleaves the acid-indestabilized groups in the exposed regions of the polymer. An acid quencher is typically added to the photoresist composition to control acid diffusion into unexposed areas, thereby improving contrast. The photolithography process results in a difference in solubility properties between exposed and unexposed areas of the resist in the developer solution. During positive development (PTD), the exposed areas of the photoresist layer dissolve in the developer and are removed from the substrate surface, while the unexposed areas, insoluble in the developer, are retained after development to form a positive image. The resulting embossed image allows for selective processing of the substrate.

[0004] Non-photoactive acid quenching materials commonly used in chemically reinforced resists include straight-chain aliphatic amines, cyclic aliphatic amines, aromatic amines, straight-chain and cyclic amides and their derivatives. Another commonly used class of acid quenching materials is photoactive quenchers, also known as photodegradable quenchers or photodegradable quenchers. Photoactive quenchers have also been used in chemically reinforced resist compositions. Photodegradable quenchers are typically salts containing a photoactive ononium cation and anion, where the anion is the conjugate base of a weak acid. Before exposure, the salt acts as a base or acid quencher. After exposure, the anionic portion of the photodegradable quencher becomes protonated and thus becomes more acidic. Therefore, when a chemically reinforced resist containing a photodegradable quencher is irradiated, the concentration of the acid quencher in the exposed area decreases sharply. On the other hand, intact photodegradable quenchers in the unexposed areas can capture acid molecules diffused from the exposed areas during photolithography, thereby improving photolithography performance.

[0005] Photoresist compositions comprising photodegradable quenchers and their uses have been described in the art. However, for many other applications, there is a need for novel photoresists that can provide high-resolution line-space characteristics with superior line edge roughness (LWR) and wider depth of focus (DOF). Summary of the Invention

[0006] A photoactive compound having formula (1a) or (1b) is provided:

[0007]

[0008] Where R 1 Is it substituted or unsubstituted C? 1-30 Alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, or C containing a substituted or unsubstituted aromatic cyclic heteroatom selected from nitrogen, oxygen, or combinations thereof. 3-30 heteroaryl; R 2 It is hydrogen, halogen, 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 3-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C1-C 30 Alkylthio, substituted or unsubstituted C3-C 10 Cycloalkenyl, substituted or unsubstituted C3-C 10 Heterocyclic alkenyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, or substituted or unsubstituted C6-C 30 aryloxy group; R 3 It is a hydrogen or non-hydrogen substituent; R 4 Is it substituted or unsubstituted C? 1-30 Alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 heteroaryl; R 2 R 3 and R 4Each of the components optionally further comprises one or more divalent linking groups as part of its structure, wherein each of the one or more divalent linking groups is independently substituted or unsubstituted; R 2 and R 3 Optionally, they form a ring, which optionally further comprises one or more divalent linking groups as part of its structure, each of said one or more divalent linking groups being substituted or unsubstituted, and said ring being substituted or unsubstituted; and M + It is an organic cation.

[0009] On the other hand, a photoresist composition is provided, comprising a photoactive compound and a solvent.

[0010] Another aspect provides a method for forming a pattern, the method comprising: (a) forming a photoresist layer from a photoresist composition; (b) exposing the photoresist layer in a patterned manner to activation radiation; and (c) developing the exposed photoresist layer to provide a photoresist relief image. Detailed Implementation

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

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

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

[0014] As used herein, "photochemical rays" or "radiation" refers to, for example, the bright-line spectrum of a mercury lamp, far-ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, particle rays (such as electron beams and ion beams), etc. Furthermore, in this invention, "light" refers to photochemical rays or radiation.

[0015] Argon fluoride lasers (ArF lasers) are a special type of excimer laser, sometimes called excimer complex lasers. "Excimer" is an abbreviation for "excited dimer," and "excimer complex" is an abbreviation for "excited complex." Excimer lasers use a mixture of rare gases (argon, krypton, or xenon) and halogen gases (fluorine or chlorine), which, under appropriate electrical stimulation and high voltage conditions, emit coherent stimulated emission (lasing) in the ultraviolet range.

[0016] Furthermore, unless otherwise stated, “exposure” in this specification includes not only exposure through a mercury lamp, far ultraviolet light represented by an excimer laser, X-rays, extreme ultraviolet light (EUV light), etc., but also writing with particle beams (such as electron beams and ion beams).

[0017] As used herein, the term "hydrocarbon" refers to an organic compound or group having at least one carbon atom and at least one hydrogen atom; "alkyl" refers to a straight-chain or branched saturated hydrocarbon group having a specified number of carbon atoms and a valence of 1; "alkylene" refers to an alkyl group having a valence of 2; "hydroxyalkyl" refers to an alkyl group substituted with at least one hydroxyl group (-OH); "alkoxy" refers to "alkyl-O-"; "carboxyl" and "carboxylic acid" refer to groups having the formula "-C(=O)-OH"; "cycloalkyl" refers to a monovalent group having one or more saturated rings in which all ring members are carbon; "cycloalkylene" refers to a cycloalkyl group having a valence of 2; "alkenyl" refers to a straight-chain or branched monovalent hydrocarbon group having at least one carbon-carbon double bond; "alkenoxy" refers to "alkenyl-O-"; "alkenylene" refers to an alkenyl group having a valence of 2. "Cycloalkenyl" refers to a non-aromatic cyclic monovalent hydrocarbon group having at least three carbon atoms and at least one carbon-carbon double bond; "alkynyl" refers to a monovalent hydrocarbon group having at least one carbon-carbon triple bond; the term "aromatic group" refers to a monocyclic or polycyclic ring system that satisfies Hückel's rule and includes a carbon atom in the ring, and optionally may include one or more heteroatoms selected from N, O, and S that replace the carbon atoms in the ring; "aryl" refers to a monovalent aromatic monocyclic or polycyclic ring system in which each ring member is carbon, and may include a group having an aromatic ring fused to at least one cycloalkyl or heterocyclic alkyl ring; "arylene" refers to an aryl group having a valence of 2; "alkylaryl" refers to an aryl group that has been substituted with an alkyl group; "arylalkyl" refers to an alkyl group that has been substituted with an aryl group; "aryloxy" refers to "aryl-O-"; and "arylthio" refers to "aryl-S-".

[0018] The prefix "hetero" means that the compound or group includes at least one member (e.g., 1, 2, 3, or 4 or more heteroatoms) that replaces a carbon atom, wherein each of the one or more heteroatoms is independently N, O, S, Si, or P; "heteroatom-containing group" refers to a substituent that includes at least one heteroatom; "heteroalkyl" refers to an alkyl group having at least one heteroatom that replaces a carbon atom; "heterocyclic alkyl" refers to a cycloalkyl group having at least one heteroatom that replaces a carbon ring member; "heterocyclic alkyl" refers to a heterocyclic alkyl group having a valence of 2.

[0019] The term "heteroaryl" refers to an aromatic 4-8 membered monocyclic, 8-12 membered bicyclic, or 11-14 membered tricyclic ring system having 1-4 heteroatoms (if monocyclic), 1-6 heteroatoms (if bicyclic), or 1-9 heteroatoms (if tricyclic), each heteroatom being independently selected from N, O, S, Si, or P (e.g., carbon atom and 1-3, 1-6, or 1-9 N, O, or S heteroatoms, respectively, if monocyclic, bicyclic, or tricyclic). Examples of heteroaryl groups include pyridyl, furanyl (furyl or furanyl), imidazole, benzimidazolyl, pyrimidinyl, thiophenyl or thienyl, quinolinyl, indole, thiazolyl, etc.

[0020] Unless otherwise explicitly stated, each of the aforementioned substituents may be optionally substituted. The term “optionally substituted” means either substituted or unsubstituted. “Substituted” means that at least one hydrogen atom in the chemical structure is substituted by another terminal substituent, typically monovalent, provided that the valence of the specified atom is not exceeded. When the substituent is oxo (i.e., =O), the two twin hydrogen atoms on the carbon atom are substituted by a terminal oxo group. Combinations of substituents or variations are permitted. Exemplary substituents that may be present at the “substituted” position include, but are not limited to, nitro (-NO2), cyano (-CN), hydroxyl (-OH), oxo (=O), amino (-NH2), mono- or di- (C 1-6 )alkylamino, alkanoyl (such as C 2-6 Alkyl groups (such as acyl groups), formyl groups (-C(=O)H), carboxylic acids or their alkali metal salts or ammonium salts; esters (including acrylates, methacrylates and lactones) such as C 2-6 Alkyl esters (-C(=O)O-alkyl or -OC(=O)-alkyl) and C 7-13 Aryl esters (-C(=O)O-alkyl or -OC(=O)-aryl), amide groups (-C(=O)NR2, where R is hydrogen or C... 1-6 Alkyl), formamido (-CH2C(=O)NR2, where R is hydrogen or C 1-6 Alkyl), halogen, mercapto (-SH), C 1-6 Alkylthio (-S-alkyl), thiocyano (-SCN), C 1-6 Alkyl, C 2-6 alkenyl, C 2-6 alkynyl group, C 1-6 Haloalkyl, C 1-9 Alkoxy, C 1-6 Haloalkoxy, C 3-12 cycloalkyl, C 5-18 Cycloalkenyl, C 2-18Heterocyclic alkenyl groups, having at least one aromatic ring, C 6-12 Aryl (e.g., phenyl, biphenyl, naphthyl, etc., each ring being substituted or unsubstituted aromatic), having 1 to 3 single or fused rings and 6 to 18 ring carbon atoms. 7-19 arylalkyl, having 1 to 3 single or fused rings and 6 to 18 cyclic carbon atoms, C 7-12 Alkyl aryl, C 3-12 Heterocyclic alkyl, C 3-12 heteroaryl, C 1-6 alkylsulfonyl (-S(O)2-alkyl), C 6-12 Arylsulfonyl (-S(=O)2-aryl), or toluenesulfonyl (CH3C6H4SO2-). When the group is substituted, the indicated number of carbon atoms is the total number of carbon atoms in the group, excluding those with any substituents. For example, the group -CH2CH2CN is a cyano-substituted C2 alkyl.

[0021] The term "halogen" refers to a monovalent substituent of fluorine (fluorinated), chlorine (chloroinated), bromine (brominated), or iodine (iodinated). The prefix "halogenated" indicates a group containing one or more of the fluorine, chlorine, bromine, or iodine substituents that replace a hydrogen atom. Combinations of halogen groups (e.g., bromine and fluorine) or only fluorine groups may be present. For example, the term "halogenated alkyl" refers to an alkyl group substituted with one or more halogens. As used herein, "substituted C" refers to an alkyl group substituted with one or more halogens. 1-8 "Halogenated alkyl" refers to a C that has been substituted with at least one halogen. 1-8 Alkyl groups, and further substituted by one or more other substituents that are not halogens. It should be understood that substitution of groups with halogen atoms should not be considered as heteroatom-containing groups, because halogen atoms do not substitute carbon atoms.

[0022] As used herein, an "acid-indestructible group" refers to a group in which a bond is broken by the catalytic action of an acid (optionally and typically in conjunction with heat treatment), resulting in the formation of a polar group (such as a carboxylic acid or alcohol group, formed on the polymer) and a portion of the bond connected to the broken bond, optionally and typically disconnected from the polymer. In other systems, nonpolymeric compounds may include acid-indestructible groups that can be cleaved by the catalytic action of an acid, resulting in the formation of a polar group, such as a carboxylic acid or alcohol group, on the cleaved portion of the nonpolymeric compound. Such acids are typically photogenerated acids under conditions of bond cleavage during post-exposure baking; however, the examples are not limited thereto, and such acids may, for example, be thermally generated. Suitable acid-indestructible groups include, for example, tertiary alkyl ester groups, secondary or tertiary aryl ester groups, secondary or tertiary ester groups having a combination of alkyl and aryl groups, tertiary alkoxy groups, acetal groups, or ketal groups. Acid-indestructible groups are also commonly referred to in the art as "acid-cleavable groups," "acid-cleavable protecting groups," "acid-indestructible protecting groups," "acid-leaving groups," "acid-decomposable groups," and "acid-sensitive groups."

[0023] As used herein, unless otherwise defined, "divalent linker" refers to -O-, -S-, -Te-, -Se-, -C(O)-, -N(R)-, etc. a -, -S(O)-, -S(O)2-, -C(S)-, -C(Te)-, -C(Se)-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 A divalent group, or one or more of a heteroaryl group or a combination thereof, wherein R a It is hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Heteroaryl groups. Typically, the divalent linking groups include -O-, -S-, -C(O)-, and -N(R-). a -, -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 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 Heteroaryl groups or combinations thereof, wherein R a It is hydrogen, substituted or unsubstituted C1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Heteroaryl groups. More typically, the divalent linking group includes at least one of the following: -O-, -C(O)-, -C(O)O-, -N(R a )-、-C(O)N(R a -, substituted or unsubstituted C 1-10 Alkylene, substituted or unsubstituted C 3-10 Cycloalkylene, substituted or unsubstituted C 3-10 Heterocyclic alkyl, substituted or unsubstituted C 6-10 aryl, substituted or unsubstituted C 3-10 heteroaryl, or combinations thereof, wherein R a It is hydrogen, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted C 1-10 Heteroalkyl, substituted or unsubstituted C 6-10 aryl, or substituted or unsubstituted C 3-10 Mixed aromatic compounds.

[0024] This invention relates to photoactive compounds, such as photodegradable quencher (PDQ) compounds. In particular, the photoactive compounds of this invention are salts comprising α,β-unsaturated carboxylate salts, which can be used in photoresist compositions to achieve improved roughness of print features and a wider DOF.

[0025] Photoactive compounds have formula (1a) or (1b):

[0026]

[0027] In equation (1a), R 1 Is it substituted or unsubstituted C? 1-30 Alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, or C containing a substituted or unsubstituted aromatic cyclic heteroatom selected from nitrogen, oxygen, or combinations thereof. 3-30 heteroaryl. Preferably, R 1 C can be substituted or unsubstituted. 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C-aryl groups containing an aromatic cyclic heteroatom selected from nitrogen or oxygen. 3-20 Heteroaryl, and typically, R 1 C can be substituted or unsubstituted.6-20 aryl or substituted or unsubstituted C-aryl groups containing an aromatic cyclic heteroatom selected from nitrogen or oxygen. 3-20 heteroaryl, wherein the substituted C 6-20 Aryl and substituted C 3-20 Each heteroaryl group can be independently converted to a halogen, hydroxyl group, or substituted or unsubstituted C. 1-10 Alkyl, substituted or unsubstituted C6-C 20 aryl, substituted or unsubstituted C6-C 20 aryloxy group, substituted or unsubstituted C3-C 20 heteroaryl or having the formula -C(O)OR 8 At least one of the groups is substituted, wherein R is a substituent of the group. 8 C can be substituted or unsubstituted. 1-10 Alkyl, substituted or unsubstituted C 3-10 cycloalkyl, substituted or unsubstituted C 6-10 aryl, or substituted or unsubstituted C 3-10 Mixed aromatic compounds.

[0028] In equation (1a), R 2 It is hydrogen, halogen, 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 3-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C1-C 30 Alkylthio, substituted or unsubstituted C3-C 10 Cycloalkenyl, substituted or unsubstituted C3-C 10 Heterocyclic alkenyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, or substituted or unsubstituted C6-C 30 Aryloxy group. Preferably, R 2 It can be hydrogen, halogen, or substituted or unsubstituted C. 1-10 Alkyl groups, and typically R 2 It could be hydrogen.

[0029] In equation (1a), R 2 and R 3 Each of the components optionally further comprises one or more divalent linking groups as part of its structure, wherein each of the one or more divalent linking groups is independently substituted or unsubstituted.

[0030] In equation (1a), R 2 and R 3 Optionally, they form a ring, which optionally further comprises one or more divalent linking groups as part of its structure, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0031] In equation (1a), R 3 It can be a hydrogen or non-hydrogen substituent. For example, R 3 It can be hydrogen, or substituted or unsubstituted C. 1-20 Organic groups. In some embodiments, R 3 It can further include -C(O)-, -C(O)O-, -C(O)N(R) 5 C of )- or combinations thereof 1-20 Organic groups, wherein R 5 It 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 Heteroaryl. In other embodiments, R 3 It can be a halogen atom, a cyano group, or a substituted or unsubstituted C atom. 1-5 Haloalkyl. In some respects, when R 1 Is it substituted or unsubstituted C? 6-30 When aryl, R 3 It is neither hydrogen nor halogen.

[0032] In equation (1b), R 4 Is it substituted or unsubstituted C? 1-30 Alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 heteroaryl. Preferably, R 4 C can be substituted or unsubstituted. 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 3-20 heteroaryl. For example, R 4 C can be substituted or unsubstituted. 6-18 aryl, or substituted or unsubstituted C 3-18 heteroaryl, wherein the substituted C 6-18 Aryl and substituted C 3-18Each of the heteroaryl groups is substituted by at least one of the following: halogen, amino (-NH2), mono- or di-(C) 1-6 )alkylamino, substituted or unsubstituted C 1-6 Alkyl, substituted or unsubstituted C 1-6 Halogenated alkyl, substituted or unsubstituted C 1-9 Alkoxy, substituted or unsubstituted C 2-6 alkenyl, substituted or unsubstituted C 6-12 aryl, substituted or unsubstituted C 3-12 heteroaryl groups, or combinations thereof. 4 Optionally further comprising one or more divalent linking groups as part of its structure, wherein each of the one or more divalent linking groups is independently substituted or unsubstituted.

[0033] In equations (1a) and (1b), M + It is an organic cation. For example, M + It can be a sulfonium cation or an iodonium cation. In some embodiments, M + It can be a sulfonium cation having formula (2a) or an iodonium cation having formula (2b):

[0034]

[0035] In equations (2a) and (2b), R 10 R 20 and R 30 Each can be either substituted or unsubstituted C independently. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 6-30 Iodinated aryl, substituted or unsubstituted C 3-30 heteroaryl, substituted or unsubstituted C 7-20 arylalkyl, or substituted or unsubstituted C 4-20 Heteroarylalkyl. R 10 R 20 and R 30 Each of them can be a single group or connected to another group R via a single bond or a divalent linker. 10 R 20 Or R 30 To form a ring. R 10 R 20 and R 30 Each of these may optionally include a divalent linker as part of its structure. R 10 R 20 and R 30Each of these groups may independently and optionally contain an acid-indestructible group selected from, for example, the following: tertiary alkyl ester group, secondary or tertiary aryl ester group, secondary or tertiary ester group having a combination of alkyl and aryl groups, tertiary alkoxy group, acetal group, or ketal group. Suitable groups for linking R... 10 R 20 and / or R 30 The divalent linking group of the group includes, for example, -O-, -S-, -Te-, -Se-, -C(O)-, -C(S)-, -C(Te)-, or -C(Se-), substituted or unsubstituted C- groups. 1-5 Alkylenes, or combinations thereof.

[0036] Exemplary sulfonium cations having formula (2a) include the following:

[0037]

[0038]

[0039] Exemplary iodonium cations having formula (2b) include the following:

[0040]

[0041]

[0042] In some respects, photoactive compounds having formula (1a) can be represented by formula (3a):

[0043]

[0044] In equation (3a), ring CY1 can be C 3-30 Carbocyclic group or C 3-30 Heterocyclic group. Preferably, ring CY1 is C 3-8 cycloalkyl, C 6-14 aryl, or C containing an aromatic cyclic heteroatom selected from nitrogen, oxygen, or combinations thereof. 3-12 Mixed aromatic compounds.

[0045] In equation (3a), each L 1 It can be a single bond or a divalent linker independently.

[0046] In equation (3a), each R 8 It can be independently a hydroxyl group, -F, -I, -CF3, substituted or unsubstituted C. 1-10 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl, substituted or unsubstituted C 6-10 aryl, or substituted or unsubstituted C 3-10 Mixed aromatic compounds.

[0047] In equation (3a), a is an integer from 0 to 10. Preferably, a is an integer from 0 to 5, and typically a is an integer from 0 to 3.

[0048] In equation (3a), L 2 It is a single bond, -C(O)-, -C(O)O-, or -C(O)N(R) 5a )-, where R 5a It is hydrogen, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted C 1-10 Heteroalkyl, substituted or unsubstituted C 6-10 aryl, or substituted or unsubstituted C 3-10 Mixed aromatic compounds.

[0049] In equation (3a), R 9 It can be hydrogen, cyano, hydroxyl, -F, -I, -CF3, substituted or unsubstituted C. 1-10 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl, substituted or unsubstituted C 6-10 aryl, or substituted or unsubstituted C 3-10 heteroaryl. In some embodiments, when R 9 It is the replacement of C 1-10 Alkyl, substituted C 3-20 cycloalkyl, substituted C 3-20 Heterocyclic alkyl, substituted C 6-10 aryl, or substituted C 3-10 When it is a heteroaryl group, the substituted R 9 At least one substituent of the group may be a hydroxyl group, -I group, or a combination thereof.

[0050] In equation (3a), M + Same as defined in equation (1a).

[0051] In some respects, photoactive compounds having formula (1b) can be represented by formula (3b):

[0052]

[0053] In equation (3b), ring CY2 can be C 3-30 Carbocyclic group or C 3-30 Heterocyclic group. Preferably, ring CY2 is C 3-8 cycloalkyl, C 6-14 aryl, or C containing an aromatic cyclic heteroatom selected from nitrogen, oxygen, or combinations thereof. 3-12 Mixed aromatic compounds.

[0054] In equation (3b), b is an integer from 0 to 10. Preferably, b is an integer from 0 to 5, and typically b is an integer from 0 to 3.

[0055] In equation (3b), L 3 It is a single bond, -C(O)-, -C(O)O-, or -C(O)N(R) 5b )-, where R 5b It is hydrogen, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted C 1-10 Heteroalkyl, substituted or unsubstituted C 6-10 aryl, or substituted or unsubstituted C 3-10 Mixed aromatic compounds.

[0056] In equation (3b), R 11 It can be hydrogen, cyano, hydroxyl, -F, -I, -CF3, substituted or unsubstituted C. 1-10 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl, substituted or unsubstituted C 6-10 aryl, or substituted or unsubstituted C 3-10 heteroaryl. In some embodiments, when R 9 It is the replacement of C 1-10 Alkyl, substituted C 3-20 cycloalkyl, substituted C 3-20 Heterocyclic alkyl, substituted C 6-10 aryl, or substituted C 3-10 When it is a heteroaryl group, the substituted R 9 At least one substituent of the group may be a hydroxyl group, -I group, or a combination thereof.

[0057] In equation (3b), M + Same as defined in equation (1b).

[0058] Non-limiting examples of the anionic moiety of a photoactive compound having formula (1a) may include one or more of the following compounds:

[0059]

[0060]

[0061]

[0062] Non-limiting examples of the anionic moiety of a photoactive compound having formula (1b) may include one or more of the following compounds:

[0063]

[0064] The present invention further relates to photoresist compositions comprising a photoactive compound and a solvent and may contain additional optional components. Typically, the photoresist composition will further comprise a polymer, a photoacid generator (PAG), or a combination thereof.

[0065] According to one aspect, the photoresist composition further includes a material whose solubility in an alkali or organic solvent is altered by the action of an acid, wherein the material is different from the photoactive compound. For example, the material may be a polymer or a molecular glass.

[0066] The polymer may contain one or more repeating units. These repeating units may be one or more units for the purpose of, for example, adjusting the properties of the photoresist composition (such as etching rate and solubility). Exemplary repeating units may include those derived from one or more of (meth)acrylates, vinyl aromatics, vinyl ethers, vinyl ketones, and / or vinyl ester monomers.

[0067] In some embodiments, the polymer may comprise repeating units containing acid-labile groups. For example, repeating units containing acid-labile groups may be derived from one or more monomers having formulas (4), (5), or (6):

[0068]

[0069] In equations (4), (5) and (6), R a To R c Each can be an independent C group consisting of hydrogen, fluorine, cyano, or substituted or unsubstituted C. 1-10 Alkyl group. Preferably, R a To R c Each can be independently hydrogen, fluorine, or substituted or unsubstituted C. 1-5 Alkyl groups, typically methyl groups.

[0070] In equation (4), L 4 It is a divalent linker. For example, L 4 It can contain 1 to 10 carbon atoms and at least one heteroatom. In a typical example, L 4 It can be -OCH2-, -OCH2CH2O-, or -N(R) 5c )-, where R 5c Is it hydrogen or C? 1-6 alkyl.

[0071] In equations (4) and (5), R 21 To R 26 Each is independently a hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C3-20 Heterocyclic alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 3-20 Cycloalkenyl, substituted or unsubstituted C 3-20 Heterocyclic alkenyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 3-20 heteroaryl, which is based on R 21 To R 23 No more than one of them can be hydrogen and R 24 To R 26 No more than one of them can be hydrogen, provided that if R 21 To R 23 If one of them is hydrogen, then R 21 To R 23 At least one of the other Cs is either substituted or unsubstituted. 6-20 aryl or substituted or unsubstituted C 3-20 heteroaryl, and if R 24 To R 26 If one of them is hydrogen, then R 24 To R 26 At least one of the other Cs is either substituted or unsubstituted. 6-20 aryl or substituted or unsubstituted C 3-20 heteroaryl. Preferably, R 21 To R 26 Each is independently either substituted or unsubstituted C 1-6 Alkyl or substituted or unsubstituted C 3-10 Cycloalkyl. R 21 To R 26 Each of them may optionally further include a divalent linker group as part of its structure.

[0072] In equation (4), R 21 To R 23 Any two of them can optionally form a ring via a single bond or a divalent linking group, wherein the ring can be substituted or unsubstituted. In formula (5), R 24 To R 26 Any two of them can optionally form a ring via a single bond or a divalent linking group, wherein the ring can be substituted or unsubstituted.

[0073] For example, R 21 To R 26 Any one or more of them can independently be of the formula -CH2C(=O)CH (3-n) Y n The group, wherein each Y is independently a substituted or unsubstituted C. 2-10Heterocyclic alkyl groups, and n is 1 or 2. For example, each Y can independently be a group having the formula -O(C a1 (C) a2 The substitution or unsubstituted C of the O- group 2-10 Heterocyclic alkyl, wherein C a1 and C a2 Each is independently hydrogen or a substituted or unsubstituted alkyl group, and wherein C a1 and C a2 They can be arranged together to form a ring.

[0074] In equations (6) and (8), R 27 R 28 R 34 and R 35 Each can be independently hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 3-20 heteroaryl; and R 16 and R 22 Each is independently either substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 3-20 Heterocyclic alkyl groups. Preferably, R 27 R 28 R 34 and R 35 Each can be independently hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 3-20 Heterocyclic alkyl. R 27 R 28 R 34 and R 35 Each of them may optionally further include a divalent linker group as part of its structure.

[0075] In equation (7), R 31 To R 33 Each can be either substituted or unsubstituted C independently. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 3-20 heteroaryl, which is based on R 31 To R 33No more than one of them can be hydrogen, provided that if R 31 To R 33 If one of them is hydrogen, then R 31 To R 33 At least one of the other Cs is either substituted or unsubstituted. 6-20 aryl or substituted or unsubstituted C 3-20 Mixed aromatics. R 31 To R 33 Each of them may optionally further include a divalent linker group as part of its structure.

[0076] In equation (7), R 31 To R 33 Any two of them may optionally form a ring together, which may further include a divalent linking group as part of its structure, wherein the ring group may be substituted or unsubstituted.

[0077] In equations (7) and (8), X a and X b Each is independently a polymerizable group containing an olefinic unsaturated double bond, such as substituted or unsubstituted C. 2-20 The norborneol is alkenyl or substituted or unsubstituted, preferably (meth)acrylate or C2 alkenyl.

[0078] In equations (7) and (8), L 5 and L 6 Each is an independent single-bonded or divalent linker, provided that X is a single bond or a divalent linker. a When it is C2 alkenyl, L 5 It is not a single bond, and when X b When it is C2 alkenyl, L 6 It is not a single bond. Preferably, L 5 and L 6 Each is independently either substituted or unsubstituted C 6-30 aryl or substituted or unsubstituted C 6-30 Cycloalkylene. In formulas (7) and (8), n1 is 0 or 1, and n2 is 0 or 1. It should be understood that when n1 is 0, L 5 The group is directly attached to the oxygen atom. It should be understood that when n² is 0, L... 6 The group is directly attached to the oxygen atom.

[0079] In equation (8), R 34 To R 36 Any two of them can optionally form a ring, wherein the ring may further include a divalent linking group as part of its structure, wherein the ring group may be substituted or unsubstituted.

[0080] In some respects, R 21To R 29 and R 31 To R 36 Each of these may optionally further include, as part of its structure, a component selected from -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R ’ One or more divalent linking groups of -C(O)N(R')- or -C(O)N(R')-, wherein R' can be hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 3-20 Heterocyclic alkyl groups.

[0081] In some respects, in repeating units containing acid-labile groups, the acid-labile group can be a tertiary alkyl ester. For example, repeating units containing tertiary alkyl ester groups can be derived from one or more monomers having formulas (4), (5), or (7), wherein R 21 To R 26 Or R 34 To R 36 Neither of them is hydrogen, and n1 is 1.

[0082] Exemplary monomers having formula (4) include one or more of the following:

[0083]

[0084]

[0085] Exemplary monomers having formula (5) include one or more of the following:

[0086]

[0087]

[0088] Where R d As in this paper, R in equation (3) b Defined; and R ’ "and R" are independently substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 3-20 Cycloalkenyl, substituted or unsubstituted C 3-20 Heterocyclic alkenyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 3-20 Mixed aromatic compounds.

[0089] Exemplary monomers having formula (6) include one or more of the following:

[0090]

[0091] Where R d R is as defined above c .

[0092] Exemplary monomers having formula (7) include one or more of the following:

[0093]

[0094] Exemplary monomers having formula (8) include one or more of the following:

[0095]

[0096] In some respects, the polymer may have an acid-instable repeating unit derived from one or more monomers having cyclic acetal or cyclic ketal groups, for example having one or more of the following structures:

[0097]

[0098]

[0099] Where R d R is as defined above a .

[0100] In some respects, the polymer may have repeating units containing acid-labile groups (including tertiary alkoxy groups), such as one or more of the following monomers:

[0101]

[0102] When present, repeating units containing acid-labile groups are typically included in the polymer in an amount of 5 to 95 mol%, more typically 20 to 80 mol%, and even more typically 30 to 50 mol% based on the total repeating units in the polymer.

[0103] In some aspects, the polymer may further comprise repeating units containing polar groups, wherein the polar groups are side-attached to the polymer backbone. For example, the polar groups may be lactone groups, hydroxyaryl groups, fluoroalcohol groups, or combinations thereof.

[0104] In one or more embodiments, the polymer may further comprise a third repeating unit derived from one or more lactone-containing monomers having formula (9):

[0105]

[0106] In equation (9), R f It is a hydrogen, fluorine, cyano group, or a substituted or unsubstituted C group. 1-10 alkyl.

[0107] In equation (9), L 7 It is a single bond or a divalent linker. Preferably, L 7 It is a single bond or one or more groups selected from the following: substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 Hybrid aryl, -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R')-, or -C(O)N(R”)-, where R ’ "R" can be hydrogen, substituted or unsubstituted C, independently. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 3-20 Heterocyclic alkyl groups. When L 7 When it is a single key, -R 37 Partially attached directly to the oxygen atom adjacent to the carbonyl group (i.e., -C(O)OR) 37 ).

[0108] In equation (9), R 37 Is it a substituted or unsubstituted C-containing compound? 4-20 The lactone group, or substituted or unsubstituted C-containing group 4-20 The group of sulfonyl lactone. Contains C. 4-20 lactone groups and C-containing groups 4-20 The functional groups of sulfonyl lactones can be monocyclic, polycyclic, or fused polycyclic.

[0109] An exemplary monomer having formula (9) may include one or more of the following:

[0110]

[0111] Where R f It is as defined for equation (9).

[0112] The polymer may contain repeating units that are alkali-soluble and / or have a pKa of less than or equal to 12. For example, repeating units containing polar groups side-attached to the polymer backbone may be derived from one or more monomers having formula (10), (11), or (12):

[0113]

[0114] In equations (10), (11), or (12), R g To R j Each can be an independent C group consisting of hydrogen, fluorine, cyano, or substituted or unsubstituted C. 1-10 Alkyl group. Preferably, R g To R j Each can be independently hydrogen, fluorine, or substituted or unsubstituted C. 1-5 Alkyl groups, typically methyl groups.

[0115] In equation (10), R 38 C can be substituted or unsubstituted. 1-100 Or C 1-20 Alkyl, typically C 1-12 Alkyl; substituted or unsubstituted C 3-30 Or C 3-20 cycloalkyl; or substituted or unsubstituted poly(C) 1-3 Epoxides). Preferably, substituted C 1-100 Or C 1-20 Alkyl, substituted C 3-30 Or C 3-20 cycloalkyl and substituted poly(C) 1-3 Epoxides are substituted with one or more of the following: halogens, fluoroalkyl groups such as C 1-4 Fluoroalkyl groups (typically desfluoromethyl), sulfonamide groups -NH-S(O)2-Y 1 , where Y 1 Is it F or C? 1-4 Perfluoroalkyl (e.g., -NHSO2CF3) or fluoroalcohol groups (e.g., -C(CF3)2OH).

[0116] In equation (11), L 8 Indicates a single bond or a multivalent linker selected from, for example, the following: optionally substituted aliphatic groups (such as C... 1-6 Alkylene or C 3-20 Cycloalkylene hydrocarbons, and aromatic hydrocarbons thereof, optionally having a group selected from -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -NR- 102 -、or-C(O)N(R) 102 One or more connecting parts of )-, where R 102 Selected from hydrogen and optionally substituted C 1-10 Alkyl groups. For example, the polymer may further comprise repeating units derived from one or more monomers having formula (10), wherein L 8 It is a single bond, or a polyvalent linker selected from the following: substituted or unsubstituted C 1-20 Alkylene, substituted or unsubstituted C3-20 Cycloalkylene, and substituted or unsubstituted C 6-24 Aryl groups, typically substituted or unsubstituted C464. 1-6 Alkylene, substituted or unsubstituted C 3-10 Cycloalkylene, or substituted or unsubstituted C 6-24 Alpha-aryl.

[0117] In equation (11), n3 is an integer from 1 to 5, typically 1. It should be understood that when n3 is 1, the group L... 8 It is a divalent linker. It should be understood that when n3 is 2, the group L... 8 It is a trivalent linker. Similarly, it should be understood that when n3 is 3, the group L... 8 It is a tetravalent linker; when n3 is 4, the group L 8 It is a pentavalent linker; and when n3 is 5, the group L 8 It is a hexavalent linker. Therefore, in the context of formula (10), the term "multivalent linker" refers to any of the divalent, trivalent, tetravalent, pentavalent, and / or hexavalent linkers. In some respects, when n is 2 or greater, the carboxylic acid group (-C(O)OH) can be attached to the linker L. 8 On the same atoms. In other respects, when n is 2 or greater, the carboxylic acid group (-C(O)OH) can be attached to the linking group L. 8 On different atoms.

[0118] In equation (12), L 9 This indicates a single bond or a divalent linker. Preferably, L 9 It can be a single bond, substituted, or unsubstituted C. 6-30 aryl, or substituted or unsubstituted C 6-30 Cycloalkylene.

[0119] In equation (12), n4 is 0 or 1. It should be understood that when n4 is 0, the part represented by -OC(O)- is a single bond, such that L... 9 It is directly attached to the alkenyl (vinyl) carbon atom.

[0120] In equation (12), Ar 1 It is the replacement of C 5-60 An aromatic group, optionally comprising one or more aromatic cyclic heteroatoms selected from N, O, S, or combinations thereof, wherein the aromatic group may be monocyclic, non-fused polycyclic, or fused polycyclic. When C 5-60 When the aromatic group is polycyclic, the ring or cyclic group can be fused (such as naphthyl), non-fused, or a combination thereof. When the polycyclic C... 5-60When aromatic groups are non-fused, rings or cyclic groups can be directly linked (e.g., biaryl, biphenyl, etc.) or bridged by heteroatoms (e.g., triphenylamino or diphenylene ether). In some respects, polycyclic C 5-60 Aromatic groups can include combinations of fused rings and directly linked rings (such as binaphthyl groups).

[0121] In equation (12), y can be an integer from 1 to 12, preferably from 1 to 6, and typically from 1 to 3. Each R x It can be hydrogen or methyl independently.

[0122] Non-limiting examples of monomers having formula (10), (11), or (12) include one or more of the following:

[0123]

[0124]

[0125] Where Y 1 As stated above, and R i It is defined as in equations (10)-(12).

[0126] When present, the polymer typically contains repeating units comprising polar groups (side-attached to the polymer backbone) in amounts of 1 to 60 mol%, typically 5 to 50 mol%, and more typically 5 to 40 mol%, based on the total repeating units in the polymer.

[0127] Non-limiting exemplary polymers of the present invention include one or more of the following:

[0128]

[0129]

[0130]

[0131] Each of x, y, and z is the mole fraction of the relevant repeating unit, and the sum of the mole fractions of each polymer is 1.

[0132] Polymers can be prepared using any suitable method or one method in the art. For example, one or more monomers corresponding to the repeating units described herein can be fed together or separately using suitable solvents or initiators and polymerized in a reactor. For example, polymers can be obtained by polymerizing the respective monomers under any suitable conditions, such as by heating at an effective temperature, irradiating with photochemical radiation at an effective wavelength, or a combination thereof.

[0133] The photoresist composition also comprises a photoacid generator (PAG). A suitable PAG generates an acid that causes the acid-indestructible groups present on the polymer of the photoresist composition to cleave during post-exposure baking (PEB). The PAG can be in a non-polymeric or polymeric form, for example, present in repeating units of the polymerization of polymers as described above, or as part of a different polymer. A suitable non-polymeric PAG compound can have the formula G. + A - G + It is an organic cation selected from iodonium cations substituted with two alkyl groups, two aryl groups, or combinations of alkyl and aryl groups; and sulfonium cations substituted with three alkyl groups, three aryl groups, or combinations of alkyl and aryl groups; and A - It is a non-polymerizable organic anion. In some embodiments, PAG may be included as a non-polymerizable PAG compound, as a repeating unit of a polymer having a PAG moiety derived from a polymerizable PAG monomer, or as a combination thereof.

[0134] Particularly suitable nonpolymeric organic anions include those whose conjugate acids have a pKa of -15 to 1. Particularly preferred anions are fluorinated alkyl sulfonates and fluorinated sulfonamides.

[0135] Useful non-polymerized PAG compounds are known in the field of chemically enhanced photoresists and include, for example, onium salts such as triphenylsulfonium trifluoromethane sulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethane sulfonate, tri(p-tert-butoxyphenyl)sulfonium trifluoromethane sulfonate, triphenylsulfonium p-toluene sulfonate; di-tert-butylphenyliodomonium perfluorobutane sulfonate and di-tert-butylphenyliodomonium camphor sulfonate. It is also known that nonionic sulfonates and sulfonyl compounds act as photoacid generators, such as nitrobenzyl derivatives, such as 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate, and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonates, such as 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives, such as bis(benzenesulfonyl)diazomethane and bis(p-toluenesulfonyl)diazomethane; ethylene glycol Oxime 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 nonpolymeric photoacid generators are further described in U.S. Patent No. 8,431,325 to Hashimoto et al., in columns 37, lines 11-47 and 41-91. Other suitable sulfonate PAGs include sulfonated esters and sulfonyloxyketones, nitrobenzyl esters, s-triazine derivatives, benzoin toluenesulfonate, α-(p-toluenesulfonyloxy)acetic acid tert-butylphenyl ester, and α-(p-toluenesulfonyloxy)acetic acid tert-butyl ester; as described in U.S. Patent Nos. 4,189,323 and 8,431,325.

[0136] Typically, when a photoresist composition contains a nonpolymerized photoacid generator, it is present in the photoresist composition in an amount of 1 to 65 wt%, more typically 2 to 20 wt%, based on the total solids of the photoresist composition.

[0137] In some embodiments, G + It can be a sulfonium cation or an iodonium cation. For example, G + It could be as described in this article regarding M. + The sulfonium cation, or G + It could be as described in this article regarding M. + The iodine-onium cation. When the photoresist composition further comprises PAG, the cation G + Can be used with M +Same, or cation G + Can be used with M + different.

[0138] PAGs that are onium salts typically contain organic anions with sulfonate groups or non-sulfonate groups, such as sulfonamidate, sulfonimidate, methylation, or borate.

[0139] Exemplary organic anions having a sulfonate group include the following:

[0140]

[0141]

[0142] Exemplary nonsulfonated anions include the following:

[0143]

[0144]

[0145] The photoresist composition may optionally contain a variety of PAGs. The PAGs may be polymeric, non-polymeric, or may include both polymeric and non-polymeric PAGs. Preferably, each of the multiple PAGs is non-polymeric.

[0146] In one or more aspects, the photoresist composition may include a first photoacid generator comprising a sulfonate group on an anion, and the photoresist composition may include a non-polymerized second photoacid generator, wherein the second photoacid generator may include an anion without a sulfonate group.

[0147] In some respects, the polymer may optionally further comprise repeating units containing a PAG moiety. For example, repeating units derived from one or more monomers having formula (13):

[0148]

[0149] In equation (13), R j It can be hydrogen, fluorine, cyano, or substituted or unsubstituted C. 1-10 Alkyl group. Preferably, R j It is hydrogen, fluorine, or substituted or unsubstituted C. 1-5 Alkyl group, typically methyl group. Q 1 It can be a single bond or a divalent linker. Preferably, Q 1 It may contain 1 to 10 carbon atoms and at least one heteroatom, more preferably -C(O)-O-.

[0150] In equation (13), A 1 It can be one or more of the following: substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Hybrid aryl. Preferably, A 1 divalent C can be arbitrarily substituted 1-30 Perfluoroalkylene groups.

[0151] In equation (13), Z - It is the anionic moiety, and its conjugate acid typically has a pKa of -15 to 1. Z - It can be a sulfonate, carboxylate, sulfonamide anion, sulfonamide anion, or methyl anion. Particularly preferred anionic moieties are fluorinated alkyl sulfonates and fluorinated sulfonamides. G + It is an organic cation as defined above. In some embodiments, G + It is an iodonium cation substituted with two alkyl groups, two aryl groups, or a combination of alkyl and aryl groups; or a sulfonium cation substituted with three alkyl groups, three aryl groups, or a combination of alkyl and aryl groups.

[0152] An exemplary monomer having formula (13) may include the following:

[0153]

[0154] Among them G + It is an organic cation.

[0155] When included, the polymer may contain repeating units comprising the PAG portion in an amount of 1 to 15 mol%, typically 1 to 8 mol%, more typically 2 to 6 mol%, based on the total repeating units in the polymer.

[0156] Photoresist compositions may contain molecular glass compounds. Molecular glass compounds are tetrameric calixarnes[4] having free hydroxyl groups modified with acetal chemistry to contain base-stable but acid-crackable aromatic protecting groups, as provided in U.S. Patent No. 8,936,000B2. Photoresist compositions may contain 50 to 99 wt%, preferably 55 to 95 wt%, more preferably 60 to 90 wt%, and even more preferably 65 to 90 wt% of the total weight of solids. It will be understood that, in this context, “molecular glass compound” as used in the context of components in a photoresist may mean only the molecular glass compound, or a combination of the molecular glass compound with another molecular glass compound or polymer useful in the photoresist.

[0157] The photoresist composition further includes a solvent for dissolving the components of the composition and promoting its coating on a substrate. Preferably, the solvent is an organic solvent commonly used in the manufacture of electronic devices. Suitable solvents include, for example: aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, and 1-chlorohexane; alcohols such as methanol, ethanol, 1-propanol, isopropanol, tert-butanol, 2-methyl-2-butanol, 4-methyl-2-pentanol, and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone); propylene glycol monomethyl ether (PGME); ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and anisole; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2- Heptanone and cyclohexanone (CHO); esters, such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), methyl hydroxyisobutyrate (HBM), and ethyl 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.

[0158] The total solvent content (i.e., the cumulative solvent content of all solvents) in the photoresist composition is typically 40 to 99 wt%, for example 70 to 99 wt%, or 85 to 99 wt%, based on the total solids of the photoresist composition. The desired solvent content will depend, for example, on the desired thickness of the photoresist layer being coated and the coating conditions.

[0159] The polymer can typically be present in the photoresist composition in an amount of 10 to 99.9 wt%, typically 25 to 99 wt%, and more typically 50 to 95 wt% of the total solids based on the photoresist composition. It will be understood that "total solids" includes the photoactive compound, the polymer, PAG, and other non-solvent components.

[0160] In some aspects, the photoresist composition may further comprise a material containing one or more base-indestructible groups (“base-indestructible material”). As mentioned herein, a base-indestructible group is a functional group that can undergo a cleavage reaction in the presence of an aqueous base developer after the exposure step and the post-exposure baking step to provide a polar group (such as hydroxyl, carboxylic acid, sulfonic acid, etc.). The base-indestructible group will not react significantly prior to the development step of the photoresist composition containing the base-indestructible group (e.g., will not undergo a bond-breaking reaction). Therefore, for example, the base-indestructible group will be substantially inert during the pre-exposure soft baking step, the exposure step, and the post-exposure baking step. “Substantially inert” means that ≤5%, typically ≤1%, of the base-indestructible group (or portion) will decompose, cleave, or react during the pre-exposure soft baking step, the exposure step, and the post-exposure baking step. The base-indestructible group is reactive under typical photoresist development conditions using, for example, an aqueous base photoresist developer (such as an aqueous solution of 0.26 standard (N) tetramethylammonium hydroxide (TMAH)). For example, a 0.26N aqueous solution of TMAH can be used for single-immersion development or dynamic development, where, for example, 0.26N of TMAH developer is dispensed onto the imaged photoresist layer for a suitable duration (e.g., 10 to 120 seconds). Exemplary base-insecure groups are ester groups, typically fluorinated ester groups. Preferably, the base-insecure material is substantially immiscible with the polymer and other solid components of the photoresist composition and has a lower surface energy than them. Thus, when coated onto a substrate, the base-insecure material can separate from the other solid components of the photoresist composition and reach the top surface of the formed photoresist layer.

[0161] In some respects, alkali-insecure materials can be polymeric materials that may contain one or more repeating units containing one or more alkali-insecure groups (also referred to herein as alkali-insecure polymers). For example, an alkali-insecure polymer may contain repeating units containing two or more identical or different alkali-insecure groups. Preferred alkali-insecure polymers contain at least one repeating unit containing two or more alkali-insecure groups, such as repeating units containing two or three alkali-insecure groups.

[0162] Base-unstable polymers can be polymers comprising repeating units derived from one or more monomers having formula (14a):

[0163]

[0164] Where X e It is selected from the following polymerizable groups: substituted or unsubstituted C 2-20 Alkenyl, or substituted or unsubstituted (meth)acryloyl, L 10It can include the following divalent linking groups: for example, substituted or unsubstituted C 1-20 Alkylene, substituted or unsubstituted C 3-20 One or more of the following: cycloalkylene, -C(O)-, or -C(O)O-; and R n Is it substituted or unsubstituted C? 1-20 Fluoroalkyl, provided that the carbon atom of the carbonyl group (C=O) bonded to formula (14a) is replaced by at least one fluorine atom.

[0165] An exemplary monomer having formula (14a) may include the following:

[0166]

[0167] Base-instable polymers may comprise repeating units containing two or more base-instable groups. For example, a base-instable polymer may comprise repeating units derived from one or more monomers having formula (14b):

[0168]

[0169] Where X f and R p These are respectively, for X in equation (14a) e and R n Defined; L 11 It includes substituted or unsubstituted C 1-20 Alkylene, substituted or unsubstituted C 3-20 One or more of the following polyvalent linkages: cycloalkylene, -C(O)-, or -C(O)O-; and n4 is an integer of 2 or greater, such as 2 or 3.

[0170] An exemplary monomer having formula (14b) may include the following:

[0171]

[0172] Base-instable polymers may comprise repeating units containing one or more base-instable groups. For example, a base-instable polymer may comprise repeating units derived from one or more monomers having formula (14c):

[0173]

[0174] Where X g and R q These are respectively, for X in equation (14a) e and R n Defined; L 12 It is a divalent linker; and L 13 Is it substituted or unsubstituted C? 1-20Fluoride, wherein the carbon atom bonded to the carbonyl group (C=O) in formula (14c) is replaced by at least one fluorine atom.

[0175] An exemplary monomer having formula (14c) may include the following:

[0176]

[0177] In another preferred aspect of the invention, the alkali-instable polymer may comprise one or more alkali-instable groups and one or more acid-instable groups, such as one or more acid-instable ester moieties (e.g., tert-butyl ester) or acid-instable acetal groups. For example, the alkali-instable polymer may comprise repeating units containing both alkali-instable and acid-instable groups, i.e., wherein both alkali-instable and acid-instable groups are present on the same repeating unit. In another example, the alkali-instable polymer may comprise a first repeating unit containing an alkali-instable group and a second repeating unit containing an acid-instable group. Preferred photoresists of the present invention can exhibit reduced defects associated with resist relief images formed from photoresist compositions.

[0178] Base-instable polymers can be prepared using any suitable method in the art, including those described herein with respect to the first and second polymers. For example, base-instable polymers can be obtained by polymerization of the respective monomers under any suitable conditions, such as by heating at an effective temperature, irradiation with photochemical radiation at an effective wavelength, or a combination thereof. Furthermore or alternatively, suitable methods can be used to graft one or more base-instable groups onto the polymer backbone.

[0179] In some respects, alkali-instable materials are single molecules comprising one or more alkali-instable ester groups, preferably one or more fluorinated ester groups. Alkali-instable materials that are single molecules typically have an M value in the range of 50 to 1,500 Da. W Exemplary alkali-instable materials include the following:

[0180]

[0181] When present, alkali-instable materials are typically present in the photoresist composition in an amount of 0.01 to 10 wt% or 1 to 5 wt% of the total solids based on the photoresist composition.

[0182] In addition or alternatively, besides alkali-instable polymers, the photoresist composition may further include one or more polymers other than those described above. For example, the photoresist composition may contain additional polymers as described above but with different compositions, or polymers similar to those described above but not containing each of the required repeating units. In addition or alternatively, the one or more additional polymers may include those well known in the field of photoresists, such as those selected from: polyacrylates, polyvinyl ethers, polyesters, polynorbornene, polyacetals, polyethylene glycol, polyamides, polyacrylamide, polyphenols, phenolic varnishes, styrene polymers, polyvinyl alcohol, or combinations thereof.

[0183] The photoresist composition may further include one or more additional optional additives. For example, optional additives may include photochemical dyes and contrast dyes, anti-stripping agents, plasticizers, accelerators, sensitizers, photodegradable quenchers (PDQ) (and also referred to as photodegradable bases), alkaline quenchers, hot acid generators, surfactants, etc., or combinations thereof. If present, optional additives are typically present in the photoresist composition in an amount of 0.01 to 10 wt% based on the total solids of the photoresist composition.

[0184] PDQ generates a weak acid upon irradiation. The acid generated by the photodegradable quencher is not strong enough to react rapidly with the acid-instable groups present in the resist matrix. Exemplary photodegradable quenchers include, for example, photodegradable cations, and are preferably also used to prepare strong acid generating compounds, which react with the anions of weak acids (pKa>1) (e.g., C). 1-20 Carboxylic acid or C 1-20 Those sulfonic acids that are paired with the anion of the sulfonic acid. Exemplary carboxylic acids include formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexanecarboxylic acid, benzoic acid, salicylic acid, etc. Exemplary carboxylic acids include p-toluenesulfonic acid, camphorsulfonic acid, etc. In a preferred embodiment, the photodegradable quencher is a photodegradable organic zwitterionic compound, such as diphenyliodonium-2-carboxylic acid ester.

[0185] Photodegradable quenchers can be in non-polymeric or polymerically bonded forms. When in polymeric form, the photodegradable quencher is present in polymeric units on a first or second polymer. Polymeric units containing the photodegradable quencher are typically present in amounts of 0.1 to 30 mol%, typically 1 to 10 mol%, and more typically 1 to 2 mol%, based on the total repeating units in the polymer.

[0186] Exemplary basic quenchers include, for example: straight-chain aliphatic amines such as tributylamine, trioctylamine, triisopropanolamine, tetra(2-hydroxypropyl)ethylenediamine, n-tert-butyldiethanolamine, tris(2-acetoxy-ethyl)amine, 2,2',2”,2”'-(ethane-1,2-diylbis(azanetriyl))tetraethanol, 2-(dibutylamino)ethanol, and 2,2',2”-nitrotriethanol; cyclic aliphatic amines, such as 1-(tert-butoxycarbonyl)-4-hydroxypiperidine, tert-butyl 1-pyrrolidinecarboxylate, tert-butyl 2-ethyl-1H-imidazolium-1-carboxylate, di-tert-butyl piperazine-1,4-dicarboxylate, and N-(2-acetoxy-ethyl)morpholine; aromatic amines, such as pyridine, di-tert-butylpyridine, and pyridinium; linear and cyclic amides and their derivatives, such as N,N-bis(2-hydroxyethyl)palmitamide, N,N-diethylacetamide, N... 1 N 1 N 3 N 3 -Tetrabutylmalonamide, 1-methylazacycloheptan-2-one, 1-allylazacycloheptan-2-one and tert-butyl 1,3-dihydroxy-2-(hydroxymethyl)propyl-2-ylcarbamate; ammonium salts, such as quaternary ammonium salts of sulfonates, aminosulfonates, carboxylates and phosphonates; imines, such as primary and secondary aldehyde imines and ketimines; diazines, such as optionally substituted pyrazines, piperazines and phenazines; diazoles, such as optionally substituted pyrazoles, thiadiazoles and imidazoles; and optionally substituted pyrrolidones, such as 2-pyrrolidone and cyclohexylpyrrolidine.

[0187] The alkaline quencher can be in non-polymeric or polymeric form. When in polymeric form, the quencher can be present in repeating units of the polymer. Repeating units containing the quencher are typically present in an amount of 0.1 to 30 mol%, preferably 1 to 10 mol%, and more preferably 1 to 2 mol%, based on the total repeating units in the polymer.

[0188] Exemplary surfactants include fluorinated and nonfluorinated surfactants and can be ionic or nonionic, with nonionic surfactants being preferred. Exemplary fluorinated nonionic surfactants include perfluorinated C4 surfactants, such as FC-4430 and FC-4432 surfactants available from 3M Corporation; and fluorinated glycols, such as POLYFOX PF-636, PF-6320, PF-656, and PF-6520 fluorinated surfactants from Omnova. In this aspect, the photoresist composition further comprises a surfactant polymer containing fluorinated repeating units.

[0189] A patterning method using the photoresist composition of the present invention will now be described. Suitable substrates on which the photoresist composition can be coated include electronic device substrates. A wide variety of electronic device substrates can be used in the present invention, such as: semiconductor wafers; polycrystalline silicon substrates; packaging substrates, such as multi-chip modules; flat panel display substrates; substrates for light-emitting diodes (LEDs) including organic light-emitting diodes (OLEDs); etc., wherein semiconductor wafers are typical. Such substrates are typically composed of one or more of silicon, polycrystalline silicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanide, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. Suitable substrates can be in the form of wafers, such as those used for manufacturing integrated circuits, optical sensors, flat panel displays, integrated optical circuits, and LEDs. Such substrates can be of any suitable size. Typical wafer substrate diameters are 200 to 300 millimeters (mm), although wafers with smaller and larger diameters can be suitably used according to the present invention. The substrate may include one or more layers or structures that may optionally include active or operable portions of the formed device.

[0190] Typically, prior to coating the photoresist composition of the present invention, one or more photolithographic layers, such as hard mask layers (e.g., spin-coated carbon (SOC), amorphous carbon, or metal hard mask layers), CVD layers (e.g., silicon nitride (SiN), silicon oxide (SiO), or silicon oxynitride (SiON) layers), organic or inorganic underlayers, or combinations thereof, are provided on the upper surface of the substrate. These layers, together with the externally coated photoresist layer, form a photolithographic material stack.

[0191] Optionally, an adhesion promoter layer may be applied to the substrate surface prior to coating the photoresist composition. If an adhesion promoter is desired, any suitable adhesion promoter for polymer films may be used, such as silanes, typically organosilanes like trimethoxyvinylsilane, triethoxyvinylsilane, hexamethyldisilazane, or aminosilane coupling agents like γ-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those sold from DuPont Electronics & Imaging (Marlborough, Massachusetts) under the names AP 3000, AP 8000, and AP 9000S.

[0192] Photoresist compositions can be coated onto a substrate by any suitable method, including spin coating, spraying, dip coating, blade coating, etc. For example, applying a photoresist layer can be accomplished by spin coating the photoresist in a solvent using a coating track, wherein the photoresist is dispensed onto a rotating wafer. During dispensing, the wafer is typically rotated at a speed of up to 4,000 rpm, for example, 200 to 3,000 rpm, for a period of 15 to 120 seconds to obtain a photoresist composition layer on the substrate. Those skilled in the art will understand that the thickness of the coated layer can be adjusted by varying the rotation speed and / or the total solids of the composition. Photoresist layers formed from the compositions of the present invention typically have a dry layer thickness of 10 to 500 nanometers (nm), preferably 15 to 200 nm, and more preferably 20 to 120 nm.

[0193] Next, the photoresist composition is typically soft-baked to minimize the solvent content in the layer, thereby forming a non-stick coating and improving the layer's adhesion to the substrate. Soft baking is typically performed, for example, on a heated plate or in an oven, with a heated plate being typical. The soft baking temperature and time will depend, for example, on the photoresist composition and thickness. Soft baking temperatures are typically 80°C to 170°C, and more typically 90°C to 150°C. Soft baking times are typically 10 seconds to 20 minutes, more typically 1 minute to 10 minutes, and even more typically 1 minute to 2 minutes. Those skilled in the art can readily determine the heating time based on the composition's components.

[0194] Next, the photoresist layer is patterned and exposed to activating radiation to create a solubility difference between the exposed and unexposed areas. The exposure of the photoresist composition to radiation that activates the composition, as described herein, indicates that radiation can form a latent image in the photoresist composition. Exposure is typically performed using a patterned photomask with optically transparent and optically opaque regions corresponding to the areas of the photoresist layer to be exposed and the areas of the unexposed photoresist layer, respectively. Alternatively, this exposure can be performed without a photomask in a direct-write method, typically used in electron beam lithography. The activating radiation typically has wavelengths less than 400 nm, less than 300 nm, or less than 200 nm, with wavelengths of 248 nm (KrF), 193 nm (ArF), 13.5 nm (EUV), or electron beam lithography being preferred. Preferably, the activating radiation is 193 nm radiation or EUV radiation. This method can be used in immersion or dry (non-immersion) lithography techniques. The energy exposed is typically 1 to 200 millijoules per square centimeter (mJ / cm²). 2 ), preferably 10 to 100 mJ / cm 2 And more preferably 20 to 50 mJ / cm 2This depends on the composition of the exposed tool and the photoresist composition.

[0195] After the photoresist layer is exposed, post-exposure baking (PEB) of the exposed photoresist layer is performed. PEB can be performed, for example, on a heated plate or in an oven, with a heated plate being typical. The conditions of PEB will depend, for example, on the photoresist composition and the layer thickness. PEB is typically performed at a temperature of 70°C to 150°C, preferably 75°C to 120°C, for a time of 30 to 120 seconds. A latent image is formed in the photoresist, defined by polarity-converted regions (exposed regions) and non-polarity-converted regions (unexposed regions).

[0196] The exposed photoresist layer is then developed with a suitable developer to selectively remove areas of the layer that are soluble in the developer while retaining insoluble areas, forming the resulting photoresist pattern relief image. In the case of a positive development (PTD) process, the exposed areas of the photoresist layer are removed during development, while the unexposed areas are retained. Conversely, in a negative development (NTD) process, the exposed areas of the photoresist layer are retained during development, while the unexposed areas are removed. The application of the developer can be accomplished by any suitable method, as described above regarding the application of the photoresist composition, with spin coating being typical. The development time is the period of time during which the soluble areas of the photoresist are effectively removed, typically 5 to 60 seconds. Development is typically performed at room temperature.

[0197] Suitable developers for PTD processes include aqueous alkaline developers, such as quaternary ammonium hydroxide solutions, such as tetramethylammonium hydroxide (TMAH) (preferably 0.26 standard (N) TMAH), tetraethylammonium hydroxide, tetrabutylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. Suitable developers for NTD processes are based on organic solvents, meaning that the cumulative content of organic solvents in the developer is 50 wt% or more, typically 95 wt% or more, 98 wt% or more, or 100 wt% based on the total weight of the developer. Suitable organic solvents for NTD developers include, for example, those selected from ketones, esters, ethers, hydrocarbons, and mixtures thereof. Typical NTD developers are 2-heptanone or n-butyl acetate.

[0198] The coated substrate can be formed from the photoresist composition of the present invention. Such a coated substrate comprises: (a) a substrate having one or more layers to be patterned on its surface; and (b) a photoresist composition layer on said one or more layers to be patterned.

[0199] Photoresist patterns can be used, for example, as an etch mask to transfer the pattern to one or more sequentially arranged underlying layers using known etch techniques, typically dry etching (such as reactive ion etching). Photoresist patterns can also be used, for example, to transfer a pattern to an underlying hard mask layer, which in turn serves as an etch mask for transferring the pattern to one or more layers below the hard mask layer. If the photoresist pattern is not lost during pattern transfer, it can be removed from the substrate using known techniques (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.

[0200] The invention is further illustrated by the following examples.

[0201] Example

[0202] Synthetic Examples. The synthetic reactions were carried out under normal pressure. All chemicals were used as is, without further purification, from the commercial suppliers.

[0203] Synthesis of Triphenylsulfonium α-cyanocinnamate (PAC1)

[0204]

[0205] A solution was prepared by combining 5 g of α-cyanocinonic acid (28.87 mmol) and tetrahydrofuran (75 mL, THF). 1 g of LiOH in 15 mL of deionized (DI) water was added to the solution, and the resulting mixture was stirred at room temperature (approximately 25 °C) for 1 hour. THF was then removed under reduced pressure to yield lithium α-cyanocinonate. 50 mL of DI water, 75 mL of dichloromethane (DCM), and 9.9 g of triphenylsulfonium bromide (28.87 mmol) were added to the lithium α-cyanocinonate solution, and the mixture was stirred at room temperature (approximately 25 °C) for 4 hours. The organic phase was then washed with DI water (5 × 50 mL). The organic phase was separated from the aqueous phase, and the solvent was removed under reduced pressure to yield the crude photoactive compound PAC1. The crude product was dissolved in 20 mL of acetone, and this solution was poured into 150 mL of heptane to produce a colorless precipitate of PAC1. The precipitate was separated by filtration and dried to provide a colorless solid. The yield of PAC1 was 3.4 g (35%). Proton nuclear magnetic resonance spectroscopy (PTN) 1¹H-NMR (in acetone-d6), chemical shifts (δ, parts per million (ppm)): 8.10 (m, 7H), 7.80 (m, 11H, ArH), 7.40 (m, 3H). Purity was 99.21% as determined by ultraviolet (UV) absorbance at 210 nm using high-performance liquid chromatography (UPLC).

[0206] Synthesis of bis(4-(tert-butyl)phenyl)iodonium α-cyanocinonate (PAC2)

[0207] A solution was prepared by combining 10.0 g of α-cyanocinonic acid (57.74 mmol) and 150 mL of THF. 2 g of LiOH in 25 mL of DI water was added to the solution, and the resulting mixture was stirred at room temperature (approximately 25 °C) for 1 hour. THF was then removed under reduced pressure to yield lithium α-cyanocinonate. 100 mL of DI water, 150 mL of DCM, and 24.8 g of bis(4-(tert-butyl)phenyl)acetic acid iodonium (54.82 mmol) were added to the lithium α-cyanocinonate solution, and the mixture was stirred at room temperature (approximately 25 °C) for 4 hours. The organic phase was then washed with DI water (5 × 100 mL). The organic phase was separated from the aqueous phase, and the solvent was removed under reduced pressure to yield the crude photoactive compound PAC2. The crude product was dissolved in 40 mL of acetone, and this solution was poured into 300 mL of heptane to produce a colorless precipitate of PAC2. The precipitate was separated by filtration and dried to provide a colorless solid. The yield of PAC2 was 21.7 g (66.5%). 1 ¹H NMR (in acetone-d6), δ (ppm): 7.89 (m, 4H, ArH), 7.78 (m, 3H, ArH), 7.38 (m, 7H), 1.21 (s, 18H, 6(CH₃)). UPLC purity was 99.30%, as determined by UV absorbance at 210 nm.

[0208] Synthesis of bis(4-(tert-butyl)phenyl)iodonium-4-trifluoromethylcinnamate (PAC3)

[0209] A solution was prepared by combining 5.0 g of 4-trifluoromethylcinnamic acid (23.13 mmol) and 150 mL of THF. 0.8 g of LiOH in 25 mL of DI water was added to the solution, and the resulting mixture was stirred at room temperature (approximately 25 °C) for 1 hour. THF was then removed under reduced pressure to yield lithium 4-trifluoromethylcinnamate. 100 mL of DI water, 150 mL of DCM, and 10.4 g of bis(4-(tert-butyl)phenyl)acetic acid iodonium (23.0 mmol) were added to the lithium 4-trifluoromethylcinnamate solution, and the mixture was stirred at room temperature (approximately 25 °C) for 4 hours. The organic phase was then washed with DI water (5 × 50 mL). The organic phase was separated from the aqueous phase, and the solvent was removed under reduced pressure to yield the crude photoactive compound PAC3. The crude product was dissolved in 20 mL of acetone, and this solution was poured into 150 mL of heptane to produce PAC3 as a colorless precipitate. The precipitate was separated by filtration and dried to provide a colorless solid. The yield of PAC3 was 8.9 g (63.5%). 1 ¹H NMR (in acetone-d6), δ (ppm): 7.90 (d, 4H, ArH), 7.53 (d, 2H, ArH), 7.49 (d, 2H, ArH), 7.38 (d, 4H, ArH), 7.22 (d, 1H, CH=CH), 6.42 (d, 1H, CH=CH), 1.19 (s, 18H, 6(CH₃)). UPLC purity was 99.30%, as determined by UV absorbance at 210 nm.

[0210] Synthesis of bis(4-(tert-butyl)phenyl)iodonium(Z)-3-fluoro-3-phenylacrylate (PAC4)

[0211] A solution was prepared by combining 1.0 g of α-fluorocinnamic acid (6.0 mmol) and 10 mL of THF. 0.2 g of LiOH in 5 mL of DI water was added to the solution, and the resulting mixture was stirred at room temperature (approximately 25 °C) for 1 hour. THF was then removed under reduced pressure to yield lithium α-fluorocinnamate. 10 mL of DI water, 10 mL of DCM, and 2.0 g of bis(4-(tert-butyl)phenyl)acetic acid iodonium (4.42 mmol) were added to the lithium α-fluorocinnamate, and the mixture was stirred at room temperature (approximately 25 °C) for 4 hours. The organic phase was then washed with DI water (5 × 15 mL). The organic phase was separated from the aqueous phase, and the solvent was removed under reduced pressure to yield a crude, optically active compound, PAC4, as a white solid. The crude product was suspended in 25 mL of heptane, separated by filtration, and dried to yield a white solid. The yield of PAC4 was 2.2 g (65.5%). 1¹H NMR (in acetone-d6), δ (ppm): 8.12 (d, 4H, ArH), 7.50 (m, 6H, ArH), 7.33–7.26 (m, 3H, ArH), 6.50 (d, 1H, CH=CF), 1.20 (s, 18H, 6(CH₃)). UPLC purity was 99.92%, as determined by UV absorbance at 210 nm.

[0212] Synthesis of bis(4-(tert-butyl)phenyl)iodonium(E)-3-cyclohexyl acrylate (PAC5)

[0213] A solution was prepared by combining 1.0 g (E)-3-cyclohexylacrylic acid (6.48 mmol) and 10 mL THF. 0.15 g LiOH in 5 mL DI water was added to the solution, and the resulting mixture was stirred at room temperature (approximately 25 °C) for 1 hour. THF was then removed under reduced pressure to yield lithium 3-cyclohexylacrylate. 10 mL DI water, 10 mL DCM, and 2.0 g bis(4-(tert-butyl)phenyl)acetic acid iodonium (4.42 mmol) were added to the lithium 3-cyclohexylacrylate, and the mixture was stirred at room temperature (approximately 25 °C) for 4 hours. The organic phase was then washed with DI water (5 × 15 mL). The organic phase was separated from the aqueous phase, and the solvent was removed under reduced pressure to yield a crude, optically active compound, PAC5, as a white solid. The crude product was suspended in 25 mL heptane, separated by filtration, and dried to yield a white solid. The yield of PAC5 was 1.7 g (47.9%). 1 ¹H NMR (in acetone-d6), δ (ppm): 7.83 (d, 4H, ArH), 7.39 (d, 4H, ArH), 6.51 (2H, CH=CH), 5.75 (d, 1H, CH=CH), 2–1.75 (6H, aliphatic-H), 1.19 (s, 18H, 6(CH3)), 1.18–1.08 (m, 5H, aliphatic-H). UPLC purity was 99.66%, as determined by UV absorbance at 210 nm.

[0214] Synthesis of bis(4-(tert-butyl)phenyl)iodonium(E)-3-(4-iodophenyl)acrylate (PAC6)

[0215] A solution was prepared by combining 1.0 g (E)-3-(4-iodophenyl)acrylic acid (3.65 mmol) and 10 mL THF. 0.15 g LiOH in 5 mL DI water was added to the solution, and the resulting mixture was stirred at room temperature (approximately 25 °C) for 1 hour. THF was then removed under reduced pressure to yield lithium 3-cyclohexylacrylate. 10 mL DI water, 10 mL DCM, and 1.5 g bis(4-(tert-butyl)phenyl)acetic acid iodonium (3.32 mmol) were added to the lithium 3-cyclohexylacrylate solution, and the mixture was stirred at room temperature (approximately 25 °C) for 4 hours. The organic phase was then washed with DI water (5 × 15 mL). The organic phase was separated from the aqueous phase, and the solvent was removed under reduced pressure to yield a crude, optically active compound, PAC6, as a white solid. The crude product was suspended in 25 mL heptane, separated by filtration, and dried to yield a white solid. The yield of PAC6 was 1.7 g (70.8%). 1 ¹H NMR (in acetone-d6), δ (ppm): 8.06 (d, 4H, ArH), 7.67 (d, 2H, ArH), 7.46 (d, 4H, ArH), 7.26 (d, 2H, ArH), 6.93 (2H, CH=CH), 6.33 (d, 1H, CH=CH), 1.21 (s, 18H, 6(CH₃)). UPLC purity was 99.88%, as determined by UV absorbance at 210 nm.

[0216] Synthesis of Triphenylsulfonium Cinnamate (PAC7)

[0217]

[0218] A solution was prepared by combining 10.0 g of cinnamic acid (67.49 mmol), 200 mL of acetone, and 200 mL of dihydrate (DI). Then, 7.0 g (30.2 mmol) of silver oxide was added to the solution in a small fraction. The resulting mixture was stirred at room temperature (approximately 25 °C) for 48 hours. The precipitate was separated by filtration, washed with acetone, and dried under reduced pressure. The yield of silver cinnamate was 13.5 g.

[0219] 5.0 g of silver cinnamate (5.0 g, 19.6 mmol) was dissolved in 150 mL of methanol and 30 mL of DI water to form a solution, and then 6.0 g of triphenylsulfonium bromide (17.47 mmol) was added to the solution. The reaction mixture was stirred at room temperature (approximately 25 °C) for 12 hours. The reaction mixture... 1¹H NMR showed that the desired product had a cation to anion ratio of 1:1. The mixture was filtered to remove undissolved salts and the solvent was removed under reduced pressure. The resulting residue was dissolved in acetone and filtered through a diatomaceous earth plug. The solvent was removed from the filtrate under reduced pressure to produce PAC7 as a colorless oil. The yield of PAC7 was 1.7 g (70.8%). 1 ¹H-NMR (in acetone-d6), δ (ppm): 8.08 (m, 6H, ArH), 7.88–7.78 (m, 9H, ArH), 7.41 (m, 2H), 7.27 (m, 2H, ArH), 7.20 (m, 2H, ArH), 6.50 (d, 1H, CH=CH). UPLC purity was 99.75%, as determined by UV absorbance at 210 nm.

[0220] Synthesis of Triphenylsulfonium Benzoate (CPAC8)

[0221] A solution was prepared by combining 5.0 g of benzoic acid (18.42 mmol), 100 mL of acetone, and 100 mL of dihydrate (DI). Then, 4.27 g (18.42 mmol) of silver oxide was added to the solution in a small fraction. The resulting mixture was stirred at room temperature (approximately 25 °C) for 48 hours. The precipitate was separated by filtration, washed with acetone, and dried under reduced pressure. The yield of silver benzoate was 7.3 g.

[0222] 2.5 g of silver benzoate (10.9 mmol) was dissolved in 100 mL of methanol and 20 mL of DI water to form a solution, and then 2.5 g of triphenylsulfonium bromide (7.28 mmol) was added to the solution. The reaction mixture was stirred at room temperature (approximately 25 °C) for 12 hours. The reaction mixture... 1 ¹H-NMR showed that the desired product had a cation to anion ratio of 1:1. The mixture was filtered to remove undissolved salts and the solvent was removed under reduced pressure. The resulting residue was dissolved in acetone and filtered through a diatomaceous earth stopper. The solvent was removed from the filtrate under reduced pressure to produce CPAC8, a colorless oil. The UPLC purity was 99.63%, as determined by UV absorbance at 210 nm.

[0223] Synthesis of triphenylsulfonium (E)-3-(thiophene-3-yl)acrylate (CPAC9)

[0224] A solution was prepared by combining 2.55 g of (E)-3-(thiophen-3-yl)acrylic acid (16.2 mmol), 50 mL of acetone, and 50 mL of DI water, and then 1.80 g (7.76 mmol) of silver oxide was added to the solution in a small fraction. The resulting mixture was stirred at room temperature (approximately 25 °C) for 48 hours. The precipitate was separated by filtration, washed with acetone, and then dried under reduced pressure. The yield of silver (E)-3-(thiophen-3-yl)acrylate was 3.30 g.

[0225] 3.30 g of (E)-3-(thiophene-3-yl)silver acrylate (10.9 mmol) was dissolved in 100 mL of methanol and 20 mL of DI water to form a solution, and then 3.48 g of triphenylsulfonium bromide (10.0 mmol) was added to the solution. The reaction mixture was stirred at room temperature (approximately 25 °C) for 12 hours. The reaction mixture... 1 ¹H-NMR analysis showed that the desired product had a cation to anion ratio of 1:1. The mixture was filtered to remove undissolved salts and then the solvent was removed under reduced pressure. The resulting residue was dissolved in acetone and filtered through a diatomaceous earth stopper. The solvent was removed from the filtrate under reduced pressure to produce CPAC9, a colorless oil. The UPLC purity was 99.64%, as determined by UV absorbance at 210 nm.

[0226]

[0227]

[0228] Photoresist Formulation 1. A photoresist composition was prepared by dissolving the solid components in a solvent to achieve a total solids content of 2.6 wt% using the materials and amounts listed in Table 1. Each mixture was vibrated using a mechanical vibrator and filtered through a PTFE disc filter with a pore size of 0.2 μm. The amounts of polymers, PAGs, and photoactive compounds were reported as wt% based on the total solids of the photoresist composition. The solvent system contained propylene glycol monomethyl ether acetate (PGMEA) (50 wt%) and methyl 2-hydroxyisobutyrate (50 wt%).

[0229] Photolithography Evaluation 1. Photolithography was performed using a CLEAN TRACK ACT8 (TEL, Tokyo Electron Co.) wafer track. A 200nm wafer coated with AR was used for photolithography testing. TM 3 BARC (DuPont Electronics & Industrial) were used and soft-baked at 205°C for 60 seconds to obtain a 60nm film. Then AR TM 40 BARC (DuPont Electronics & Industries) coating deposited on ARTM A second BARC layer with a thickness of 80 nm was formed by soft baking at 205 °C for 60 seconds on a 3-layer substrate. A photoresist composition was then coated onto the double BARC stack and soft baked at 110 °C for 60 seconds to obtain a photoresist film layer with a thickness of 70 nm. The wafer was exposed to 248 nm radiation using a mask with a 1:1 line-space (L / S) pattern (120 nm linewidth) on a Canon FPA-5000ES4 scanner (NA = 0.8, outer sigma = 0.85, inner sigma = 0.57). The exposed wafer was then baked at 100 °C for 60 seconds, developed with 0.26 NTMAH solution for 60 seconds, rinsed with DI water, and spin-dried to form the photoresist pattern. The critical dimension (CD) linewidth of the formed pattern was measured using a HITACHIS-9380CD-SEM. Line width roughness (LWR) is determined by the deviation of the width of a line measured over a given length, and is evaluated using a 3-sigma (3σ) deviation of the width from a distribution of a total of 100 arbitrary line width measurement points. LWR data are shown in Table 1.

[0230] Table 1

[0231]

[0232] * indicates a comparison instance.

[0233] Photoresist Formulation 2. A photoresist composition was prepared by dissolving the solid components in a solvent to achieve a total solids content of 4.2 wt% using the materials and amounts listed in Table 2. Each mixture was vibrated using a mechanical vibrator and then filtered through a PTFE disc filter with a pore size of 0.2 μm. The amounts of polymers, PAGs, and photoactive compounds were reported as wt% based on the total solids of the photoresist composition. The solvent system contained PGMEA (50 wt%) and methyl 2-hydroxyisobutyrate (50 wt%).

[0234] Photolithography Evaluation 2. Photolithography was performed using a CLEAN TRAC ACT8 (TEL, Tokyo Electron Ltd.) wafer track. A 200nm wafer used for photolithography testing was coated with AR... TM 3BARC (DuPont Electronics & Industrial) was used and soft-baked at 205°C for 60 seconds to obtain a 60nm film. Then AR TM 40A BARC (DuPont Electronics & Industries) coating deposition on AR TMA second BARC layer with a thickness of 80 nm was formed by soft baking at 2050 °C for 60 seconds on the three layers. Then, a photoresist composition was coated on the double BARC stack and soft baked at 110 °C for 60 seconds to obtain a photoresist film with a thickness of 120 nm.

[0235] On a CANON FPA-5000ES4 scanner (NA = 0.8, outer sigma = 0.85, inner sigma = 0.57), a wafer was exposed to 248 nm radiation using a mask with a 1:1 L / S pattern (120 nm linewidth). The exposed wafer was then baked at 100°C for 60 seconds, developed with 0.26 N TMAH solution for 60 seconds, rinsed with DI water, and spin-dried to form a photoresist pattern. The CD linewidth of the formed pattern was measured using a HITACHI S-9380CD-SEM. LWR was determined by the deviation of the linewidth measured over a given length and evaluated using a 3σ deviation of the width from a distribution of a total of 100 arbitrary linewidth measurement points. The LWR data are shown in Table 2.

[0236] Table 2

[0237]

[0238] * indicates a comparison instance.

[0239] Photoresist Formulation 3. A photoresist composition was prepared by dissolving the solid components in a solvent to achieve a total solids content of 1.55 wt% using the materials and amounts listed in Table 3. Each mixture was vibrated using a mechanical vibrator and filtered through a PTFE disc filter with a pore size of 0.2 μm. The amounts of polymers, PAGs, and photoactive compounds were reported as wt% based on the total solids of the photoresist composition. The solvent system contained PGMEA (50 wt%) and methyl 2-hydroxyisobutyrate (50 wt%).

[0240] 3. Photolithography evaluation was performed using a CLEAN TRAC ACT8 (TEL, Tokyo Electron Ltd.) wafer track. A 300nm wafer for photolithography testing was coated with an organic BARC film to obtain a 60nm film, and then a silicon-containing antireflective coating (SiARC) film was deposited on the organic BARC film to form a second layer with a thickness of 20nm. A photoresist composition was then spin-coated onto the BARC / SiARC bilayer stack and soft-baked at 110°C for 60 seconds to obtain a photoresist film with a thickness of 40nm.

[0241] The wafer was exposed to 13.5 nm radiation using an ASML NXE3400B scanner, a CD with a 20.25 nm resist, and a mask with a 36-pitch trench pattern. The exposed wafer was then baked at 100°C for 60 seconds, developed with 0.26 N TMAH solution for 60 seconds, rinsed with DI water, and spin-dried to form the resist trench pattern. The CD linewidth of the formed trench pattern was measured using a HITACHI CG5000 CD-SEM.

[0242] Table 3 shows the EUV sizing energy (E) determined for the examples. 尺寸 The irradiation energy is measured in millijoules per square centimeter (mJ / cm²) when the groove pattern is resolved to 18 nm. 2 Table 3 also shows the depth of focus (DOF) of the examples, which is the total focusing distance range that keeps the printed features free from any printing defects.

[0243] Table 3

[0244]

[0245] * indicates a comparison instance.

[0246] As demonstrated by the comparison of the results in Tables 1, 2, and 3, the photoactive compounds of the present invention provide photoresist compositions with unexpected lithographic properties and achieve a reduction in LWR of up to 20%. The improvement in LWR was observed to have no effect on photosensitivity and improved DOF.

[0247] While this disclosure has been described in conjunction with exemplary embodiments now considered to be practical, it should be understood that the invention is not limited to the disclosed embodiments, but rather is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A photoactive compound having formula (3a): (3a) in, Ring CY1 is C 3-8 cycloalkyl or C 6-14 Aryl; Each L 1 It is a single bond on its own; Each R 8 It is independently a hydroxyl group, -F, -I, -CF3, or an unsubstituted C. 1-10 alkyl; a is an integer from 0 to 3; L 2 It is a single key; R 9 It is hydrogen, cyano, hydroxyl, -F, -I, -CF3 or unsubstituted C 1-10 Alkyl groups; and M + It is a sulfonium cation or an iodonium cation; The condition is when R 8 When it is a hydroxyl group, R 9 It is not cyano.

2. A photoresist composition comprising: The photoactive compound as claimed in claim 1; and Solvent.

3. The photoresist composition of claim 2, further comprising a material whose solubility in an alkali or organic solvent is altered by an acid, wherein the material is different from the photoactive compound.

4. The photoresist composition of claim 3, further comprising a photoacid generator different from the photoactive compound.

5. A method for forming a pattern, the method comprising: (a) A photoresist layer is formed on a substrate using the photoresist composition as described in claim 2; (b) Expose the photoresist layer to activation radiation in a patterned manner; as well as (c) Develop the exposed photoresist layer to provide a photoresist relief image.

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