Iodine-containing acid-cleavable compounds, polymers derived therefrom, and photoresist compositions

Abstract

Disclosed is a compound containing an aromatic group or a heteroaromatic group, wherein the aromatic group or the heteroaromatic group includes a first substituent containing an ethylenically unsaturated double bond, a second substituent which is an iodine atom, and a third substituent containing an acid-labile group, wherein the first substituent, the second substituent, and the third substituent are each bonded to a different carbon atom of the aromatic group or the heteroaromatic group.

Description

Technical Field

[0001] The present invention relates to iodine-containing acid-cleavable compounds, polymers derived from these compounds, photoresist compositions containing these polymers, and pattern forming methods using these photoresist compositions. The present invention finds particular applicability in photolithographic applications in the semiconductor manufacturing industry. Background Art

[0002] Photoresist compositions are light-sensitive materials used to transfer images to one or more lower layers (such as metal, semiconductor or dielectric layers) arranged on a substrate. Positive chemically enhanced photoresist compositions are commonly used for high-resolution processing. Such resist compositions typically include a polymer with an acid-labile group and a photoacid generator (PAG). The layer of the photoresist composition is exposed to activating radiation in a patterned manner and the PAG generates acid in the exposed area. During post-exposure baking, the acid cracks the acid-labile group of the polymer. This creates a difference in solubility characteristics between the exposed area and the unexposed area of ​​the photoresist layer in the developer solution. In the positive development (PTD) process, the exposed area of ​​the photoresist layer becomes soluble in the developer (typically an aqueous alkaline developer) and is removed from the substrate surface. The unexposed area that is insoluble in the developer is retained to form a positive relief image after development. The resulting relief image allows selective processing of the substrate.

[0003] In order to increase the integration density of semiconductor devices and allow the formation of structures with dimensions in the nanometer (nm) range, photoresists and photolithography processing tools with high-resolution capabilities have been and continue to be developed. One method of achieving nm-level feature sizes in semiconductor devices is to use activating radiation with a short wavelength (e.g., 193 nm or shorter) to expose the photoresist layer. To further improve photolithography performance, immersion photolithography tools have been developed to effectively increase the numerical aperture (NA) of the lens of the imaging device. This can be achieved by using a fluid with a higher refractive index (typically water) between the final surface of the imaging device and the upper surface of the semiconductor wafer.

[0004] By using multiple (double, triple or more) patterning techniques, deep ultraviolet argon fluoride (ArF) excimer laser immersion tools are currently pushing the boundaries of lithography processing to 16nm and 14nm device nodes. However, using multiple patterning can be expensive in terms of increasing material usage and the number of process steps required (compared to single-step, direct imaging patterns). Therefore, for advanced device nodes, the demand for photoresist compositions for next-generation (e.g., extreme ultraviolet, EUV) lithography, which use activating radiation with an extremely short wavelength of 13.5nm, is becoming increasingly important. At the extreme feature sizes associated with these nodes, the performance requirements of photoresist compositions are becoming increasingly stringent. The required performance characteristics include, for example, high sensitivity to activating radiation, low unexposed film thickness loss (UFTL), good contrast, high resolving power, and good line width roughness (LWR).

[0005] One way to increase the sensitivity of EUV photoresists is by increasing the absorption cross-section at 13.5nm. The absorption of a material at 13.5nm is an atomic property and can be theoretically calculated using known atomic absorption. Typical atoms that make up resist materials (such as carbon, oxygen, hydrogen, and nitrogen) have very weak EUV absorption. Fluorine atoms have slightly higher absorption and have been used to find photoresists with high EUV absorption. Iodine has a very high absorption cross-section under EUV radiation. JP2015-161823; US 10,095,109B1; and US 10,495,968B2 describe iodine-containing monomers and corresponding polymers that can be used for photolithography. In addition, JP 2018-95851A describes iodine-containing monomers with carboxylic acid groups. However, connecting highly alkali-soluble carboxylic acid groups may cause loss of unexposed film thickness and therefore poor resolution.

[0006] Therefore, there remains a continuing need in the art for acid-labile compounds to provide EUV photoresist polymers with good absorption at 13.5 nm, reduced unexposed film thickness loss (UFTL), improved LWR, or a combination thereof. Summary of the Invention

[0007] Provided is a compound containing an aromatic group or a heteroaromatic group, wherein the aromatic group or the heteroaromatic group includes a first substituent containing an ethylenically unsaturated double bond, a second substituent which is an iodine atom, and a third substituent containing an acid-labile group, wherein the first substituent, the second substituent, and the third substituent are each bonded to a different carbon atom of the aromatic group or the heteroaromatic group.

[0008] A polymer is also provided, comprising a first repeating unit derived from the compound of the present invention. In another aspect, a photoresist composition is provided, comprising the polymer of the present invention, a photoacid generator (PAG), and a solvent.

[0009] Yet another aspect provides a method for forming a pattern, the method comprising applying a layer of the photoresist composition of the present invention to a substrate to provide a photoresist composition layer; exposing the photoresist composition layer to activating radiation in a pattern manner to provide an exposed photoresist composition layer; and developing the exposed photoresist composition layer to provide a photoresist pattern. DETAILED DESCRIPTION

[0010] Reference will now be made in detail to exemplary embodiments, examples of which are shown in this specification. In this regard, the exemplary embodiments may have different forms and should not be construed as being limited to the description shown herein. Therefore, exemplary embodiments will be described below only with reference to the accompanying drawings to explain aspects of this specification. As used herein, the term "and / or" includes any and all combinations of one or more of the relevant listed items. When a statement such as "at least one of..." precedes a list of elements, it modifies the entire list of elements and does not modify a single element in the list.

[0011] As used herein, the terms "a / an" and "the" do not represent a limit to quantity and are interpreted as including both the singular and the plural unless otherwise indicated herein or clearly contradictory to the context. Unless otherwise expressly stated, "or" means "and / or". The modifier "about" used in conjunction with quantity includes the value and has the meaning specified by the context (e.g., including the degree of error associated with the measurement of a specific quantity). The full range disclosed herein includes endpoints, and the endpoints are independently combinable with each other. The suffix "(s)" is intended to include both the singular and the plural of the term it modifies, thereby including at least one of the terms. "Optional" or "optionally" means that the event or situation described subsequently may or may not occur, and the description includes examples of the occurrence of the event and examples in which it does not occur. The terms "first", "second" and similar terms do not represent order, quantity, or importance in this article, but are used to distinguish one element from another. When an element is referred to as being "on" another element, it can be in direct contact with the other element or an intervening element may be present therebetween. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present. It will be understood that the components, elements, limitations, and / or features of the described aspects may be combined in any suitable manner in the various aspects.

[0012] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms (such as those defined in commonly used dictionaries) should be interpreted as having a meaning consistent with their meaning in the context of the relevant art and this disclosure, and will not be interpreted as an idealized or overly formal meaning unless expressly defined as such herein.

[0013] As used herein, "actinic rays" or "radiation" means, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays, extreme ultraviolet rays (EUV light) represented by an excimer laser, X-rays, particle rays (such as electron beams and ion beams), etc. In addition, in the present invention, "light" means actinic rays or radiation. A krypton fluoride laser (KrF laser) is a special type of excimer laser, sometimes referred to as an excimer laser. "Excimer" is an abbreviation for "excimer dimer", and "excimer" is an abbreviation for "excimer complex". An excimer laser uses a mixture of a rare gas (argon, krypton or xenon) and a halogen gas (fluorine or chlorine), which emits coherent stimulated radiation (laser) in the ultraviolet range under appropriate electrical stimulation and high voltage conditions. In addition, unless otherwise specified, "exposure" in this specification includes not only exposure by a mercury lamp, far ultraviolet rays, X-rays, extreme ultraviolet rays (EUV light) represented by an excimer laser, etc., but also writing with particle rays (such as electron beams and ion beams).

[0014] 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 or branched saturated hydrocarbon group having the specified number of carbon atoms and having 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 (-OH) group; "alkoxy" refers to "alkyl-O-"; "carboxyl" and "carboxylic acid group" refer to groups of 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 or branched monovalent hydrocarbon group having at least one carbon-carbon double bond; "alkenyloxy" refers to "alkenyl-O-"; "alkenylene" refers to an alkenyl group having a valence of 2; "cycloalkenyl" refers to a cycloalkyl group having at least three carbon atoms. , a non-aromatic cyclic divalent hydrocarbon group having 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 aromatic ring system that satisfies Huckel's rule (4n + 2π electrons) and includes carbon atoms in the ring; the term "heteroaromatic group" refers to an aromatic group that includes one or more heteroatoms (e.g., 1-4 heteroatoms) selected from N, O, and S replacing carbon atoms in the ring; "aryl" refers to a monovalent monocyclic or polycyclic aromatic ring system in which each ring member is carbon and may include a group having an aromatic ring fused to at least one cycloalkyl or heterocycloalkyl ring; "arylene" refers to an aryl group with a valence of 2; "alkylaryl" refers to an aryl group that has been substituted by an alkyl group; "arylalkyl" refers to an alkyl group that has been substituted by an aryl group; "aryloxy" refers to "aryl-O-"; and "arylthio" refers to "aryl-S-".

[0015] 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 is a heteroatom replacing a carbon atom, wherein each of these heteroatoms is independently N, O, S, Si, or P; a "heteroatom-containing group" refers to a substituent that includes at least one heteroatom; and a "heteroalkyl" refers to an alkyl group having at least one heteroatom replacing a carbon.

[0016] The term "heterocycloalkyl" refers to a cycloalkyl group having at least one heteroatom independently selected from N, O, or S as a ring member replacing a carbon; "heterocycloalkylene" refers to a heterocycloalkyl group having a valence of 2. Exemplary 3-membered heterocycloalkyl groups containing one heteroatom include aziridinyl, oxiranyl, and thiirane. Exemplary 4-membered heterocycloalkyl groups containing one heteroatom include azetidinyl, oxiranyl, and thiirane. Exemplary 5-membered heterocycloalkyl groups containing one heteroatom include tetrahydrofuranyl, dihydrofuranyl, tetrahydrothienyl, dihydrothienyl, pyrrolidinyl, dihydropyrrolyl, and pyrrolyl-2,5-dione. Exemplary 5-membered heterocycloalkyl groups containing two heteroatoms include dioxolanyl, oxathiolanyl, and dithiolanyl. Exemplary 5-membered heterocycloalkyl groups containing three heteroatoms include triazolinyl, oxadiazolinyl, and thiadiazolinyl. Exemplary 6-membered heterocycloalkyl groups containing one heteroatom include piperidinyl, tetrahydropyranyl, dihydropyridinyl, and thianyl. Exemplary 6-membered heterocycloalkyl groups containing two heteroatoms include piperazinyl, morpholinyl, dithianyl, and dioxanyl. Exemplary 6-membered heterocycloalkyl groups containing three heteroatoms include triazinyl. Exemplary 7-membered heterocycloalkyl groups containing one heteroatom include azepanyl, oxepanyl, and thiepanyl. Exemplary 8-membered heterocycloalkyl groups containing one heteroatom include azocanyl, oxepanyl, and thiepanyl. Exemplary bicyclic heterocycloalkyl groups include indolinyl, isoindolinyl, dihydrobenzofuranyl, dihydrobenzothiophenyl, tetrahydrobenzothiophenyl, tetrahydrobenzofuranyl, tetrahydroindolyl, tetrahydroquinolyl, tetrahydroisoquinolyl, decahydroquinolyl, decahydroisoquinolyl, octahydrochromenyl, octahydroisochromenyl, decahydronaphthyridinyl, decahydro-1,8-naphthyridinyl, octahydropyrrolo[3,2-b]pyrrole, indolinyl, phthalimidyl, naphthylimidyl, chromanyl, chromenyl, 1H-benzo[e][1,4]diazepinyl, 1,4,5,7-tetrahydropyrano[3,4-b]pyrrolyl, 5-[[1,4]-benzo[e][1,4]diazepinyl] ...1,4,5,7-tetrahydropyrano[3,4-b]pyrrolyl, 1,4,5,7-tetrahydropyrano[3,4-b]pyrrolyl, 1,4,5,7-tetrahydropyrano[3,4-b]pyrrolyl, 1,4,5,7- ,6-dihydro-4H-furo[3,2-b]pyrrolyl, 6,7-dihydro-5H-furo[3,2-b]pyranyl, 5,7-dihydro-4H-thieno[2,3-c]pyranyl, 2,3-dihydro-1H-pyrrolo[2,3-b]pyridinyl, 2,3-dihydrofuro[2,3-b]pyridinyl, 4,5,6,7-tetrahydro-1H-pyrrolo[2,3-b]pyridinyl, 4,5,6,7-tetrahydrofuro[3,2-c]pyridinyl, 4,5,6,7-tetrahydrothieno[3,2-b]pyridinyl and 1,2,3,4-tetrahydro-1,6-naphthyridinyl.

[0017] The term "heteroaryl" means a 4-8 membered monocyclic, 8-12 membered bicyclic, or 11-14 membered tricyclic aromatic ring system having 1-4 heteroatoms (if monocyclic), 1-6 heteroatoms (if bicyclic), or 1-9 heteroatoms (if tricyclic), each of which is independently selected from N, O, or S (e.g., carbon atoms and 1-3, 1-6, or 1-9 heteroatoms independently selected from N, O, or S, respectively, if monocyclic, bicyclic, or tricyclic). Exemplary 5-membered heteroaryls containing 1 heteroatom include pyrrolyl, furanyl, and thienyl. Exemplary 5-membered heteroaryls containing 2 heteroatoms include imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, and isothiazolyl. Exemplary 5-membered heteroaryls containing 3 heteroatoms include triazolyl, oxadiazolyl, and thiadiazolyl. Exemplary 5-membered heteroaryl groups containing 4 heteroatoms include tetrazolyl. Exemplary 6-membered heteroaryl groups containing 1 heteroatom include pyridinyl. Exemplary 6-membered heteroaryl groups containing 2 heteroatoms include pyridazinyl, pyrimidinyl, and pyrazinyl. Exemplary 6-membered heteroaryl groups containing 3 or 4 heteroatoms include triazinyl and tetrazinyl, respectively. Exemplary 7-membered heteroaryl groups containing 1 heteroatom include azepinyl, oxepinyl, and thiapezyl. Exemplary 5,6-bicyclic heteroaryl groups include indolyl, isoindolyl, indazolyl, benzotriazolyl, benzothiophenyl, isobenzothiophenyl, benzofuranyl, benzisofuranyl, benzimidazolyl, benzoxazolyl, benzisoxazolyl, benzoxadiazolyl, benzothiazolyl, benzisothiazolyl, benzothiadiazolyl, indolizinyl, and purinyl. Exemplary 6,6-bicyclic heteroaryl groups include naphthyridinyl, pteridinyl, quinolyl, isoquinolyl, cinnolinyl, quinoxalinyl, phthalazinyl, and quinazolinyl. Exemplary tricyclic heteroaryl groups include, but are not limited to, phenanthridinyl, dibenzofuranyl, carbazolyl, acridinyl, phenothiazinyl, phenoxazinyl, and phenazinyl.

[0018] The term "halogen" means a monovalent substituent of fluorine (fluoro), chlorine (chloro), bromine (bromo), or iodine (iodo). The prefix "halo" means a group containing one or more of fluorine, chlorine, bromine, or iodine substituents replacing a hydrogen atom. A combination of halides (e.g., bromine and fluorine) or only fluorine groups can be present. For example, the term "haloalkyl" refers to an alkyl group substituted with one or more halogens. As used herein, a "substituted C 1-8 "Haloalkyl" refers to a C 1-8 Alkyl, and further substituted with one or more other substituent groups that are not halogen. It should be understood that substitution of a group with a halogen atom should not be considered a heteroatom-containing group because the halogen atom is not replacing a carbon atom.

[0019] The term "fluorinated" means having one or more fluorine atoms incorporated into the group instead of hydrogen. For example, when C 1-18When a fluoroalkyl group is present, the fluoroalkyl group can include one or more fluorine atoms, such as a single fluorine atom, two fluorine atoms (e.g., 1,1-difluoroethyl), three fluorine atoms (e.g., 2,2,2-trifluoroethyl), or a fluorine atom on each valence of the carbon (e.g., a perfluorinated group such as, -CF3, -C2F5, -C3F7, or -C4F9). "Substituted fluoroalkyl" is understood to mean a fluoroalkyl group that is further substituted with at least one additional substituent that does not contain a fluorine atom.

[0020] Unless otherwise expressly provided, each of the aforementioned substituent groups can be optionally substituted. The term "optionally substituted" refers to being substituted or unsubstituted. "Substituted" means that at least one hydrogen atom of a chemical structure or group is replaced by another typically monovalent terminal substituent group, provided that the normal valence of the specified atom is not exceeded. When the substituent is an oxo (i.e., O), then the two geminal hydrogen atoms on the carbon atom are replaced by a terminal oxo group. Further note that the oxo group is bonded to the carbon via a double bond to form a carbonyl (C=O), wherein the carbonyl is represented herein as -C(O)-. Combinations of substituents or variables are permissible. Exemplary substituent groups that may be present in a "substituted" position include, but are not limited to, nitro (-NO2), cyano (-CN), hydroxyl (-OH), oxo (O), amino (-NH2), mono- or di-(C 1-6 ) alkylamino, alkanoyl (such as C 2-6 Alkanoyl such as acyl), formyl (-C(O)H), carboxylic acid or its alkali metal or ammonium salt; ester (including acrylate, methacrylate and lactone) such as C 2-6 Alkyl esters (-C(O)O-alkyl or -OC(O)-alkyl) and C 7-13 Aryl esters (-C(O)O-aryl or -OC(O)-aryl); amides (-C(O)NR2, where R is hydrogen or C 1-6 alkyl), carboxamido (-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, C 1-6 Halogenated alkyl, C 1-9 Alkoxy, C 1-6 Halogenated alkoxy, C 3-12 Cycloalkyl, C 5-18 Cycloalkenyl, C 2-18 Heterocycloalkenyl, C 6-12Aryl (e.g., phenyl, biphenyl, naphthyl, etc., each ring is substituted or unsubstituted aromatic), C having 1 to 3 separate or fused rings and 6 to 18 ring carbon atoms 7-19 Arylalkyl, arylalkoxy having 1 to 3 separate or fused rings and 6 to 18 ring carbon atoms, C 7-12 Alkyl aryl, C 3-12 Heterocycloalkyl, C 3-12 Heteroaryl, C 1-6 Alkylsulfonyl (-S(O)2-alkyl), C 6-12 Arylsulfonyl (-S(O)2-aryl), or tosyl (CH3C6H4SO2-). When a group is substituted, the number of carbon atoms indicated is the total number of carbon atoms in the group, excluding those of any substituents. For example, the group -CH2CH2CN is a cyano-substituted C2 alkyl group.

[0021] As used herein, when no definition is otherwise provided, a "divalent linking group" refers to a group including -O-, -S-, -Te-, -Se-, -C(O)-, C(O)O-, -N(R ’ )-、-C(O)N(R ’ )-, -S(O)-, -S(O)2-, -C(S)-, -C(Te)-, -C(Se)-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocycloalkylene, substituted or unsubstituted C 6-30 Arylene, substituted or unsubstituted C 3-30 heteroarylene, or one or more divalent groups in a combination thereof, wherein each R ’ are independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 3-30 Typically, the divalent linking group includes -O-, -S-, -C(O)-, -N(R')-, -S(O)-, -S(O)2-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocycloalkylene, substituted or unsubstituted C 6-30 Arylene, substituted or unsubstituted C 3-30 heteroarylene, or one or more of a combination thereof, wherein R' is hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20Heteroalkyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 3-30 More typically, the divalent linking group includes -O-, -C(O)-, -C(O)O-, -N(R ’ )-、-C(O)N(R')-、substituted or unsubstituted C 1-10 Alkylene, substituted or unsubstituted C 3-10 Cycloalkylene, substituted or unsubstituted C 3-10 Heterocycloalkylene, substituted or unsubstituted C 6-10 Arylene, substituted or unsubstituted C 3-10 heteroarylene, or one or more of a combination thereof, wherein R' is hydrogen, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted C 1-10 Heteroalkyl, substituted or unsubstituted C 6-10 Aryl, substituted or unsubstituted C 3-10 Heteroaryl.

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

[0023] The term "unsaturated bond" refers to a double bond or a triple bond. The term "unsaturated" or "partially unsaturated" refers to a moiety that includes at least one double bond or triple bond. The term "saturated" refers to a moiety that does not contain double or triple bonds, i.e., the moiety contains only single bonds.

[0024] As used herein, the term "(meth)acrylic" includes both acrylic and methacrylic species (ie, acrylic and methacrylic monomers), and the term "(meth)acrylate" includes both acrylate and methacrylate species (ie, acrylate and methacrylate monomers).

[0025] Iodine has a very high absorption cross section (i.e. 13.5nm) to EUV radiation. However, functionalization with iodine increases the hydrophobicity of organic molecules. For example, the iodine-rich byproducts produced after the post-exposure baking step may not allow alkaline developer to develop the exposed area completely or cleanly. In order to overcome these difficulties, the invention provides a kind of acid-unstable compound, which comprises one or more iodine substituents and one or more carboxylic acid functional groups protected by acid-unstable groups. Acid-unstable can be used to provide a photoresist polymer with increased resist absorption under EUV exposure wavelength without damaging the unexposed film thickness. The acid-catalyzed deprotection of the repeating unit derived from the acid-unstable compound produces an iodine-containing structural unit, which is hydrophilic and soluble in alkaline developer. In addition, during deprotection, the iodine-containing structural unit remains connected to the backbone of the polymer, and therefore the deprotection product remaining after the post-exposure baking does not contain iodine.

[0026] The iodine-containing compound of the present invention comprises an aromatic group or a heteroaromatic group, wherein the aromatic group or the heteroaromatic group comprises a first substituent comprising an ethylenically unsaturated double bond, a second substituent being an iodine atom, and a third substituent comprising an acid-labile group. The first substituent, the second substituent, and the third substituent are each bonded to a different carbon atom of the aromatic group or the heteroaromatic group.

[0027] As used herein, "aromatic group or heteroaromatic group" refers to a monocyclic or polycyclic C 6-60 Aromatic group or monocyclic or polycyclic C 3-60 Heteroaromatic group. When C 6-60 When the aromatic group is polycyclic, one or more ring groups may be fused (such as naphthyl, etc.) or directly connected (such as biaryl, biphenyl, etc.). In an embodiment, the polycyclic aromatic group may include a combination of fused and directly connected rings or ring groups (such as binaphthyl, etc.). When C 3-60 When the heteroaromatic group is polycyclic, the rings or ring groups may be fused, directly linked, or a combination of fused and directly linked rings or ring groups.

[0028] The first substituent of the aromatic group or heteroaromatic group includes an ethylenically unsaturated double bond. As used herein, "ethylenically unsaturated double bond" refers to a polymerizable group containing a vinyl group and can typically be selected from substituted or unsubstituted C 2-20 substituted or unsubstituted norbornyl, substituted or unsubstituted (meth)acrylic, substituted or unsubstituted vinyl ether, substituted or unsubstituted vinyl ketone, substituted or unsubstituted vinyl ester, or substituted or unsubstituted vinyl aromatic.

[0029] The second substituent of aromatic group or heteroaromatic group is iodine atom (-I).It should be understood that the second substituent can include one or more iodine atoms.In some aspects, the second substituent can include 1 to 9 iodine atoms or 1 to 5 iodine atoms or 1 to 3 iodine atoms or 1 or 2 iodine atoms.In other words, iodine-containing compound can include 1 to 9 iodine atoms or 1 to 5 iodine atoms or 1 to 3 iodine atoms or 1 or 2 iodine atoms.

[0030] The 3rd substituent of aromatic group or heteroaromatic group comprises acid-labile group.Should be appreciated that the 3rd substituent can comprise an acid-labile group, or can comprise 2 or more acid-labile groups that are identical or different from each other.In some respects, the 3rd substituent can contain 1 to 5 different acid-labile groups, or 1 to 3 different acid-labile groups, or 2 different acid-labile groups, or single acid-labile group (i.e. an acid-labile group).In other words, iodine-containing compound can comprise 1 to 5 different acid-labile groups, or 1 to 3 different acid-labile groups, or 2 different acid-labile groups, or single acid-labile group (i.e. an acid-labile group).

[0031] Suitable acid labile groups for the third substituent include, for example, one or more of a tertiary alkyl ester group, a secondary or tertiary aryl ester group, a secondary or tertiary ester group having a combination of alkyl and aryl groups, a tertiary alkoxy group, an acetal group, or a ketal group.

[0032] In some embodiments, the number of second substituents and the number of third substituents when combined are equal to 10 or less, or are from 2 to 6, or are from 2 to 4. In other words, the iodine-containing compound can include a total of 10 or less iodine atoms and acid-labile groups combined, or, for example, the total number of iodine atoms and acid-labile groups is from 2 to 6, more typically from 2 to 4.

[0033] In some aspects, the first substituent does not include an acid-labile group or an acid-leaving group. In other words, in some aspects, the iodine-containing compound includes a polymerizable group (i.e., an ethylenically unsaturated double bond) that is not a tertiary alkyl ester group, a secondary or tertiary aryl ester group, a secondary or tertiary ester group having a combination of an alkyl and an aryl group, a tertiary alkoxy group, an acetal group, or a ketal group. For example, the first substituent of the compound of the present invention can be (meth)acrylic acid or vinyl (e.g., substituted or unsubstituted C 2-12 alkenyl).

[0034] In some aspects, the compound can be represented by formula (1):

[0035]

[0036] In formula (1), Ar 1 is an aromatic group or a heteroaromatic group, the first substituent is -L1 -X, the second substituent is represented by -I, and the third substituent is represented by -L 2 -R 1 express.

[0037] Ar 1 It is C 6-30 Aryl or C 3-30 heteroaryl, and each optionally further substituted by one or more of the following: substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 1-30 Heterocycloalkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 7-30 Alkylaryl, substituted or unsubstituted C 3-30 Heteroaryl, substituted or unsubstituted C 4-30 Alkyl heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl.

[0038] It should be understood that "further substitution" means that C 6-30 Aryl or C 3-30 The heteroaryl group is replaced by at least the first substituent (-L 1 -X), the second substituent (I) n and the third substituent (-L 2 -R 1 ) is replaced, and C 6-30 Aryl or C 3-30 The heteroaryl group may optionally be further substituted with one or more other substituents that are different from the first substituent, the second substituent, and the third substituent. 1 It is C 6-30 Aryl, and optionally further substituted by one or more of the following: substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 1-30 heterocycloalkyl, or a combination thereof.

[0039] In formula (1), X is a polymerizable group containing the ethylenically unsaturated double bond. Preferably, X is (meth)acrylic acid or substituted or unsubstituted C 2-12 Alkenyl.

[0040] In formula (1), L 1 is a single bond or a divalent linking group. For example, L 1 It may be a divalent linking group comprising one or more of the following: substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 1-30 Heterocycloalkylene, substituted or unsubstituted C 6-30 Arylene, substituted or unsubstituted C 1-30 Heteroarylene, -O-, -C(O)-, -C(O)O-, -C(O)NR 1a -, or -N(R 1b )-, where R 1a and R 1b are each independently hydrogen or C 1-6 alkyl.

[0041] In formula (1), the first substituent may be -L 1 -X part definition, where L 1 is a single bond or a divalent linking group, and X is a polymerizable group containing an ethylenically unsaturated double bond. Typically, X is a substituted or unsubstituted C 2-20 For example, when the first substituent includes a substituted or unsubstituted vinyl aromatic group, in the first substituent -L 1 -X,L 1 is a substituted or unsubstituted divalent C7 alkylaryl group (or C7 arylalkyl group), and X is a C2 alkenyl group.

[0042] In formula (1), n ​​represents the number of iodine atoms directly bonded to the aromatic group or heteroaromatic group, and n is an integer greater than or equal to 1. In some aspects, n is an integer from 1 to 9, or an integer from 1 to 7, or an integer from 1 to 5, or an integer from 1 to 4, or an integer from 1 to 3, or 1 or 2. Preferably, n is 1 or 2.

[0043] In formula (1), m represents the number of the third substituent, wherein the third substituent can be -L 2 -R 1 Part is defined, and m is an integer greater than or equal to 1. In some aspects, m is preferably an integer from 1 to 5, or an integer from 1 to 4, or an integer from 1 to 3, or 1 or 2. Preferably, m is an integer from 1 to 3.

[0044] In formula (1), the sum of n and m (n+m) is an integer of 10 or less. For example, the sum of n and m (n+m) may be an integer of 2 to 8, or 2 to 6, or 2 or 4. Preferably, the sum of n and m (n+m) is an integer of 2 to 4.

[0045] In formula (1), k is an integer from 1 to 5. Typically, k is 1.

[0046] In formula (1), R 1 Acid labile groups are included. Exemplary acid labile groups include 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.

[0047] In some respects, R 1 It may have a structure represented by one of formula (2) or formula (3):

[0048]

[0049] In formula (2), R 2 to R 4 are each independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C 3-20 Heterocycloalkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 3-20 Cycloalkenyl, substituted or unsubstituted C 3-20 Heterocycloalkenyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 2-20 Heteroaryl, provided that it is selected from R 2 to R 4 Not more than one of them is hydrogen, and provided that if R 2 to R 4 If one of them is hydrogen, then R 2 to R 4 At least one of the other is a substituted or unsubstituted C 6-20 Aryl or substituted or unsubstituted C 3-20 Heteroaryl. R 2 to R 4 Each of may optionally further include a divalent linking group as part of its structure. For example, R 2 to R 4 Each of may further include as part of its structure a radical selected from -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R 2a )-or-C(O)N(R 2b)-, wherein R 2a and R 2b are each independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, or substituted or unsubstituted C 3-20 Typically, R 2 to R 4 are each independently hydrogen, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted C 3-8 Cycloalkyl, or substituted or unsubstituted C 6-14 Aryl.

[0050] In formula (3), R 5 and R 6 are each independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C 3-20 Heterocycloalkyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 2-20 Heteroaryl. R 5 and R 6 Each of may optionally further include a divalent linking group as part of its structure. For example, R 5 and R 6 Each of may further include as part of its structure a radical selected from -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R 3a )-or-C(O)N(R 3b )-, wherein R 3a and R 3b are each independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, or substituted or unsubstituted C 3-20 Typically, R 5 and R 6 are each independently hydrogen, or substituted or unsubstituted C 1-10 alkyl.

[0051] In formula (3), R 7 is substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C 3-20 Heterocycloalkyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 3-20 Heteroaryl. R 7Optionally, it may further include a divalent linking group as part of its structure. Typically, R 7 C may be substituted or unsubstituted 1-10 Alkyl, substituted or unsubstituted C 3-8 Cycloalkyl, or substituted or unsubstituted C 6-14 Aryl.

[0052] In formula (2), R 2 、R 3 or R 4 Any two of the R-1 and R-2 may optionally form a ring via a single bond or a divalent linking group, wherein the ring is substituted or unsubstituted. 5 and R 6 Together, they may optionally form a ring via a single bond or a divalent linking group, wherein the ring is substituted or unsubstituted. 5 or R 6 Any one or more of R 7 Together, they may optionally form a ring via a single bond or a divalent linking group, wherein the ring is substituted or unsubstituted.

[0053] In formulas (2) and (3), * and *' each represent 2 It should be understood that when L 2 When it is a single bond, the corresponding * or *' indicates that it is 1 binding site.

[0054] In one or more embodiments, in formulas (1), (2) and (3), n is 1 or 2; X is (meth)acrylic acid or substituted or unsubstituted C 2-12 Alkenyl; L 1 is a single bond; L 2 Is a single bond or -C(O)OC(X 1 X 2 )-, where X 1 and X 2 are independently hydrogen, fluorine, unsubstituted C 1-6 Alkyl, C 1-6 Fluoroalkyl, unsubstituted C 3-6 Cycloalkyl, or C 3-6 Fluorocycloalkyl, and typically, X 1 and X 2 is hydrogen; and Ar 1 It is C 6-10 Aryl, optionally further substituted with one or more of the following: substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted C 1-10 Heteroalkyl, substituted or unsubstituted C 3-10 Cycloalkyl, or substituted or unsubstituted C3-10 In this embodiment, R 2 to R 4 are each independently hydrogen, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted C 3-8 Cycloalkyl, or substituted or unsubstituted C 6-14 Aryl, provided that it is selected from R 2 to R 4 Not more than one of them is hydrogen, and provided that if R 2 to R 4 If one of them is hydrogen, then R 2 to R 4 At least one of the other is a substituted or unsubstituted C 6-14 Aryl; R 2 to R 4 Any two of R are taken together, optionally via a single bond or a divalent linking group, to form a ring, wherein the ring is substituted or unsubstituted; 5 and R 6 are each independently hydrogen, or substituted or unsubstituted C 1-10 alkyl; and R 7 is substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted C 3-8 Cycloalkyl, or substituted or unsubstituted C 6-14 Aryl.

[0055] Exemplary iodine-containing compounds can include the following:

[0056]

[0057]

[0058] Also provided is a polymer comprising a first repeating unit derived from a compound of the present invention described herein. As will be understood in the art, the compound of the present invention can be used as a monomer for preparing a polymer, wherein the resulting polymer comprises a first repeating unit derived from a compound of the present invention. For convenience, the compound of the present invention is also referred to herein as a monomeric compound of the present invention, or simply as a "monomeric compound." The compound of the present invention may also be referred to herein as a "first monomer."

[0059] The first repeat unit derived from the monomeric compound of the present invention is typically present in the polymer in an amount of 0.1 to 50 mole percent (mol%), more typically 1 to 25 mol%, still more typically 5 to 15 mol%, based on the total repeat units in the polymer.

[0060] When a polymer comprises a first repeating unit derived from a monomeric compound of the present invention, the structural unit comprises an iodine-containing aromatic or heteroaromatic moiety that is not acid-cleavable from the polymer backbone. The present inventors have surprisingly discovered that when the polymer comprising the first repeating unit is exposed to radiation (and subsequently PEB), the iodine-substituted aromatic group remains attached to the polymer backbone and, therefore, enhances EUV absorption.

[0061] In some aspects, the polymer can further include repeating units comprising an acid-labile group. In other words, the polymer can include a first repeating unit derived from a monomeric compound of the present invention comprising a first acid-labile group (e.g., a third substituent) and a second repeating unit comprising a second acid-labile group, wherein the second acid-labile group is different from the first acid-labile group.

[0062] In one or more embodiments, the polymer may include acid-labile repeating units derived from monomers represented by one or more of formulas (4), (5), (6), (7), or (8):

[0063]

[0064] In formulas (4), (5) and (6), R a 、R b and R c Each independently may be hydrogen, fluorine, cyano, or substituted or unsubstituted C 1-10 Preferably, R a 、R b and R c Each independently may be hydrogen, fluorine, or substituted or unsubstituted C 1-5 Alkyl, typically methyl.

[0065] In formula (4), L 3 is a divalent linking group. For example, L 3 It may include 1 to 10 carbon atoms and at least one heteroatom. In a typical embodiment, L 1 It can be -OCH2-, -OCH2CH2O-, or -N(R 4a )-, where R 4a is hydrogen or C 1-6 alkyl.

[0066] In formulas (4) and (5), R 8 to R 13 are each independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C 3-20 Heterocycloalkyl, substituted or unsubstituted C 2-20Alkenyl, substituted or unsubstituted C 3-20 Cycloalkenyl, substituted or unsubstituted C 3-20 Heterocycloalkenyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 3-20 Heteroaryl, provided that R 8 to R 10 Not more than one of them may be hydrogen and R 11 to R 13 Not more than one of them may be hydrogen, and provided that if R 8 to R 10 If one of them is hydrogen, then R 8 to R 10 At least one of the others is a substituted or unsubstituted C 6-20 Aryl or substituted or unsubstituted C 3-20 heteroaryl, and if R 11 to R 13 If one of them is hydrogen, then R 11 to R 13 At least one of the others is a substituted or unsubstituted C 6-20 Aryl or substituted or unsubstituted C 3-20 Preferably, R 8 to R 13 are each independently substituted or unsubstituted C 1-6 Alkyl or substituted or unsubstituted C 3-10 Cycloalkyl. R 8 to R 13 Each of may optionally further comprise a divalent linking group as part of its structure.

[0067] For example, R 8 to R 13 Any one or more of may independently be of the formula -CH2C(O)CH (3-n) Y n or -CH2C(O)OCH (3-n) Y n wherein each Y is independently substituted or unsubstituted C 3-10 Heterocycloalkyl, and n is 1 or 2. For example, each Y can independently be substituted or unsubstituted including the formula -O(C a1 )(C a2 )O- 3-10 Heterocycloalkyl, wherein C a1 and C a2 are each independently hydrogen or substituted or unsubstituted alkyl, and wherein C a1 and C a2 together optionally forming a ring.

[0068] In formula (4), R 8 to R 10 Any two of the R 's together may optionally form a ring, wherein the ring may further include a divalent linking group as part of its structure, and wherein the ring may be substituted or unsubstituted. 11 to R 13 Any two of the together optionally may 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.

[0069] In formulas (6) and (8), R 14 、R 15 、R 20 and R 21 Each independently may be hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C 3-20 Heterocycloalkyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 3-20 heteroaryl; and R 16 and R 22 are each independently substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, or substituted or unsubstituted C 3-20 Preferably, R 14 、R 15 、R 20 and R 21 Each independently may be hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, or substituted or unsubstituted C 3-20 Heterocycloalkyl. 14 、R 15 、R 20 and R 21 Each of may optionally further comprise a divalent linking group as part of its structure.

[0070] In formula (4), R 14 to R 16 Any two of the together optionally may 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.

[0071] In formula (7), R 17 to R 19 Each independently may be substituted or unsubstituted C 1-20Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C 3-20 Heterocycloalkyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 3-20 Heteroaryl, provided that R 17 to R 19 Not more than one of them may be hydrogen, and provided that if R 17 to R 19 If one of them is hydrogen, then R 17 to R 19 At least one of the other is a substituted or unsubstituted C 6-20 Aryl or substituted or unsubstituted C 3-20 Heteroaryl. R 17 to R 19 Each of may optionally further comprise a divalent linking group as part of its structure.

[0072] For example, R 17 to R 19 Any one or more of may independently be of the formula -CH2C(O)CH (3-n) Y n or -CH2C(O)OCH (3-n) Y n wherein each Y is independently substituted or unsubstituted C 3-10 Heterocycloalkyl, and n is 1 or 2. For example, each Y can independently be substituted or unsubstituted including the formula -O(C a1 )(C a2 )O- 3-10 Heterocycloalkyl, wherein C a1 and C a2 are each independently hydrogen or substituted or unsubstituted alkyl, and wherein C a1 and C a2 together optionally forming a ring.

[0073] In formula (7), R 17 to R 19 Any two of the together optionally may 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.

[0074] In equations (7) and (8), X a and X b Each is independently a polymerizable group containing an ethylenically unsaturated double bond, preferably a (meth)acrylate or a C2 alkenyl group.

[0075] In equations (7) and (8), L 4 and L5 Each independently is a single bond or a divalent linking group, provided that when X a When it is a C2 alkenyl group, L 4 is not a single bond, and when X b When it is a C2 alkenyl group, L 5 is not a single bond. Preferably, L 4 and L 5 are each independently substituted or unsubstituted C 6-30 Arylene or substituted or unsubstituted C 6-30 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 4 It is understood that when n2 is 0, L 5 The group is directly attached to the oxygen atom.

[0076] In formula (8), R 18 to R 20 Any two of the together optionally may 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.

[0077] In some respects, R 8 to R 22 Each of the optionally further comprises as part of its structure a radical selected from -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -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 Heterocycloalkyl.

[0078] In some aspects, in the repeating unit comprising an acid labile group, the acid labile group can be a tertiary alkyl ester. For example, the repeating unit comprising a tertiary alkyl ester group can be derived from one or more monomers having formula (4), (5), or (7), wherein R 8 to R 13 or R 17 to R 19 All are not hydrogen, and n1 is 1. In one or more embodiments, the polymer further includes a second repeating unit comprising a tertiary alkyl ester group.

[0079] Exemplary monomers having formula (4) include one or more of the following:

[0080]

[0081] Exemplary monomers having formula (5) include one or more of the following:

[0082]

[0083]

[0084] where R d As in this paper, R in formula (3) b defined; and R ’ and R" are each independently substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C 3-20 Heterocycloalkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 3-20 Cycloalkenyl, substituted or unsubstituted C 3-20 Heterocycloalkenyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 3-20 Heteroaryl.

[0085] Exemplary monomers having formula (6) include one or more of the following:

[0086]

[0087] where R d is R as defined above c .

[0088] Exemplary monomers having formula (7) include one or more of the following:

[0089]

[0090] Exemplary monomers having formula (8) include one or more of the following:

[0091]

[0092] In some aspects, the polymer can have acid-labile repeat units derived from one or more monomers having a cyclic acetal or cyclic ketal group, such as one or more of the following structures:

[0093]

[0094] where R d is R as defined above a .

[0095] In some aspects, the polymer can have repeating units containing acid-labile groups (including tertiary alkoxy groups), such as one or more of the following monomers:

[0096]

[0097] The second repeat unit having an acid labile group and different from the first repeat unit is typically present in the polymer in an amount of 25 to 65 mol %, more typically 30 to 50 mol %, still more typically 30 to 45 mol %, based on the total repeat units in the polymer.

[0098] In some aspects, the polymer can further include a repeating unit comprising a polar group (i.e., a "third repeating unit"), wherein the polar group is attached to the backbone of the polymer. For example, the polar group can be a lactone group, a hydroxyaryl group, a fluoroalcohol group, or a combination thereof.

[0099] 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):

[0100]

[0101] where R f is hydrogen, fluorine, cyano, or substituted or unsubstituted C 1-10 alkyl.

[0102] In formula (9), L 6 Is a single bond or a divalent linking group. 6 Exemplary divalent linking groups include substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 1-30 Heteroalkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocycloalkylene, substituted or unsubstituted C 6-30 Arylene, substituted or unsubstituted C 3-30 Heteroarylene, -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R 9a )-、or--C(O)N(R 9b )-one or more, wherein R 9a and R 9b Each independently may be hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, or substituted or unsubstituted C 3-20 Heterocycloalkyl.

[0103] It should be understood that when L 6 When it is a single bond, -R23 The moiety is directly attached to the oxygen atom adjacent to the carbonyl group (i.e. -C(O)OR 23 ).

[0104] In formula (9), R 23 Contains substituted or unsubstituted C 4-20 The lactone group contains substituted or unsubstituted C 4-20 Sultone group. Contains C 4-20 Lactone groups and C 4-20 The sultone group may be monocyclic, polycyclic or condensed polycyclic.

[0105] Exemplary monomers having formula (9) may include one or more of the following:

[0106]

[0107]

[0108] where R f is defined as for equation (9).

[0109] The polymer may include repeat units that are alkali soluble and / or have a pKa less than or equal to 12. For example, repeat units comprising polar groups pendant to the polymer backbone may be derived from one or more monomers having formula (10), (11), or (12):

[0110]

[0111] Each R g It can be hydrogen, fluorine, cyano, or substituted or unsubstituted C 1-10 Preferably, R g It can be hydrogen, fluorine, or substituted or unsubstituted C 1-5 The alkyl group is typically a methyl group.

[0112] In formula (10), R 24 C may 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 Preferably, the substituted C 1-100 or C 1-20 Alkyl, substituted C 3-30 or C 3-20 Cycloalkyl, and substituted poly (C 1-3 alkylene oxide) is substituted by one or more of the following: halogen, fluoroalkyl such as C 1-4Fluoroalkyl (typically fluoromethyl), sulfonamide group -NH-S(O)2-Y 1 , where Y 1 Is F or C 1-4 perfluoroalkyl groups (eg, -NHSO2CF3) or fluoroalcohol groups (eg, -C(CF3)2OH).

[0113] In formula (11), L 7 represents a single bond or a multivalent linking group selected from, for example, an optionally substituted aliphatic group (such as C 1-6 Alkylene or C 3-20 Cycloalkylene), and aromatic hydrocarbons, and combinations thereof, optionally having a radical selected from -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -NR 102 -, or -C(O)N(R 102 )-one or more linking moieties, wherein R 102 is selected from hydrogen and optionally substituted C 1-10 For example, the polymer may further comprise repeating units derived from one or more monomers having formula (10), wherein L 7 is a single bond or a multivalent linking group selected from the following: substituted or unsubstituted C 1-20 Alkylene, typically C 1-6 Alkylene; substituted or unsubstituted C 3-20 Cycloalkylene; typically C 3-10 Cycloalkylene; and substituted or unsubstituted C 6-24 Arylene.

[0114] In formula (11), n3 is an integer from 1 to 5, typically 1. It should be understood that when n3 is 1, the group L 7 It should be understood that when n3 is 2, the group L 7 is a trivalent linking group. Similarly, it should be understood that when n3 is 3, the group L 7 Is a tetravalent linking group; when n3 is 4, the group L 7 is a pentavalent linking group; and when n3 is 5, the group L 7 is a hexavalent linking group. Thus, in the context of formula (10), the term "multivalent linking group" refers to any of a divalent, trivalent, tetravalent, pentavalent, and / or hexavalent linking group. In some aspects, when n is 2 or greater, a carboxylic acid group (-C(O)OH) may be attached to the linking group L. 7 In other aspects, when n is 2 or greater, the carboxylic acid group (-C(O)OH) can be attached to the linking group L. 7 on different atoms.

[0115] In formula (12), L8 represents a single bond or a divalent linking group. 8 Can be a single bond, substituted or unsubstituted C 6-30 Arylene, or substituted or unsubstituted C 6-30 Cycloalkylene.

[0116] In formula (12), n4 is 0 or 1. It should be understood that when n4 is 0, the moiety represented by -OC(O)- is a single bond, so that L 8 Directly attached to the alkenyl (vinyl) carbon atom.

[0117] In formula (12), Ar 1 is substituted C 5-60 An aromatic group, which optionally includes one or more aromatic ring heteroatoms selected from N, O, S, or a combination thereof, wherein the aromatic group can be a monocyclic, non-fused polycyclic, or fused polycyclic. 5-60 When the aromatic group is polycyclic, the rings or ring groups may be fused (such as naphthyl, etc.), non-fused, or a combination thereof. 5-60 When the aromatic group is non-fused, the ring or ring groups may be directly connected (such as biaryl, biphenyl, etc.) or may be bridged by heteroatoms (such as triphenylamino or diphenylene ether). 5-60 Aromatic groups can include a combination of fused rings and directly linked rings (eg, binaphthyl, etc.).

[0118] In formula (12), y may be an integer from 1 to 12, preferably from 1 to 6, and typically from 1 to 3. Each R x may independently be hydrogen or methyl.

[0119] Non-limiting examples of monomers having formula (10), (11), or (12) include one or more of the following:

[0120]

[0121]

[0122]

[0123] where Y 1 As described above, and R i For example, for R in formulas (10)-(12) g defined.

[0124] When present, the polymer typically comprises repeat units comprising polar groups (pendant to the backbone of the polymer) in an amount of 1 to 60 mol%, typically 5 to 50 mol%, more typically 5 to 40 mol%, based on the total repeat units in the polymer.

[0125] Non-limiting exemplary polymers of the present invention include one or more of the following:

[0126]

[0127] wherein a, b and c or a, b, c and d represent the mole fractions of the respective repeating units of the polymer.

[0128] The polymer typically has a weight average molecular weight (MW) of 1,000 to 50,000 Daltons (Da), preferably 2,000 to 30,000 Da, more preferably 4,000 to 25,000 Da, and still more preferably 5,000 to 25,000 Da. w ). The polydispersity index (PDI) of the first polymer (which is M w and number average molecular weight (M n ) is typically 1.1 to 3, and more typically 1.1 to 2. Molecular weight values ​​are determined by gel permeation chromatography (GPC) using polystyrene standards.

[0129] The polymers can be prepared using any suitable method or methods known in the art. For example, one or more monomers corresponding to the repeating units described herein can be combined or fed separately using a suitable solvent or solvents and initiators and polymerized in a reactor. For example, the polymers can be obtained by polymerizing the corresponding monomers under any suitable conditions, such as by heating at an effective temperature, irradiating with actinic radiation at an effective wavelength, or a combination thereof.

[0130] Also provided is a photoresist composition comprising the polymer of the present invention, a photoacid generator (PAG), and a solvent.

[0131] Suitable PAGs are capable of generating an acid that causes cleavage of acid-labile groups present on the polymer of the photoresist composition during post-exposure baking (PEB). The PAG can be in a non-polymeric form or in a polymeric form, for example, present in a polymeric repeat unit of a polymer as described above, or as part of a different polymer. In some embodiments, the PAG can be included in the composition as a non-polymeric PAG compound, as a repeat unit of a polymer having a PAG moiety derived from a polymerizable PAG monomer, or as a combination thereof.

[0132] Suitable non-polymeric PAG compounds may have the formula G + A - , where G +is an organic cation selected from iodonium cations substituted with two alkyl groups, two aryl groups, or a combination of alkyl and aryl groups; and sulfonium cations substituted with three alkyl groups, three aryl groups, or a combination of alkyl and aryl groups; and A - is a non-polymerizable organic anion. Particularly suitable non-polymeric organic anions include those whose conjugate acid has a pKa of -15 to 1. Particularly preferred anions are fluorinated alkylsulfonates and fluorinated sulfonimides.

[0133] Useful non-polymeric PAG compounds are known in the art of chemically amplified photoresists and include, for example, onium salts such as triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; di-tert-butylphenyliodonium perfluorobutanesulfonate, and di-tert-butylphenyliodonium camphorsulfonate. Also known are nonionic sulfonates and sulfonyl compounds that act as photoacid generators, such as nitrobenzyl derivatives, for example, 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate, and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonic acid esters, for example, 1,2,3-tris(methylsulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives, for example, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane; ethylenediamine derivatives, for example, bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane; and ethylenediamine derivatives. 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 non-polymeric photoacid generators are further described in U.S. Patent No. 8,431,325 to Hashimoto et al., at column 37, lines 11-47 and columns 41-91. Other suitable sulfonate PAGs include sulfonated esters and sulfonyloxyketones, nitrobenzyl esters, s-triazine derivatives, benzoin tosylate, tert-butylphenyl α-(p-toluenesulfonyloxy)acetate, and tert-butyl α-(p-toluenesulfonyloxy)acetate; as described in U.S. Pat. Nos. 4,189,323 and 8,431,325.

[0134] Typically, when the photoresist composition includes a non-polymeric photoacid generator, it is present in the photoresist composition in an amount of 0.3 to 65 wt %, more typically 1 to 20 wt %, based on the total solids of the photoresist composition.

[0135] In some embodiments, G + It may be a sulfonium cation having the formula (13) or an iodonium cation having the formula (14):

[0136]

[0137] In equations (13) and (14), each R aa are independently substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 3-30 Heteroaryl, substituted or unsubstituted C 7-20 Arylalkyl, or substituted or unsubstituted C 4-20 Heteroarylalkyl. Each R aa can be alone or connected to another group R via a single bond or a divalent linking group aa To form a ring. Each R aa Optionally, a divalent linking group may be included as part of its structure. aa Independently, it may optionally contain an acid labile group selected from, for example, a tertiary alkyl ester group, a secondary or tertiary aryl ester group, a secondary or tertiary ester group having a combination of alkyl and aryl groups, a tertiary alkoxy group, an acetal group, or a ketal group.

[0138] Exemplary sulfonium cations having formula (13) may include one or more of the following:

[0139]

[0140]

[0141] Exemplary iodonium cations having formula (14) may include one or more of the following:

[0142]

[0143]

[0144] PAGs that are onium salts typically contain organic anions having a sulfonate group or a non-sulfonate group such as sulfonamidate, sulfonimidate, methide, or borate.

[0145] Exemplary organic anions having a sulfonate group include one or more of the following:

[0146]

[0147]

[0148] Exemplary non-sulfonated anions include one or more of the following:

[0149]

[0150] The photoresist composition may optionally include a plurality of PAGs. The plurality of PAGs may be polymeric, non-polymeric, or may include polymeric and non-polymeric PAGs. Preferably, each of the plurality of PAGs is non-polymeric.

[0151] In one or more aspects, the photoresist composition can include a first photoacid generator including a sulfonate group on the anion, and the photoresist composition can include a non-polymeric second photoacid generator, wherein the second photoacid generator can include an anion that does not include a sulfonate group.

[0152] In some aspects, the polymer optionally can further comprise repeating units comprising a PAG-containing moiety, such as repeating units derived from one or more monomers having formula (15):

[0153]

[0154] where R m It can be hydrogen, fluorine, cyano, or substituted or unsubstituted C 1-10 Preferably, R m is hydrogen, fluorine, or substituted or unsubstituted C 1-5 Alkyl, typically methyl.

[0155] In formula (15), Q 1 It can be a single bond or a divalent linking group. For example, Q 1 A may include 1 to 10 carbon atoms and at least one heteroatom, more preferably -C(O)-O-. 1 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 3-30 Heterocycloalkylene, substituted or unsubstituted C 6-30 Arylene, or substituted or unsubstituted C 3-30 Preferably, A 1 It may be an optionally substituted divalent C 1-30 Perfluoroalkylene. Z - is an anionic moiety whose conjugate acid typically has a pKa of -15 to 1. For example, Z -It can be a sulfonate, carboxylate, sulfonamide anion, sulfonimide anion, or methide anion. Particularly preferred anion moieties are fluorinated alkylsulfonates and fluorinated sulfonimides. + 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 it is a sulfonium cation substituted with three alkyl groups, three aryl groups, or a combination of alkyl and aryl groups.

[0156] Exemplary monomers having formula (15) may include one or more of the following:

[0157]

[0158] Among them G + is an organic cation as defined herein.

[0159] When used, repeat units comprising a PAG moiety may be included in the polymer in an amount of 1 to 15 mol%, typically 1 to 8 mol%, more typically 2 to 6 mol%, based on the total repeat units in the polymer.

[0160] The photoresist composition further comprises a solvent for dissolving the components of the composition and promoting its coating on the substrate. Preferably, the solvent is an organic solvent conventionally used in the manufacture of electronic devices. Suitable solvents include, for example: aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane and 1-chlorohexane; alcohols such as methanol, ethanol, 1-propanol, isopropanol, tert-butanol, 2-methyl-2-butanol, 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 cyclohexane. The solvents include ketone (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 non-cyclic carbonates such as propylene carbonate, dimethyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate and propylene carbonate; polar aprotic solvents such as dimethyl sulfoxide and dimethylformamide; water; and combinations thereof. Among these, preferred solvents are PGME, PGMEA, EL, GBL, HBM, CHO, and combinations thereof.

[0161] The total solvent content (i.e., the cumulative solvent content of all solvents) in the photoresist composition is typically 40 to 99 wt %, such as 60 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 applied photoresist layer and the coating conditions.

[0162] The polymer is typically present in the photoresist composition in an amount of 10 to 99.9 wt %, typically 25 to 99 wt %, and more typically 40 to 95 wt % based on the total solids of the photoresist composition. It will be understood that "total solids" includes polymer, PAG, additives and other non-solvent components.

[0163] In some respects, the photoresist composition can further include a material (" alkali unstable material ") comprising one or more alkali unstable groups. As mentioned herein, alkali unstable groups are functional groups that can undergo cracking reactions to provide polar groups (such as hydroxyl, carboxylic acid, sulfonic acid, etc.) in the presence of aqueous alkali developers after the exposure step and the post-exposure baking step. Alkali unstable groups will not undergo significant reactions (such as, will not experience bond cleavage reactions) before the developing step of the photoresist composition comprising alkali unstable groups. Therefore, for example, alkali unstable groups will be substantially inert during the soft baking step, exposure step, and post-exposure baking step before exposure. "Substantially inert" means that ≤5%, typically ≤1% of alkali unstable groups (or parts) will decompose, crack, or react during the soft baking step, exposure step, and post-exposure baking step before exposure. Alkali unstable groups are reactive under the photoresist developing conditions of typical use, for example, aqueous alkali photoresist developers (such as 0.26 standard (N) tetramethylammonium hydroxide (TMAH) aqueous solution). In one embodiment, the present invention relates to a kind of photoresist that can be used for the photoresist layer of photoresist.For example, the 0.26N aqueous solution of TMAH can be used for single immersion development or dynamic development, for example, wherein the TMAH developer of 0.26N is distributed to the photoresist layer of imaging and continues suitable time (as 10 to 120 seconds (s)).Exemplary alkali labile group is ester group, is typically fluorinated ester group.Preferably, the labile material of alkali is not miscible with the polymer and other solid components of photoresist composition basically and has surface energy lower than them.Thereby when being coated on substrate, the labile material of alkali can be separated with other solid components of photoresist composition and arrive the top surface of the photoresist layer formed.

[0164] In some aspects, the base-labile material can be a polymeric material (also referred to herein as a base-labile polymer) that can include one or more repeating units comprising one or more base-labile groups. For example, the base-labile polymer can include repeating units containing 2 or more identical or different base-labile groups. Preferred base-labile polymers include at least one repeating unit comprising 2 or more base-labile groups, for example, repeating units comprising 2 or 3 base-labile groups.

[0165] The base labile polymer may be a polymer comprising repeating units derived from one or more monomers having formula (16):

[0166]

[0167] where X e is a polymerizable group selected from C2 alkenyl and (meth) acrylic acid, L 9 is a divalent linking group; and R n is substituted or unsubstituted C 1-20 Fluoroalkyl, provided that the carbon atom bonded to the carbonyl group (-C(O)-) in formula (16) is substituted with at least one fluorine atom. Exemplary monomers having formula (16) may include one or more of the following:

[0168]

[0169] The base-labile polymer may comprise repeating units comprising two or more base-labile groups. For example, the base-labile polymer may comprise repeating units derived from one or more monomers having formula (17):

[0170]

[0171] where X f and R p As in formula (16), for X e and R n Defined; L 10 is a substituted or unsubstituted C 1-20 Alkylene, substituted or unsubstituted C 3-20 a polyvalent linking group selected from the group consisting of a cycloalkylene group, -C(O)-, or -C(O)O-; and n3 may be an integer of 2 or greater, such as 2 or 3. Exemplary monomers of formula (17) may include one or more of the following:

[0172] The base-labile polymer may comprise repeating units comprising one or more base-labile groups. For example, the base-labile polymer may comprise repeating units derived from one or more monomers having formula (18):

[0173]

[0174] where X g and R q As in formula (16), for X e and R n Defined; L 11 is a divalent linking group; and L 12 is substituted or unsubstituted C 1-20 A fluoroalkylene group, wherein the carbon atom bonded to the carbonyl group (-C(O)-) in formula (18) is substituted with at least one fluorine atom. Exemplary monomers having formula (18) may include one or more of the following:

[0175]

[0176] In some respects, the unstable polymer of alkali can comprise one or more unstable groups of alkali and one or more unstable groups of acid, such as one or more unstable ester moieties of acid (such as tert-butyl ester) or unstable acetal groups of acid.For example, the unstable polymer of alkali can comprise the repeating unit that comprises unstable groups of alkali and unstable groups of acid, that is, wherein unstable groups of alkali and unstable groups of acid are present on same repeating unit.In another example, the unstable polymer of alkali can comprise the first repeating unit that contains unstable groups of alkali and the second repeating unit that contains unstable groups of acid.Preferred photoresist of the present invention can show the defect relevant with the resist relief image formed by photoresist composition of reduction.

[0177] Base-labile polymers can be prepared using any suitable method in the art, including those described herein for the first and second polymers. For example, base-labile polymers can be obtained by polymerization of the corresponding monomers under any suitable conditions, such as by heating at an effective temperature, irradiation with actinic radiation at an effective wavelength, or a combination thereof. Additionally or alternatively, one or more base-labile groups can be grafted onto the polymer backbone using a suitable method.

[0178] In some aspects, the base labile material is a single molecule comprising one or more base labile ester groups, preferably one or more fluorinated ester groups. Base labile materials that are single molecules typically have an M in the range of 50 to 1,500 Da. W Exemplary base-labile materials include one or more of the following:

[0179]

[0180] When present, the base labile material is typically present in the photoresist composition in an amount of 0.01 to 10 wt %, typically 1 to 5 wt %, based on the total solids of the photoresist composition.

[0181] In addition, or alternatively, except alkali unstable polymer, photoresist composition can further include except and be different from one or more polymers of photoresist polymer described above.For example, photoresist composition can comprise other polymer as above-mentioned but composition is different, or be similar to above-mentioned those but do not comprise each polymer in essential repeating unit.In addition or alternatively, these one or more other polymers can include those well-known in the photoresist field, for example, be selected from following item: polyacrylate, polyvinyl ether, polyester, polynorbornene, polyacetal, polyethylene glycol, polyamide, polyacrylamide, polyphenol, novolac, styrene polymer, polyvinyl alcohol or its combination.

[0182] The photoresist composition may further include one or more additional optional additives. For example, the optional additives may include actinic and contrast dyes, anti-striation agents, plasticizers, speed enhancers, sensitizers, photodegradable quenchers (PDQ) (also known as photodegradable bases), alkaline quenchers, thermal acid generators, surfactants, etc., or combinations thereof. If present, the 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.

[0183] PDQ generates a weak acid upon irradiation. The acid generated by the photodegradable quencher is not strong enough to react rapidly with the acid-labile groups present in the resist matrix. Exemplary photodegradable quenchers include, for example, photodegradable cations, and preferably can also be used to prepare strong acid generator compounds, with anions of weak acids (pKa>1) (e.g., C 1-20 Carboxylic acid or C 1-20 Examples of the photodegradable quencher include those that are paired with an anion of a sulfonic acid. Exemplary carboxylic acids include formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexanecarboxylic acid, benzoic acid, salicylic acid, and the like. Exemplary carboxylic acids include p-toluenesulfonic acid, camphorsulfonic acid, and the like. In a preferred embodiment, the photodegradable quencher is a photodegradable organic zwitterionic compound, such as diphenyliodonium-2-carboxylate.

[0184] The photodecomposable quencher can be in a non-polymeric or polymer-bound form. When in a polymeric form, the photodecomposable quencher is present in polymerized units on the first polymer or the second polymer. The polymerized units containing the photodecomposable quencher are typically present in an amount 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.

[0185] Exemplary basic quenchers include, for example, linear aliphatic amines such as tributylamine, trioctylamine, triisopropanolamine, tetrakis(2-hydroxypropyl)ethylenediamine: n-tert-butyldiethanolamine, tris(2-acetoxyethyl)amine, 2,2',2",2"'-(ethane-1,2-diylbis(azanetriyl))tetraethanol, 2-(dibutylamino)ethanol, and 2,2',2"-nitrilotriethanol; cyclic aliphatic amines such as 1-(tert-Butoxycarbonyl)-4-hydroxypiperidine, tert-butyl 1-pyrrolidinecarboxylate, tert-butyl 2-ethyl-1H-imidazole-1-carboxylate, di-tert-butyl piperazine-1,4-dicarboxylate, and N-(2-acetoxy-ethyl)morpholine; aromatic amines such as pyridine, di-tert-butylpyridine, and pyridinium; linear and cyclic amides and their derivatives such as N,N-bis(2-hydroxyethyl)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)propan-2-ylcarbamate; ammonium salts such as quaternary ammonium salts of sulfonates, sulfamates, carboxylates and phosphonates; imines such as primary and secondary aldimines and ketimines; diazines such as optionally substituted pyrazines, piperazines, and phenazines; diazoles such as optionally substituted pyrazoles, thiadiazoles and imidazoles; and optionally substituted pyrrolidones such as 2-pyrrolidone and cyclohexylpyrrolidine.

[0186] The basic quencher may be in a non-polymeric or polymer-bound form. When in polymeric form, the quencher may be present in the repeating units of the polymer. The repeating units containing the quencher are typically present in an amount of 0.1 to 30 mol %, preferably 1 to 10 mol %, and more preferably 1 to 2 mol %, based on the total repeating units in the polymer.

[0187] Exemplary surfactants include fluorinated and non-fluorinated surfactants and can be ionic or non-ionic, with non-ionic surfactants being preferred. Exemplary fluorinated non-ionic surfactants include perfluorinated C4 surfactants such as FC-4430 and FC-4432 surfactants available from 3M Corporation; and fluorodiols such as POLYFOX PF-636, PF-6320, PF-656, and PF-6520 fluorosurfactants from Omnova. In one aspect, the photoresist composition further includes a surfactant polymer containing fluorinated repeating units.

[0188] A patterning method using the photoresist composition of the present invention will now be described. Suitable substrates on which the photoresist composition can be applied 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., with semiconductor wafers being typical. Such substrates are typically made of one or more of silicon, polycrystalline silicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. Suitable substrates can be in the form of wafers, such as those used to manufacture 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 appropriately used according to the present invention. The substrate can include one or more layers or structures, which can optionally include an active or operable portion of the device being formed.

[0189] Typically, prior to coating the photoresist composition of the present invention, one or more photoresist layers, such as a hard mask layer (e.g., spin-on carbon (SOC), amorphous carbon, or a metal hard mask layer), a CVD layer (e.g., a silicon nitride (SiN), silicon oxide (SiO), or silicon oxynitride (SiON) layer), an organic or inorganic underlayer, or a combination thereof, are provided on the upper surface of the substrate. Such layers, together with the overcoated photoresist layer, form a photoresist material stack.

[0190] Optionally, an adhesion promoter layer can be applied to the substrate surface before applying the photoresist composition. If an adhesion promoter is desired, any suitable adhesion promoter for the polymer film can be used, such as silanes, typically organosilanes such as trimethoxyvinylsilane, triethoxyvinylsilane, hexamethyldisilazane, or aminosilane coupling agents such as gamma-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those sold under the names of AP 3000, AP 8000, and AP 9000S available from DuPont Electronics & Imaging (Marlborough, Massachusetts).

[0191] Can be by any suitable method, comprise that spin coating, spraying, dip coating, scraper etc. photoresist composition is coated on substrate.For example, applying photoresist layer can be by using coating track in solvent spin coating photoresist to complete, and wherein photoresist is distributed on the wafer of rotation.During distribution, wafer typically with up to 4,000 revs / min (rpm), for example 200 to 3,000rpm, for example 1,000 to 2, the time period of the speed rotation of 500rpm to obtain photoresist composition layer on substrate.It will be appreciated by those skilled in the art that the thickness of the layer applied can be regulated by changing the total solids of rotation speed and / or composition.The photoresist composition layer formed by composition of the present invention typically has 3 to 30 microns (μm), is preferably greater than 5 to 30 μm and more preferably 6 to 25 μm dry layer thickness.

[0192] Next, the photoresist composition is typically soft-baked to minimize the solvent content in the layer, thereby forming a tack-free coating and improving the adhesion of the layer to the substrate. Soft baking is carried out, for example, on a hot plate or in an oven, where a hot plate is typical. The soft baking temperature and time will depend on, for example, the photoresist composition and thickness. The soft baking temperature is typically 80°C to 170°C and more typically 90°C to 150°C. The soft baking time is typically 10 seconds to 20 minutes, more typically 1 minute to 10 minutes and still more typically 1 minute to 2 minutes. One of ordinary skill in the art can easily determine the heating time based on the composition of the composition.

[0193] Next, the photoresist layer is exposed to activating radiation in a patterned manner to produce a solubility difference between the exposed area and the unexposed area. The exposure of the photoresist composition to the radiation that activates the composition mentioned herein shows that radiation can form a latent image in the photoresist composition. Exposure is typically carried out by a patterned photomask, and the photomask has optically transparent areas and optically opaque areas corresponding to the resist layer area to be exposed and the unexposed resist layer area respectively. Alternatively, this exposure can be carried out in a direct write method without a photomask, and the direct write method is typically used for electron beam lithography. The activating radiation typically has a wavelength less than 400nm, less than 300nm or less than 200nm, wherein the wavelength of 248nm (KrF), 193nm (ArF), 13.5nm (EUV) or electron beam lithography is preferred. Preferably, the activating radiation is 248nm radiation. The method can be used in immersion or dry (non-immersion) lithography. The energy of the exposure is typically 1 to 200 mJ / cm2. 2 ), preferably 10 to 100 mJ / cm 2 , and more preferably 20 to 50 mJ / cm 2, which depends on the exposure tool and the components of the photoresist topcoat composition.

[0194] After exposing the photoresist layer, a post-exposure bake (PEB) of the exposed photoresist layer is performed. PEB can be performed, for example, on a hot plate or in an oven, with a hot plate being typical. The conditions for 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., and for a time of 30 to 120 seconds. A latent image defined by polarity-switched regions (exposed regions) and polarity-unswitched regions (unexposed regions) is formed in the photoresist.

[0195] Then, the exposed photoresist layer is developed with a suitable developer to selectively remove those regions of the layer that are soluble in the developer while retaining insoluble regions, to form the photoresist pattern relief image of resulting. In the case of a positive tone development (PTD) process, the exposed regions of the photoresist layer are removed during development and unexposed regions are retained. On the contrary, in a negative tone development (NTD) process, the exposed regions of the photoresist layer are retained during development and unexposed regions are removed. The application of the developer can be completed by any suitable method, as described above for the application of photoresist compositions, wherein spin coating is typical. The developing time is the time period for effectively removing the soluble regions of the photoresist, wherein typically 5 to 60 seconds. Development is typically carried out at room temperature.

[0196] Suitable developers for the PTD process 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 the NTD process 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. The developer is typically 2-heptanone or n-butyl acetate.

[0197] A coated substrate can be formed from the photoresist composition of the present invention. Such a coated substrate comprises: (a) a substrate having one or more layers to be patterned on its surface; and (b) a photoresist composition layer on the one or more layers to be patterned.

[0198] The photoresist pattern can be used as, for example, an etching mask, so that the pattern is transferred to one or more sequentially arranged lower layers by known etching techniques, typically dry etching (such as reactive ion etching). The photoresist pattern can be, for example, used to transfer the pattern to an underlying hard mask layer, which is then used as an etching mask for transferring the pattern to one or more layers below the hard mask layer. If, during pattern transfer, the photoresist pattern does not have loss, it can be removed from substrate by known technology (such as oxygen plasma ashing). When used for one or more such patterning processes, the photoresist composition can be used to manufacture semiconductor devices, such as storage devices, processor chips (CPUs), graphics chips, optoelectronic chips, LEDs, OLEDs and other electronic devices.

[0199] The present invention is further illustrated by the following non-limiting examples.

[0200] Examples

[0201] Example 1

[0202] The synthesis scheme of the monomer designated as MD2 is shown in Scheme 1.

[0203] Solution 1

[0204] Under a nitrogen atmosphere, cesium carbonate (15 g, 77.75 mmol) was added in one portion to a mixture of 3,5-diiodo-4-(methacryloyloxy)benzoic acid (MD1, 20 grams (g), 43.66 millimoles (mmol)) and 1-ethylcyclopentyl 2-chloroacetate (13 g, 68.18 mmol) in 150 milliliters (mL) of N,N-dimethylformamide (DMF). The reaction mixture was stirred at room temperature for 24 hours. The resulting mixture was filtered to remove insoluble inorganic matter, and the filtrate was poured into 200 mL of deionized (DI) water to produce a crude product as an oily residue. The crude product was purified by filtration through a short plug of silica gel (using heptane / ethyl acetate with a volume ratio of 10: 1 as eluent). 100 mg of the inhibitor dibutylhydroxytoluene (BHT) was added to the combined fractions of the pure product, and the solvent was removed under reduced pressure to produce 13.0 g (49%) of monomer MD2 as a colorless solid. 1 H NMR (acetone-d6), δ: 8.52 (s, 2H, 2ArH), 6.49 (s, 1H, CH=CH), 6.06 (s, 1H, CH=CH), 4.86 (s ,2H,CH2),2.15(m,4H,2CH2),2.08(m,4H,2CH2)1.63(m,2H,CH2),0.88(t,3H,CH).

[0205] Example 2

[0206] The synthesis scheme of the monomer designated as MD3 is shown in Scheme 2.

[0207] Scheme 2 Chloromethyl ether (1.0 g, 10.57 mmol) was added to a mixture of 3,5-diiodo-4-(methacryloyloxy)benzoic acid (5 g, 10.91 mmol) in 50 mL of tetrahydrofuran (THF). Diiodopropylamine (1.11 g, 10.96 mmol) was then slowly added thereto, and the mixture was stirred at room temperature overnight. The ammonium salt obtained was removed by filtration, and THF was removed under reduced pressure. The obtained residue was dissolved in 50 mL of dichloromethane (DCM) and washed with an aqueous solution (50 mL) of 0.1 mol (M) of ammonium chloride. The DCM solution was then filtered through a short pad of silica gel. The solvent was removed under reduced pressure to produce the product MD3 as a white solid. Yield 3.3 g. 1 H NMR (acetone-d6), δ: 8.51 (s, 2H, ArH), 6.51 (s, 1H, CH=CH), 5.87 (s, 1H, CH=CH), 5.60 (s, 2H, CH2), 3.79 (t, 2H, CH2), 2.17 (s, 3h, CH3) 1.23 (q, 2H, CH3).

[0208] Example 3

[0209] The synthesis scheme of the monomer designated as MD4 is shown in Scheme 3.

[0210] Option 3

[0211] To a solution of tert-butyl 2-hydroxy-3,5-diiodobenzoate (TBDISA) (16.0 g, 35.67 mmol) in 150 mL of THF was added a solution of N, N-dimethylaminopyridine in 5 mL of DCM. Methacrylic anhydride (6.47 g, 41.88 mmol) was added to the mixture. The contents were stirred at room temperature for 24 hours, and the reaction mixture was then concentrated to produce a light yellow oil (23.7 g). The crude product was dissolved in 30 mL of DCM and purified by filtration through a short plug of silica gel. 100 mg of inhibitor butylated hydroxytoluene (BHT) was added to the combined fractions of the pure product, and the solvent was removed under reduced pressure to produce 16.0 g (86.7%) of monomer MD4 as a light yellow solid. 1 H NMR (acetone-d6), δ: 8.45 (s, 1H, ArH), 8.25 (s, 1H, ArH), 6.48 (s, 1H, CH=CH), 5.90 (s, 1H, CH=CH), 2.50 (s, 3H, CH3), 1.50 (s, 9H, C (CH3) 3).

[0212] Example 4

[0213] The synthesis scheme of the monomer designated as MD5 is shown in Scheme 4.

[0214] Option 4

[0215] 2-Hydroxy-5-iodo-benzoic acid (30.7 g, 116.28 mmol) and carbonyldiimidazole (CDI, 28.28 g, 174.42 mmol) were dissolved in DMF (150 mL). The resulting solution was heated to 50 ° C, stirred for 2.5 h, and then cooled to room temperature. 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU, 7.08 g, 151.16 mmol) and ECP-OH (17.26 g, 151.16 mmol) were then added and the reaction mixture was stirred at room temperature for 48 h. The reaction mixture was washed with heptane to extract the product and concentrated to produce 24.5 g of crude ECPISA, which was used in the next step without further purification.

[0216] Under a nitrogen atmosphere, potassium carbonate (8.63 g, 62.47 mmol) was added to a mixture of crude ECPISA (15.0 g, 41.64 mmol) and 4-vinylbenzyl chloride (7.63 g, 49.97 mmol) in 150 mL of DMF. The reaction mixture was stirred at room temperature for 24 hours. The mixture was diluted with 200 mL of ethyl acetate and washed twice with 250 mL of DI water. The water layer was washed with another 200 mL of ethyl acetate. The combined organic layer was then washed twice with 400 mL of DI water and dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure to produce a crude product as a light yellow liquid. The crude product was filtered and purified through a short plug of silica gel (using heptane / ethyl acetate with a volume ratio of 10: 1 as eluent). 100 mg of BHT was added to the combined fractions of the pure product, and the solvent was removed under reduced pressure to produce 13 g (86.7%) of monomer MD5 as a colorless solid. 1 H NMR (acetone-d6), δ: 7.81 (s, 1H, ArH), 7.73 (d, 2H, ArH), 7.46 (d, 2H, ArH), 7.39 (d, 2H, ArH), 7.01 (d, 1H, ArH), 6.74 (d, 1H, -CH=CH), 5.8 3(d,1H,CH=CH),5.25(d,1H,CH=CH),5.23(s,2H,CH2),2.08(m,2H,CH2),1.95(m,2H,CH2)1.63-1.44(m,6H,3CH2),0.80(t,3H,CH).

[0217] Example 5

[0218] The synthesis scheme of the monomer designated as MD6 is shown in Scheme 5.

[0219] Option 5

[0220] A mixture of 3,5-diiodosalicylic acid (25.0 g, 64 mmol) and carbonyldiimidazole (CDI, 15.59 g, 96.17 mmol) was dissolved in DMF (150 mL). The resulting solution was stirred under a nitrogen atmosphere for 1 h. 1,8-diazabicyclo(5.4.0)undec-7-ene (DBU, 3.9 g, 25.65 mmol) and ECP-OH (9.52 g, 83.35 mmol) were then added, and the reaction mixture was stirred at room temperature for 96 h. The reaction mixture was washed with heptane (4 x 150 mL) to extract the product, and the combined extracts were washed with DI water (2 x 250 mL). The organic layer was concentrated to produce 21.3 g of crude ECPDISA, which was used in the next step without further purification.

[0221] Under a nitrogen atmosphere, potassium carbonate (5.12 g, 24.69 mmol) was added to a mixture of crude ECPDISA (12.0 g, 24.69 mmol) and 4-vinylbenzyl chloride (4.52 g, 29.62 mmol) in 150 mL of DMF. The reaction mixture was stirred at room temperature for 24 hours. The mixture was diluted with 200 mL of ethyl acetate and washed twice with 250 mL of DI water. The water layer was washed with another 200 mL of ethyl acetate. The combined organic layer was then washed twice with 250 mL of DI water, dried over sodium sulfate, filtered, and the solvent was removed under reduced pressure to produce a crude product in a liquid form. The crude product was filtered and purified by a short plug of silica gel (using heptane containing 5 wt% ethyl acetate as eluent). 100 mg of BHT was added to the combined fractions of the pure product, and the solvent was removed under reduced pressure to produce 11.2 g (75.3%) of monomer MD5 as a colorless solid. 1 H NMR (acetone-d6), δ:8.35(s,1H,ArH),7.89(s,1H,ArH),7.52-7.43(m,4H,4ArH),6.78(d,1H,-CH=CH),5.88(d,1H,CH=CH ),5.29(d,1H,CH=CH),4.95(s,2H,CH2),2.05(m,2H,CH2),1.99(m,2H,CH2)1.72-1.55(m,6H,3CH2),0.83(t,3H,CH).

[0222] Example 6

[0223] This example describes the synthesis of comparative polymers P1, P2, and P5 and inventive polymers P3, P4, P6, P7, P8, and P9. The following monomers represent one or more structures used to prepare each of the comparative and inventive polymers.

[0224]

[0225] Comparative polymer P1 was prepared from monomers MA1, MB1, and MC1 in a 50 / 40 / 10 molar feed ratio. The feed solution was prepared by dissolving MA1 (15.0 g, 100 mmol), MB1 (14.561 g, 80 mmol), and MC1 (4.44 g, 20 mmol) in 35 g of PGMEA. Separately, an initiator solution was prepared by dissolving 1.79 g of the azo initiator 2,2'-azobis(2-methylpropionate) (obtained as V-601 from Wako Pure Chemical Industries, Ltd., Japan) in 6.43 g of a 1:1 mixture of PGMEA and tetrahydrofuran (wt%).

[0226] Polymerization is carried out in a 3-neck round-bottom flask equipped with a water condenser and a thermometer to monitor the reaction in the flask. 17.9g of PGMEA is loaded into the reactor and the reactor is heated to 75°C. A syringe pump is used to feed the feed solution and the initiator solution to the reactor within 4 hours. The contents are then stirred for another 2 hours. The contents are subsequently cooled to room temperature, diluted with 20g of THF, and precipitated into a 7:3 (w / w) mixture of 800mL of heptane and isopropanol. The resulting copolymer P1 is separated by filtration. By dissolving the crude polymer in 50g of THF and precipitating into a 7:3 (w / w) mixture of 800mL of DI water / methanol, a second precipitation is performed.

[0227] Each polymer in Table 1 was prepared using a procedure similar to that described above for the preparation of Comparative Polymer P1, except that the monomers and molar feed ratios specified in Table 1 were used.

[0228] Table 1

[0229]

[0230] Photoresist compositions and evaluation

[0231] A photoresist composition was prepared by combining the components shown in Table 2, wherein the amounts are expressed in weight percent (wt%) based on 100 wt% of the total non-solvent components. The total solid content of the photoresist composition was 3.3 wt%. The photoresist composition was prepared in a solvent mixture of propylene glycol monomethyl ether acetate (PGMEA) and methyl 2-hydroxyisobutyrate in a weight ratio of 1:1.

[0232] The obtained photoresist composition was vibrated on a mechanical vibrator and then filtered through a PTFE disc filter having an aperture of 0.2 micron. Each 200 mm silicon wafer coated with a BARC stack (AR3 antireflective agent of 60 nm thickness on an AR40A antireflective agent of 80 nm thickness, DuPont Electronics & Industrial) was spin-coated with the corresponding photoresist composition on a TEL Clean Track ACT 8 wafer track and baked at 110°C for 60 seconds to provide a photoresist layer with a target thickness of approximately 100 nm. The resist layer thickness was measured using a THERMA-WAVE OP7350. The resist layer thickness was measured using a Canon FPA-5000ES4 scanner with 248 nm radiation at 3 to 53 mJ / cm². 2 ) exposure dose to the wafer. The wafer was subjected to a post-exposure bake (PEB) at 100°C for 60 seconds, developed with MF-CD26 TMAH developer (DuPont Electronics & Imaging) for 60 seconds, rinsed with DI water, and dried. Photoresist layer thickness measurements were taken in the exposed and unexposed areas of the layer. A comparison curve for each wafer was generated by plotting the remaining photoresist layer thickness in the exposed area versus the dose. The dose-to-clear (E0) was determined from the comparison curve as the exposure dose at which the remaining photoresist layer thickness was less than 10% of the initial coated thickness. The unexposed film thickness loss (UFTL) was determined based on the photoresist layer thickness measurements in the unexposed areas. The results are shown in Table 2.

[0233] Table 2

[0234]

[0235] * indicates comparative photoresist composition

[0236] The structures of PAG (PAG-1) and additive (Q1) are as follows:

[0237]

[0238] As shown in Table 2 above, photoresist compositions PR-3 and PR-4 comprising polymers derived from compounds of the present invention achieved improved UFTL and improved E2 relative to comparative photoresist compositions PR-1 and PR-2 comprising polymers not derived from compounds of the present invention. o (Increased E o ).

[0239] Photoresist compositions PR-1, PR-2, PR-3, and PR-4 were evaluated for line / space patterning under KrF exposure. 200 mm silicon wafers coated with a BARC stack (60 nm thick AR3 antireflective agent on 80 nm thick AR40A antireflective agent (DuPont Electronics & Industries)) were spin-coated with the corresponding photoresist compositions on a TEL Clean Track ACT 8 wafer track and baked at 110° C. for 60 seconds to provide a photoresist layer having a thickness of approximately 90 nm. Each wafer was exposed to 248 nm radiation using a mask having a 120 nm line / space (1 / s) pattern on a CANNONFPA-5000ES4 scanner (NA=0.8, outer sigma=0.85, inner sigma=0.57). The wafer was post-exposure baked at 100°C for 60 seconds, developed with MF-CD26 TMAH developer (DuPont Electronics & Imaging) for 60 seconds, rinsed with DI water, and dried. Critical dimension (CD) measurements of the formed l / s patterns were performed using a Hitachi S-9380 CD SEM. The sizing energy (E) was determined based on the CD measurements. 尺寸 ) and line width roughness (LWR). The sizing energy is the radiation energy at which the target 120nm l / s pattern is resolved.

[0240] Table 3 shows the results.

[0241] Table 3

[0242]

[0243] * indicates comparative photoresist composition

[0244] As shown in Table 3 above, photoresist compositions PR-3 and PR-4 comprising polymers derived from compounds of the present invention achieved improved LWR (i.e., reduced LWR) and improved E(R) relative to photoresist compositions PR-1 and PR-2 comprising polymers not derived from compounds of the present invention. 尺寸 (Increased E 尺寸 ).

[0245] Photoresist compositions were prepared by dissolving the solid components in a solvent to a total solid content of 3.5 wt % using the materials and proportions described in Table 4 (expressed in wt %, based on 100 wt % total solid components). The resulting mixture was shaken on a mechanical shaker and then filtered through a PTFE disc filter with a pore size of 0.2 microns. 200 mm silicon wafers coated with a BARC stack (60 nm thick AR3 antireflective agent on 80 nm thick AR40A antireflective agent (DuPont Electronics & Imaging)) were spin-coated with the corresponding photoresist composition on a TEL Clean TrackACT 8 wafer track and baked at 110° C. for 60 seconds to provide a photoresist layer having a thickness of approximately 100 nm. Each wafer was exposed to 248 nm radiation using a mask having a 120 nm CD and a 240 nm pitch groove pattern on a CANON FPA-5000ES4 scanner (NA=0.8, outer sigma=0.85, inner sigma=0.57). The wafer was post-exposure baked at 100°C for 60 seconds, developed with MF-CD26 TMAH developer (DuPont Electronics & Imaging) for 60 seconds, rinsed with DI water, and dried. Critical dimension (CD) measurements of the formed l / s patterns were performed using a Hitachi S-9380 CD SEM. The sizing energy (E) was determined based on the CD measurements. 尺寸 ) and line width roughness (LWR). The sizing energy is the radiation energy at which the target 120 nm 1 / s pattern is resolved. The results are shown in Table 4.

[0246] Table 4

[0247]

[0248] * indicates comparative photoresist composition

[0249] The structure of PAG (PAG-2) is as follows:

[0250]

[0251] As shown above, photoresist compositions PR-6 to PR-9 comprising polymers derived from compounds of the present invention achieved improved LWR (i.e., reduced LWR) and improved E(R) relative to photoresist compositions comprising polymers not derived from compounds of the present invention. 尺寸 (Increased E 尺寸 ).

[0252] EUV transmittance calculation

[0253] The following transmittance calculations illustrate the effect of incorporating the compounds of the present invention on film absorption under EUV radiation. Using the online calculation tool on the website of the Center for X-Ray Optics at Lawrence Berkeley National Laboratory, the calculated composition formula was entered and the film density was assumed to be 1.30 g / cm 3 The transmittance of films made from composition examples PR-5 to PR-9 under EUV exposure (13.5 nm) was calculated with a film thickness of 60 nm. The results are shown in Table 5 as percent transmittance (%).

[0254] Table 5

[0255] Photoresist composition Transmittance (%) PR-5* 77.53 PR-6 74.50 PR-7 75.16 PR-8 76.58 PR-9 75.50

[0256] * indicates comparative photoresist composition

[0257] As shown in Table 5, the inventive photoresist compositions PR-6 to PR-9 were calculated to have greater absorption of 13.5 nm radiation compared to PR-5.

Claims

1. A compound having formula (1): in, In formula (1), X is (meth)acrylic acid and L 1 It is a single bond; Ar 1 is a C6 aryl group; n is an integer from 1 to 3; m is 1 or 2; k is 1; L 2 Is a single bond or -C(O)OC(X 1 X 2 )-, where X 1 and X 2 are independently hydrogen, fluorine, unsubstituted C 1-6 Alkyl, or C 1-6 Fluoroalkyl; R 1 It is expressed by one of the formulas (2) or (3): In formulas (2) and (3), R 2 to R 4 are each independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C 3-20 Heterocycloalkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 3-20 Cycloalkenyl, substituted or unsubstituted C 3-20 Heterocycloalkenyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 2-20 Heteroaryl, where R 2 to R 4 Each of which optionally further comprises as part of its structure a divalent linking group; The premise is to select R 2 to R 4 Not more than one of them is hydrogen, and provided that if R 2 to R 4 When one of them is hydrogen, then R 2 to R 4 At least one of the other is a substituted or unsubstituted C 6-20 Aryl or substituted or unsubstituted C 3-20 heteroaryl; R 2 to R 4 Any two of the amines taken together, optionally via a single bond or a divalent linking group, form a ring, wherein the ring is substituted or unsubstituted; R 5 and R 6 are each independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C 3-20 Heterocycloalkyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 2-20 Heteroaryl, where R 5 and R 6 Each of which optionally further comprises as part of its structure a divalent linking group; R 5 and R 6 together, optionally via a single bond or a divalent linking group, to form a ring, wherein the ring is substituted or unsubstituted; R 7 is substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C 3-20 Heterocycloalkyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 2-20 Heteroaryl, where R 7 optionally further comprising a divalent linking group as part of its structure; R 5 or R 6 Any one or more of R 7 together, optionally via a single bond or a divalent linking group, to form a ring, wherein the ring is substituted or unsubstituted; * and *' respectively represent L 2 binding site; or The compound of formula (1) has the following formula:

2. The compound according to claim 1, wherein The compound of formula (1) is selected from the group consisting of:

3. A polymer comprising a first repeating unit derived from the compound according to any one of claims 1 to 2.

4. The polymer according to claim 3, wherein The polymer further comprises a second repeating unit comprising a tertiary alkyl ester group.

5. The polymer according to claim 3 or 4, wherein The polymer further comprises a third repeating unit comprising a polar group pendant to the polymer backbone, and wherein the polar group is a lactone, hydroxyaryl, or fluoroalcohol group.

6. A photoresist composition comprising: The polymer according to any one of claims 3 to 5; photoacid generators; and solvent. 7 . The photoresist composition according to claim 6 , further comprising a photodegradable quencher or a basic quencher.

8. A method for forming a pattern, the method comprising: applying a layer of the photoresist composition according to claim 6 or 7 to a substrate to provide a photoresist composition layer; exposing the photoresist composition layer to activating radiation in a pattern-wise manner to provide an exposed photoresist composition layer; as well as The exposed photoresist composition layer is developed to provide a photoresist pattern.

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