Polymer, photoresist composition, and pattern forming method

Abstract

The present invention provides polymers, photoresist compositions, and pattern formation methods. [Solution] A polymer comprising a first repeating unit derived from a polymerizable compound containing an aromatic group and a second repeating unit containing a base-unstable group, wherein the aromatic group is substituted with a first substituent containing an ethylenically unsaturated double bond, a second substituent which is a hydroxyl group, and a third substituent which is a carbonyl group, and the carbonyl groups of the first substituent, the second substituent, and the third substituent are bonded to different carbon atoms of the aromatic group, and the first repeating unit and the second repeating unit are structurally different.

Description

[Technical Field]

[0001] This invention relates to a polymer containing a functional group switchable by a base, and a photoresist composition containing the same. This invention is particularly applicable to lithography applications in the semiconductor manufacturing industry. [Background technology]

[0002] Photoresist compositions are photosensitive materials used to transfer patterns onto one or more underlying layers, such as metal, semiconductor, or dielectric layers, placed on a substrate. Positive-type chemically amplified photoresist compositions have traditionally been used for high-resolution processing. Such resist compositions typically contain a polymer with acid-unstable groups and a photoacid generator (PAG). A layer of the photoresist composition is exposed to activating radiation in a patterned manner, and the PAG generates acid in the exposed areas. During post-exposure baking, the acid causes cleavage of the acid-unstable groups of the polymer. This creates a difference in solubility between the exposed and unexposed areas of the photoresist layer in the developer solution. In a positive-type development (PTD) process, the exposed areas of the photoresist layer become soluble in the developer, typically an aqueous base developer, and are removed from the substrate surface. The unexposed areas, which are insoluble in the developer, remain after development and form a positive-type relief image. The resulting relief image allows for selective processing of the substrate.

[0003] To increase the integration density of semiconductor devices and enable the formation of structures with dimensions in the nanometer (nm) range, high-resolution photoresists and photolithography processing tools have been and continue to be developed. One method for achieving nm-scale shape sizes in semiconductor devices is to use activation radiation with short wavelengths, e.g., 193 nm or less, for exposure of the photoresist layer. To further improve lithography performance, immersion lithography tools have been developed to effectively increase the numerical aperture (NA) of the lens of the imaging device. This is achieved by using a fluid with a relatively high refractive index, typically water, between the final surface of the imaging device and the top surface of the semiconductor wafer.

[0004] Deep ultraviolet argon fluoride (ArF) excimer laser immersion tools are currently pushing the limits of lithography processing up to 16nm and 14nm device nodes using multiple (double, triple, or higher-order) patterning techniques. However, the use of multiple patterning can be costly in terms of increased material usage and the number of required process steps compared to single-step direct imaging patterns. Therefore, for advanced device nodes, the need for next-generation (e.g., extreme ultraviolet, EUV) lithography photoresist compositions using ultrashort wavelength activation radiation as low as 13.5nm is becoming increasingly important.

[0005] With the extreme feature sizes associated with these advanced device nodes, the performance requirements for photoresist compositions are becoming even more stringent. Desired performance characteristics include, for example, high sensitivity to activation radiation, low unexposed film thickness reduction (UFTL), good contrast, high resolution, and good linewidth roughness (LWR). For example, stochastic variations in conventional chemically amplified photoresist materials for extreme ultraviolet lithography have been shown to produce patterns with high pattern roughness, resulting in insufficient pattern fidelity of etched features and potentially negatively impacting the device's performance characteristics. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] U.S. Patent No. 8,431,325 [Patent Document 2] U.S. Patent No. 4,189,323 [Non-patent literature]

[0007] [Non-Patent Document 1] Wallow,T.et al Proc.SPIE 6921,69211F,2008 [Overview of the project] [Problems that the invention aims to solve]

[0008] Therefore, there is a continuous need for polymers that address one or more problems associated with the conventional technology, and for photoresists containing such polymers. [Means for solving the problem]

[0009] One embodiment provides a polymer comprising a first repeating unit derived from a polymerizable compound containing an aromatic group and a second repeating unit containing a base-unstable group, wherein the aromatic group is substituted with a first substituent containing an ethylenically unsaturated double bond, a second substituent which is a hydroxyl group, and a third substituent which is a carbonyl group, and the carbonyl groups of the first substituent, the second substituent, and the third substituent are bonded to different carbon atoms of the aromatic group, respectively, and the first repeating unit and the second repeating unit are structurally different.

[0010] Another embodiment provides a photoresist composition comprising a polymer, a photoacid generator, and a solvent.

[0011] Further embodiments also provide a method for forming a pattern, comprising: coating a layer of the photoresist composition described in claim 8 or 9 onto a substrate to obtain a photoresist composition layer; pattern-exposing the photoresist composition layer to activating radiation to obtain an exposed photoresist composition layer; and developing the exposed photoresist composition layer to obtain a photoresist pattern. [Modes for carrying out the invention]

[0012] Here, exemplary embodiments are referenced in detail, and examples thereof are illustrated in this description. In this regard, exemplary embodiments may take different forms and should not be construed as being limited to the descriptions expressed herein. Accordingly, exemplary embodiments are described below by reference to the figures in order to illustrate aspects of this description. As used herein, the terms “and / or” encompass any and all combinations of one or more of the enumerated items relating to them. Expressions such as “at least one” qualify the entire list of elements, but not the individual elements of the list, when preceding a list of elements.

[0013] As used herein, the terms “one (a),” “one (an),” and “it” do not imply a limitation of quantity and should be interpreted as encompassing both singular and plural forms unless otherwise specifically indicated herein or the context clearly contradicts this. “Or” means “and / or” unless otherwise specified. The modifying phrase “about” used in relation to quantity includes the expressed value and has meaning determined by the context (e.g., the degree of error associated with the measurement of a particular quantity). All scopes disclosed herein include endpoints, which are independently combinable with one another. The suffix “(s)” includes both singular and plural forms of the term it modifies, thereby intended to include at least one of those terms. “Optional” or “optionally” means that the event or situation described thereafter may or may not occur, and that the description includes both the cases in which the event occurs and the cases in which the event does not occur. The terms “first,” “second,” etc., used herein do not imply order, quantity, or importance, but rather are used to distinguish one element from another. When an element is said to be “on” another element, it may be in direct contact with the other element, or an intervening element may exist between them. In contrast, when an element is said to be “directly on” another element, no intervening element is present. It should be understood that the components, elements, limitations, and / or features described in the embodiments may be combined in any preferred manner in various embodiments.

[0014] Unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as those generally understood by those skilled in the art to which the invention pertains. Terms such as those defined in commonly used dictionaries should be interpreted as having the same meaning as those defined in the relevant art and in relation to this disclosure, and it will be further understood that unless explicitly defined herein, they should not be interpreted in an ideal or overly formal sense.

[0015] As used herein, "chemical beam" or "radiation" means, for example, the emission spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet (EUV) light, X-rays, particle beams such as electron beams and ion beams. Furthermore, in this invention, "light" means chemical beam or radiation. A krypton fluoride laser (KrF laser) is a specific type of excimer laser that may be called an exciplex laser. "Excimer" is an abbreviation for "excitation dimer," while "exciplex" is an abbreviation for "excitation complex." An excimer laser uses a mixture of a noble gas (argon, krypton, or xenon) and a halogen gas (fluorine or chlorine) and emits coherent stimulating radiation (laser light) in the ultraviolet range under suitable conditions of electrical stimulation and high pressure. Furthermore, unless otherwise specified, "exposure" in this specification includes not only exposure using mercury lamps, excimer lasers (such as far ultraviolet light, X-rays, and extreme ultraviolet (EUV) light), but also writing using particle beams such as electron beams and ion beams.

[0016] As used herein, the term "hydrocarbon" means an organic compound or group having at least one carbon atom and at least one hydrogen atom; "alkyl" means a linear or branched saturated hydrocarbon group having a specified number of carbon atoms and a valency of 1; "alkylene" means an alkyl group having a valency of 2; "hydroxyalkyl" means an alkyl group substituted with at least one hydroxyl group (-OH); "alkoxy" means "alkyl-O-"; "carboxyl" and "carbone" "Acid group" refers to a group having the formula "-C(=O)-OH"; "cycloalkyl" refers to a monovalent group having one or more saturated rings in which all ring constituent elements are carbon; "cycloalkylene" refers to a cycloalkyl group with a valency of 2; "alkenyl" refers to a monovalent hydrocarbon group that is straight-chain or branched-chain and has at least one carbon-carbon double bond; "alkenoxy" refers to "alkenyl-O-"; "alkenylene" refers to an alkenyl group with a valency of 2; "cycloalkenyl" refers to a group with at least one carbon-carbon double bond The term "alkynyl" refers to a non-aromatic cyclic divalent hydrocarbon group having a primary double bond and at least three carbon atoms; "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 Hückel's rule (4n + 2π electrons) and contains carbon atoms in the ring; the term "heteroaromatic group" refers to an aromatic group that contains one or more heteroatoms (e.g., 1 to 4 heteroatoms) selected from N, O, and S instead of carbon atoms in the ring; "ally" "Lu" refers to a monovalent monocyclic or polycyclic aromatic ring system in which all ring constituent elements are carbon, which may include a group having an aromatic ring fused to at least one cycloalkyl ring or heterocycloalkyl ring; "Arylene" refers to a divalent aryl group; "Alkylaryl" refers to an aryl group substituted with an alkyl group; "Arylalkyl" refers to an alkyl group substituted with an aryl group; "Aryloxy" refers to "aryl-O-"; and "Arylthio" refers to "aryl-S-".

[0017] The prefix "hetero" means that a compound or group contains at least one constituent atom that is a heteroatom (e.g., 1, 2, 3, or 4 or more heteroatoms) instead of a carbon atom, and that each heteroatom is independently N, O, S, Si, or P; "heteroatom-containing group" refers to a substituent that contains at least one heteroatom; and "heteroalkyl" refers to an alkyl group that has at least one heteroatom instead of a carbon.

[0018] The term "heterocycloalkyl" refers to a cycloalkyl group having at least one heteroatom independently selected from N, O, or S as a ring constituent atom instead of carbon; "heterocycloalkylene" refers to a divalent heterocycloalkyl group. Exemplary three-membered heterocycloalkyl groups containing one heteroatom include azilidinyl, oxylanil, and thiranil. Exemplary four-membered heterocycloalkyl groups containing one heteroatom include azetidinyl, oxetanil, and thietanil. Exemplary five-membered heterocycloalkyl groups containing one heteroatom include tetrahydrofuranil, dihydrofuranil, tetrahydrothiophenyl, dihydrothiophenyl, pyrrolidinyl, dihydropyrrolyl, and pyrrolyl-2,5-dione. Exemplary five-membered heterocycloalkyl groups containing two heteroatoms include dioxolanil, oxathiolanil, and dithiolanil. Exemplary five-membered heterocycloalkyl groups containing three heteroatoms include triazolinil, oxadiazolinil, and thiadiazolinil. Examples of six-membered heterocycloalkyl groups containing one heteroatom include piperidinyl, tetrahydropyranil, dihydropyridinyl, and thianil. Examples of six-membered heterocycloalkyl groups containing two heteroatoms include piperazinyl, morpholinil, dithianil, and dioxanil. An example of a six-membered heterocycloalkyl group containing three heteroatoms is triazinyl. Examples of seven-membered heterocycloalkyl groups containing one heteroatom include azepanil, oxepanil, and thiepanil. Examples of eight-membered heterocycloalkyl groups containing one heteroatom include azokanil, oxecanil, and thiokanil.Examples of bicyclic heterocycloalkyl groups include indolinyl, isoindolinyl, dihydrobenzofuranyl, dihydrobenzothienyl, tetrahydrobenzothienyl, tetrahydrobenzofuranyl, tetrahydroindolyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, decahydroisoquinolinyl, octahydroclomenyl, octahydroisoclomenyl, decahydronaphthilidinyl, decabihydro-1,8-naphthilidinyl, octahydropyrrolo[3,2-b]pyrrole, indolinyl, phthaliumidyl, naphthaliumidyl, chromanyl, clomenyl, and 1H-benzo[e][1,4]diazepinyl Examples include 1,4,5,7-tetrahydropyrano[3,4-b]pyrrolyl, 5,6-dihydro-4H-floo[3,2-b]pyrrolyl, 6,7-dihydro-5H-floo[3,2-b]pyranyl, 5,7-dihydro-4H-thieno[2,3-c]pyranyl, 2,3-dihydro-1H-pyrrolo[2,3-b]pyridinyl, 2,3-dihydrofloo[2,3-b]pyridinyl, 4,5,6,7-tetrahydro-1H-pyrrolo[2,3-b]pyridinyl, 4,5,6,7-tetrahydrofloo[3,2-c]pyridinyl, 4,5,6,7-tetrahydrothieno[3,2-b]pyridinyl, and 1,2,3,4-tetrahydro-1,6-naphthilidinyl.

[0019] The term "heteroaryl" refers to a 4-8 membered monocyclic, 8-12 membered bicyclic, or 11-14 membered tricyclic aromatic ring system having 1-4 heteroatoms (for monocyclics), 1-6 heteroatoms (for bicyclics), or 1-9 heteroatoms (for tricyclics), each independently selected from N, O, or S (for example, in the case of monocyclics, bicyclics, or tricyclics, a carbon atom and 1-3, 1-6, or 1-9 heteroatoms independently selected from N, O, or S, respectively). Examples of 5-membered heteroaryl groups containing one heteroatom include pyrrolyl, furanyl, and thiophenyl. Examples of 5-membered heteroaryl groups containing two heteroatoms include imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, and isothiazolyl. Examples of 5-membered heteroaryl groups containing three heteroatoms include triazolyl, oxadiazolyl, and thiadiazolyl. Exemplary five-membered heteroaryl groups containing four heteroatoms include tetrazolyl. Exemplary six-membered heteroaryl groups containing one heteroatom include pyridinyl. Exemplary six-membered heteroaryl groups containing two heteroatoms include pyridazinyl, pyrimidinyl, and pyrazinyl. Exemplary six-membered heteroaryl groups containing three or four heteroatoms include triazinyl and tetradinyl, respectively. Exemplary seven-membered heteroaryl groups containing one heteroatom include azepinyl, oxepinyl, and thiepinyl. Exemplary 5,6-bicyclic heteroaryl groups include indolyl, isoindolyl, indazolyl, benzotriazolyl, benzothiophenyl, isobenzothiophenyl, benzofuranil, benzoisofuranil, benzimimidazolyl, benzoxazolyl, benzisoxazolyl, benzoxadiazolyl, benzthiazolyl, benzisothiazolyl, benzthiadiazolyl, indolidinyl, and prinyl. Examples of 6,6-bicyclic heteroaryl groups include naphthilidinyl, pteridinyl, quinolinyl, isoquinolinyl, synnolinyl, quinoxalinyl, phthalazinyl, and quinazolinyl.Examples of tricyclic heteroaryl groups include, but are not limited to, phenanthridine, dibenzofuranil, carbazolyl, acridinil, phenothiazinil, phenoxadinil, and phenazinil.

[0020] The term "halogen" refers to a monovalent substituent that is fluorine (fluoro), chlorine (chloro), bromine (bromo), or iodine (iodo). The prefix "halo" refers to a group that contains one or more fluoro, chloro, bromo, or iodo substituents instead of a hydrogen atom. Combinations of halo groups (e.g., bromo and fluoro) or fluoro groups alone may exist. For example, the term "haloalkyl" refers to an alkyl group substituted with one or more halogens. As used herein, "substituted C 1~8 "Haloalkyl" refers to C substituted with at least one halogen. 1~8 This refers to an alkyl group that is further substituted with one or more other substituents that are not halogens. It should be understood that because halogen atoms do not replace carbon atoms, substitution of a group at a halogen atom is not considered a heteroatom-containing group.

[0021] The term "fluorination" means having one or more fluorine atoms incorporated into the base in place of a halogen. For example, C 1~18 Where a fluoroalkyl group is indicated, it may contain one or more fluorine atoms, e.g., a single fluorine atom, two fluorine atoms (e.g., a 1,1-difluoroethyl group), three fluorine atoms (e.g., a 2,2,2-trifluoroethyl group), or a fluorine atom at each valence of carbon (e.g., as a perfluoro group such as -CF3, -C2F5, -C3F7, or -C4F9). “Substituting fluoroalkyl group” is understood to mean a fluoroalkyl group further substituted by at least one additional substituent that does not contain a fluorine atom.

[0022] Each of the substituents described above may be optionally substituted, unless otherwise explicitly indicated. The term "optionally substituted" refers to being either substituted or unsubstituted. "Substituted" means that at least one hydrogen atom of a chemical structure or group is replaced with another terminal substituent, typically monovalent, provided that it does not exceed the normal valence of the specified atom. When the substituent is oxo (i.e., O), two geminal hydrogen atoms on a carbon atom are replaced with a terminal oxo group. The oxo group is bonded to carbon via a double bond to form a carbonyl (C=O), and it is further noted that the carbonyl group is represented herein as -C(O)-. Combinations of substituents or variables are allowed. Exemplary substituents that may be present at the "substituted" position include, but are not limited to, nitro (-NO2), cyano (-CN), hydroxyl (-OH), oxo (O), amino (-NH2), mono- or di(C 1~6 )alkylamino, alkanoyl (e.g., C 2~6 alkanoyl group such as acyl), formyl (-C(O)H), carboxylic acid or its alkali metal salt or ammonium salt; C 2~6 alkyl ester (-C(O)O-alkyl or -OC(O)-alkyl) and C 7~13 aryl ester (-C(O)O-aryl or -OC(O)-aryl) such as esters (including acrylates, methacrylates, and lactones); amide (-C(O)NR2 (R is hydrogen or C 1~6 alkyl)), carboxamide (-CH2C(O)NR2 (R is halogen or C 1~6 alkyl)), halogen, thiol (-SH), C 1~6 alkylthio (-S-alkyl), thiocyano (-SCN), C 1~6 alkyl, C 2~6 alkenyl, C 2~6 alkynyl, C 1~6 haloalkyl, C 1~9 alkoxy, C 1~6 haloalkoxy, C 3~12 cycloalkyl, C 5~18 cycloalkenyl, C 2~18Heterocycloalkenyl, a C having at least one aromatic ring 6~12 Aryls (e.g., phenyl, biphenyl, naphthyl, etc., where each ring is substituted or unsubstituted aromatic), C having 1 to 3 independent or fused rings and 6 to 18 ring carbon atoms. 7~19 Arylalkyls, arylalkoxys having 1-3 independent or fused rings and 6-18 ring carbon atoms, C 7~12 Alkylaryl, C 3~12 Heterocycloalkyl, C 3~12 Heteroaryl, C 1~6 Alkylsulfonyl (-S(O)2-alkyl), C 6~12 Examples include arylsulfonyl (-S(O)2-aryl) or tosyl (CH3C6H4SO2-). When a group is substituted, the number of carbon atoms indicated is the total number of carbon atoms in the group, excluding the carbon atoms of any substituents. For example, the group -CH2CH2CN is a cyanosubstituted C2 alkyl group.

[0023] In this specification, unless otherwise defined, "divalent linking group" refers to -O-, -S-, -Te-, -Se-, -C(O)-, -N(R ’ )-, C(O)N(R ’ )-, -S(O)-, -S(O)2-, -C(S)-, -C(Te)-, -C(Se)-, substitution or non-substitution C 1~30 Alkylene, substituted, or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 This refers to a divalent group containing one or more heteroarylenes or combinations thereof, where each R ’ These are, independently, hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl or substituted or unsubstituted C 3~30It is a heteroaryl compound. Typically, the divalent linking group is -O-, -S-, -C(O)-, -N(R')-, -S(O)-, -S(O)2-, substituted or unsubstituted C 1~30 Alkylene, substituted, or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 It comprises one or more heteroarylenes or combinations thereof, where R' is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl or substituted or unsubstituted C 3~30 It is a heteroaryl compound. More typically, the divalent linking groups are -O-, -S-, -C(O)-, -C(O)O-, -N(R ’ )-, -C(O)N(R')-, substitution or non-substitution C 1~10 Alkylene, substituted, or unsubstituted C 3~10 Cycloalkylene, substituted or unsubstituted C 3~10 Heterocycloalkylene, substituted or unsubstituted C 6~10 Arylene, substituted or unsubstituted C 3~10 The compound comprises at least one heteroarylene or a combination thereof, where R is hydrogen, substituted or unsubstituted C 1~10 Alkyl, substituted, or unsubstituted C 1~10 Heteroalkyl, substituted, or unsubstituted C 6~10 Aryl or substituted or unsubstituted C 3~10 It is a heteroaryl compound.

[0024] As used herein, “acid-unstable group” refers to a group whose bond is optionally and typically cleaved by the action of an acid during heat treatment, resulting in the formation of a polar group such as a carboxylic acid group or an alcohol group. When this type of group is a pendant on a polymer, the formation of the polar group occurs on the polymer. Optionally and typically, the site that was linked to the cleaved bond is detached from the polymer. In other systems, nonpolymer compounds may contain acid-unstable groups that can be cleaved by the action of an acid, resulting in the formation of a polar group such as a carboxylic acid group or an alcohol group on the cleaved portion of the nonpolymer compound. Such acids are typically photo-generated acids in which bond cleavage occurs during post-exposure baking (PEB). However, embodiments are not limited thereto, and for example, such acids may be thermally generated. Preferred acid-unstable groups include, for example, tertiary alkyl ester groups, secondary or tertiary aryl ester groups, secondary or tertiary ester groups having a combination of alkyl and aryl groups, tertiary alkoxy groups, acetal groups, or ketal groups. In this technical field, acid-unstable groups are generally referred to as "acid-cleavable groups," "acid-cleavable protecting groups," "acid-unstable protecting groups," "acid-leaving groups," "acid-degradable groups," and "acid-sensitive groups."

[0025] The term "unsaturated bond" refers to a double or triple bond. The terms "unsaturated" or "partially unsaturated" refer to a site containing at least one double or triple bond. The term "saturated" refers to a site that does not contain a double or triple bond, i.e., a site containing only single bonds.

[0026] As used herein, the term "(meth)acrylic" includes both acrylic species and methacrylic species (i.e., acrylic monomers and methacrylic monomers), and the term "(meth)acrylate" includes both acrylate species and methacrylate species (i.e., acrylate monomers and methacrylate monomers).

[0027] Embedded barrier layers (EBLs) for photolithography were typically designed and developed for use in ArF (193 nm) immersion compounding techniques. EBLs are formed using low surface energy materials that can be directly added to the photoresist composition and segregate onto the surface of the resulting film during spin coating. These materials can be switchable developers that can switch from hydrophobic to hydrophilic during the development process, or base-switchable polymers. To reduce defects in compounding other than ArF photoresist compositions, there has been a need for the development of base-switchable polymer additives to further improve photolithography performance at other exposure wavelengths such as KrF and / or EUV by utilizing base-switchable polymer-based additives.

[0028] The polymer of the present invention comprises a first repeating unit having substituents including aromatic groups and carbonyl groups substituted with hydroxyl groups, and a second repeating unit containing a base-unstable group. In some embodiments, the base-unstable group comprises a base-cleavable phenol ester containing one or more electron-withdrawing fluorine substituents. Before cleavage of the base-unstable group, the substance is relatively hydrophobic, while after cleavage, the resulting hydroxyaromatic group increases the substance's hydrophilicity. The polymer of the present invention can be used as a base-switchable polymer in photoresist compositions, resulting in improved LWR and / or a decrease in the pseudo-Z factor. The polymer of the present invention also showed improved dissolution rate when coated as a film, soft-baked, and treated with a developer.

[0029] In one embodiment, a polymer is provided comprising a first repeating unit derived from a polymerizable compound containing an aromatic group. This aromatic group is substituted with a first substituent containing an ethylenically unsaturated double bond. The aromatic group is substituted with a second substituent which is a hydroxyl group. This aromatic group is also substituted with a third substituent which is a carbonyl group. The carbonyl groups of the first, second, and third substituents are each bonded to different carbon atoms of the aromatic group. The polymer also comprises a second repeating unit containing a base-unstable group. The first and second repeating units of the polymer are structurally distinct from each other. It should be noted that the polymer may also contain one or more additional repeating units in addition to the first and second repeating units, such additional repeating units as described herein. Furthermore, it should be understood that while the aromatic group is substituted with the first, second, and third substituents, the aromatic group may be further substituted with other groups as described herein.

[0030] As used herein, the term "aromatic group" refers to C 6~60 Aryl group or C 3~60 This refers to a heteroaryl group. Aromatic groups can be monocyclic or polycyclic. C 6~60 When the aryl group is polycyclic, the ring or ring group may be condensed (e.g., naphthyl group), directly bonded (e.g., biaryl, biphenyl), or a combination of condensed and directly bonded rings or ring groups (e.g., binaphthyl). 3~60 When the heteroaryl group is polycyclic, the ring or ring group may be fused, directly bonded, or a combination of a fused ring or ring group and a directly bonded ring or ring group.

[0031] The first repeating unit of the polymer is derived from a polymerizable compound containing an aromatic group substituted with a first substituent containing an ethylenically unsaturated double bond, a second substituent which is a hydroxyl group, and a third substituent which is a carbonyl group.

[0032] The first substituent of the aromatic group contains an ethylenically unsaturated double bond. As used herein, "ethylenically unsaturated double bond" refers to a vinyl-containing polymerizable group, typically a substituted or unsubstituted C2- 20 The polymerizable group may be selected from alkenyls, substituted or unsubstituted norbornene, substituted or unsubstituted (meth)acrylics, substituted or unsubstituted vinyl ethers, substituted or unsubstituted vinyl ketones, substituted or unsubstituted vinyl esters, or substituted or unsubstituted vinyl aromatics. The polymerizable group may form a ring with the aromatic group.

[0033] The second substituent of the aromatic group is a hydroxyl (-OH) group. It should be understood that the second substituent may include one or more hydroxyl groups. In some embodiments, the second substituent may include 1 to 9 hydroxyl groups, or 1 to 5 hydroxyl groups, or 1 to 3 hydroxyl groups, or 1 or 2 hydroxyl groups.

[0034] The third substituent of the aromatic group includes a carbonyl group (-C(=O)-). It should be understood that the third substituent may include a carbonyl group, or may include two or more carbonyl groups that are the same or different from each other. In some embodiments, the third substituent may include 1 to 9 different carbonyl groups, or 1 to 5 different carbonyl groups, or 1 to 3 different carbonyl groups, or 2 different carbonyl groups, or a single carbonyl group (i.e., one carbonyl group). In some embodiments, the carbonyl group may be directly bonded to the aromatic group.

[0035] It is understood that the third substituent containing the carbonyl group may further include a hydrocarbon group which may be optionally substituted with 1 to 3 heteroatoms. In some embodiments, the third substituent containing the carbonyl group may further include an acid-unstable group. Suitable acid-unstable groups for the third substituent include, for example, one or more of the following: a tertiary alkyl ester group, a secondary or tertiary aryl ester group, a secondary or tertiary ester group having a combination of an alkyl group and an aryl group, a tertiary alkoxy group, an acetal group, or a ketal group.

[0036] In polymerizable compounds containing aromatic groups, the carbonyl groups of the first, second, and third substituents are each bonded to different carbon atoms of the aromatic group.

[0037] In some embodiments, the total number of second and third substituents in a polymerizable compound containing an aromatic group is 10 or less. For example, in a polymerizable compound containing an aromatic group, the total number of second and third substituents may be 5 or less, or 4 or less, or 3 or less, or 2. In some embodiments, the total number of second substituents and third substituents may be 2 to 6, or 2 to 4.

[0038] In some embodiments, the first substituent does not contain an acid-unstable or acid-leaving group. In other words, in some embodiments, the polymerizable compound contains a polymerizable group 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 group and an aryl group, a tertiary alkoxy group, an acetal group, or a ketal group (i.e., an ethylenically unsaturated double bond). For example, the first substituent of the compound of the present invention is (meth)acrylic or vinyl (e.g., substituted or unsubstituted C) 2~12 It may be alkenil.

[0039] In some embodiments, the first repeating unit can be derived from the monomer of formula (1): [ka]

[0040] In formula (1), P 1 contains a group containing an ethylenically unsaturated double bond, and P 1 may optionally form a ring with Ar 1 . Preferably, P 1 is (meth)acrylic or substituted or unsubstituted C 2~12 alkenyl. In some embodiments, P 1 may further contain a divalent linking group between the group containing an ethylenically unsaturated double bond and Ar 1 . For example, P 1 contains, in addition to the group containing an ethylenically unsaturated double bond, 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 )- and contains a divalent linking group containing one or more of them, and R 1a and R 1b are each independently hydrogen or C 1~6 alkyl.

[0041] In formula (1), Ar 1 is substituted or unsubstituted C 6~60 aryl or substituted or unsubstituted C 3~60 heteroaryl, and each may optionally be 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 6~30Aryl, 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 Alkylheteroaryl, or substituted or unsubstituted C 4~30 It may be further substituted with one or more of heteroarylalkyl.

[0042] "Further substituted" means that a C 6~50 aryl group or a C 3~50 heteroaryl group is optionally substituted with at least a first substituent (-P 1 ), a second substituent (OH) a , and a third substituent (-C(O)-L 1 -R 1 ), and that a C 6~60 aryl group or a C 3~60 heteroaryl group may optionally be further substituted with one or more other substituents different from the first substituent, the second substituent, and the third substituent. Typically, Ar 1 is C 6~30 aryl, optionally substituted or unsubstituted C 1~30 alkyl, substituted or unsubstituted C 1~30 heteroalkyl, substituted or unsubstituted C 3~30 cycloalkyl, substituted or unsubstituted C 1~30 heterocycloalkyl, or a combination thereof, may be further substituted.

[0043] In formula (1), a represents the number of hydroxyl groups directly bonded to the aromatic group (Ar 1 ), and is an integer of 1 or more. In some embodiments, a 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, a is 1 or 2.

[0044] In formula (1), each L 1These are independently single or divalent linking groups. For example, L 1 is a substitution or non-substitution 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 2a -, or -N(R 2b )- may be a divalent linking group containing one or more of the following, R 2a and R 2b Each of them independently consists of hydrogen or C 1~6 It is alkyl.

[0045] In equation (1), each R 1 These are independently substituted or unsubstituted C 1~30 Alkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 1~30 Heteroalkyl, substituted, or unsubstituted C 2~30 Heterocycloalkyl, substituted, or unsubstituted C 6~60 Aryl, or substituted or unsubstituted C 3~60 It is a heteroaryl compound.

[0046] In formula (1), b represents the number of third substituents, and the third substituent is moiety-C(O)-L 2 -R 1 It can be defined by , which is an integer greater than or equal to 1. In some embodiments, b 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, b is an integer from 1 to 3.

[0047] In equation (1), the sum of a and b (a+b) is an integer less than or equal to 10. For example, the sum of a and b (a+b) can be an integer between 2 and 8, or between 2 and 6, or between 2 and 4. Preferably, the sum of a and b (a+b) is an integer between 2 and 4.

[0048] In equation (1), r is an integer greater than or equal to 1. For example, in equation (1), r can be an integer between 1 and 5. Typically, r is 1.

[0049] In some embodiments, the part of formula (1) -C(O)-L 1 -R 1 This includes acid-unstable groups. Examples of acid-unstable 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.

[0050] In some embodiments, part of formula (1) -C(O)-L 1 -R 1 It may have a structure represented by one of equations (2) or (3): [ka]

[0051] In equation (2), R 2 ~R 4 These are, independently, hydrogen, substituted or unsubstituted C. 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, substituted, or unsubstituted C 3~20 Heterocycloalkyl, substituted, or unsubstituted C 2~20 Alkenyl, substituted, or unsubstituted C 3~20 Cycloalkenyl, substituted or unsubstituted C 3~20 Heterocycloalkenyl, substituted or unsubstituted C 6~20 Aryl, or substituted or unsubstituted C 2~20 It is a heteroaryl, but R 2 ~R 4 The condition is that only one selected from is hydrogen, 2 ~R 4 If one of them is hydrogen, then R 2 ~R 4 At least one other is substitution or non-substitution C 6~20 Aryl or substituted or unsubstituted C3~20 The condition is that it is a heteroaryl compound. Each R 2 ~R 4 It may optionally further include a divalent linking group as part of its structure. For example, each R 2 ~R 4 As part of its structure, -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R 3a )- or -C(O)N(R 3b )- may further include one or more groups selected from, R 3a and R 3b These are, independently, hydrogen, substituted or unsubstituted C. 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl or substituted or unsubstituted C 3~20 It is a heterocycloalkyl group. Typically, R 2 ~R 4 These are, independently, hydrogen, substituted or unsubstituted C. 1~10 Alkyl, substituted, or unsubstituted C 3~8 Cycloalkyl or substituted or unsubstituted C 6~14 It is Ariel.

[0052] In equation (3), R 5 and R 6 These are, independently, hydrogen, substituted or unsubstituted C. 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, substituted, or unsubstituted C 3~20 Heterocycloalkyl, substituted, or unsubstituted C 6~20 Aryl, or substituted or unsubstituted C 2~20 It is a heteroaryl. Each R 5 and R 6 It may optionally further include a divalent linking group as part of its structure. For example, each R 5 and R 6 As part of its structure, -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R 3a )-, or -C(O)N(R 3b )- may further include one or more groups selected from R 3a and R3b These are, independently, hydrogen, substituted or unsubstituted C. 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 3~20 It is a heterocycloalkyl group. Typically, R 5 and R 6 Each of these is independently hydrogen or substituted or unsubstituted C 1~10 It is alkyl.

[0053] In equation (3), R 7 is a substitution or non-substitution C 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, substituted, or unsubstituted C 3~20 Heterocycloalkyl, substituted, or unsubstituted C 6~20 Aryl, or substituted or unsubstituted C 3~20 It is a heteroaryl. 7 It may optionally further include a divalent linking group as part of its structure. Typically, R 7 is a substitution or non-substitution C 1~10 Alkyl, substituted, or unsubstituted C 3~8 Cycloalkyl or substituted or unsubstituted C 6~14 It could be Ariel.

[0054] In equation (2), R 2 , R 3 , or R 4 Any two of these may optionally form a ring together via a single bond or a divalent linking group, and the ring may be substituted or unsubstituted. In equation (3), R 5 and R 6 R may optionally form a ring together via a single bond or a divalent linking group, and the ring may be substituted or unsubstituted. In equation (3), R 5 or R 6 One or more of these are optionally connected via a single bond or a divalent linking group to R 7 They may form a ring together, and the ring may be substituted or unsubstituted.

[0055] In equations (2) and (3), * and *' are Ar 1 This represents the binding site to [the target].

[0056] Examples of polymerizable compounds containing aromatic groups include the following: [ka] [ka] [ka]

[0057] The polymer of the present invention also includes a second repeating unit, the second repeating unit containing a base-unstable group. The base-unstable group referred to herein is a functional group that can provide polar groups such as hydroxyl, carboxylic acid, and sulfonic acid via a cleavage reaction in the presence of an aqueous alkaline developer after the exposure and post-exposure bake steps. The base-unstable group will not react significantly (e.g., not undergo bond cleavage) before the development step of the photoresist composition containing the base-unstable group. Therefore, for example, the base-unstable group will be substantially inert during the pre-exposure soft bake, exposure, and post-exposure bake steps. "Substantially inert" means that 5% or less, typically 1% or less of the base-unstable group (or portion thereof) decompose, cleave, or react during the pre-exposure soft bake, exposure, and post-exposure bake steps. The base-unstable group reacts well under typical photoresist development conditions using an aqueous alkaline photoresist developer, such as an aqueous solution of 0.26 N (N) tetramethylammonium hydroxide (TMAH). For example, a 0.26N aqueous solution of TMAH can be used for single-paddle development or dynamic development, where, for instance, the 0.26N TMAH developer is distributed to the imaged photoresist layer for an appropriate time, such as 10 to 120 seconds (s). Exemplary base-unstable groups are ester groups, typically fluorinated ester groups or fluorinated alcohol groups. In some embodiments, base-unstable groups may include fluorinated alkyl ester groups, fluorinated aryl ester groups, or hexafluoroalcohol groups.

[0058] The second repeating unit may contain one or more base-degradable groups. For example, in some embodiments, the second repeating unit may contain two or more base-unstable groups, for instance, two or three base-unstable groups. Each of the base-unstable groups in the second repeating unit may be the same or different.

[0059] In some embodiments, the second repeating unit can be derived from one or more polymerizable compounds, each containing a polymerizable group having an ethylenically unsaturated double bond and a base-unstable group having a structure represented by formula (4). [ka]

[0060] In equation (4), X 1 is O, S, or -N(R c )- and R c is hydrogen or C 1~6 It is alkyl. Typically, X 1 It is O.

[0061] In equation (4), R f R is a substituted or unsubstituted fluoroalkyl group containing a fluorine atom or fluoroalkyl group bonded to the carbon atom at the α-position relative to the carbonyl group (i.e., the carbon atom bonded to the carbonyl (-C(O)-) is substituted with at least one fluorine atom or fluoroalkyl group). In some embodiments, each R f Independently, C is either substituted or unsubstituted. 1~20 It is a fluoroalkyl group, provided that at least one carbon atom bonded to the carbonyl (-C(O)-) is substituted with a fluorine atom or a fluoroalkyl group. For example, R f C is either substituted or unsubstituted. 1~20 , C 1~10 , C 1~5 , C 1~4 , or C 1~3 It may be a fluoroalkyl group. Typically, R f These are -CF3, -CH2CF3, -CF2CH3, -CF2CF2H, -C2F5, -C3F7, or -C4F9.

[0062] For example, the second repeating unit is given by equation (5): [ka] It can be derived from one or more polymerizable compounds.

[0063] In equation (5), P 2 P is a group containing an ethylenically unsaturated double bond, 2 L is optional.2 They may form a ring.

[0064] In equation (5), L 2 is a single bond or linking group. Typically, L 2 is a substitution or non-substitution C 1~20 Alkylene, substituted, or unsubstituted C 3~20 Cycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 A linking group containing one or more of heteroarylene, -C(O)-, or -C(O)O-. Typically, L 2 is a substitution or non-substitution C 1~20 Alkylene, or substituted or unsubstituted C 6~30 The linking group may contain one or more arylenes.

[0065] In some embodiments, L 2 is an aromatic group substituted with at least one halogen, for example, a C substituted with at least one halogen. 6~30 Arylene, or C substituted with at least one halogen 3~30 It may contain heteroarylenes. For example, L 2 This may include aromatic groups substituted with 1 to 9 halogen atoms, or 1 to 6 halogen atoms, or 1 to 4 halogen atoms, or 1 to 3 halogen atoms, or 1 to 2 halogen atoms. Preferably, at least one halogen atom is iodine. As used herein, "aromatic group substituted with at least one halogen" refers to an aromatic group directly bonded to at least one halogen atom.

[0066] In equation (5), each X 1 These are independently O, S, or -N(R c )- and R c is hydrogen or C 1~6 It is alkyl. Typically, X 1 It is O.

[0067] In equation (5), each R fR is a substituted or unsubstituted fluoroalkyl group containing a fluorine atom or fluoroalkyl group bonded to the carbon atom at the α-position relative to the carbonyl group (i.e., the carbon atom bonded to the carbonyl (-C(O)-) is substituted with at least one fluorine atom or fluoroalkyl group). In some embodiments, each R f Independently, C is either substituted or unsubstituted. 1~20 It is a fluoroalkyl group, provided that the carbon atoms bonded to the carbonyl (-C(O)-) are substituted with at least one fluorine atom or a fluoroalkyl group. For example, R f C is either substituted or unsubstituted. 1~20 , C 1~10 , C 1~5 , C 1~4 , or C 1~3 It may be a fluoroalkyl group. Typically, R f These are -CF3, -CH2CF3, -CF2CH3, -CF2CF2H, -C2F5, -C3F7, or -C4F9.

[0068] In equation (5), each d is an integer greater than or equal to 1. For example, each d may be an integer between 1 and 3.

[0069] In equation (5), e is an integer greater than or equal to 1. Preferably, e is 1 or 2. Typically, e is 1.

[0070] Examples of polymerizable compounds of formula (5) include the following: [ka] [ka] [ka]

[0071] The first repeating unit is typically present in the polymer in amounts of 0.1 to 30 mole percent (mol%), more typically 1 to 25 mol%, and even more typically 5 to 20 mol%, relative to the total number of repeating units in the polymer.

[0072] The second repeating unit is typically present in the polymer in amounts of 0.1–95 mol%, more typically 20–95 mol%, and even more typically 50–90 mol%, relative to the total repeating units in the polymer.

[0073] The polymer may optionally further contain one or more additional repeating units that are different from both the first and second repeating units. For example, the second may optionally contain one or more additional repeating units as described below. If the one or more additional units are present in the polymer, they may be used in an amount of up to 70 mol%, typically 3 to 50 mol%, based on the total repeating units in the polymer.

[0074] In one or more embodiments, the polymer may contain acid-unstable repeating units derived from monomers represented by one or more of formulas (6), (7), (8), (9), or (10). [ka]

[0075] In equations (6), (7), and (8), R a , R b , and R c These are, independently, hydrogen, fluorine, cyano, or substituted or unsubstituted C. 1~10 It may be alkyl. Preferably, R a , R b , and R c These are, independently, hydrogen, fluorine, or substituted or unsubstituted C. 1~5 Alkyl, typically methyl, may be used.

[0076] In equation (6), L 4L is a divalent linking group. For example, L 4 It may contain 1 to 10 carbon atoms and at least one heteroatom. A typical example is L 4 is -OCH2-, -OCH2CH2O-, or -N(R 6a )(in the formula -, R 6a is hydrogen or C 1~6 It may be alkyl.

[0077] In equations (6) and (7), R 8 ~R 13 These are, independently, hydrogen, substituted or unsubstituted C. 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, substituted, or unsubstituted C 3~20 Heterocycloalkyl, substituted, or unsubstituted C 2~20 Alkenyl, substituted, or unsubstituted C 3~20 Cycloalkenyl, substituted or unsubstituted C 3~20 Heterocycloalkenyl, substituted or unsubstituted C 6~20 Aryl, or substituted or unsubstituted C 3~20 It is a heteroaryl, but R 8 ~R 10 Only one of them can be hydrogen, and R 11 ~R 13 Only one of them can be hydrogen, and R 8 ~R 10 If one of them is hydrogen, then the other R 8 ~R 10 At least one of them is a substituted or unsubstituted C 6~20 Aryl or substituted or unsubstituted C 3~20 It is a heteroaryl, and R 11 ~R 13 If one of them is hydrogen, then the other R 11 ~R 13 At least one of them is a substituted or unsubstituted C. 6~20 Aryl or substituted or unsubstituted C 3~20 It is required that it be a heteroaryl compound. Preferably, R 8 ~R 13 These are, independently, substituted or unsubstituted C.1~6 Alkyl or substituted or unsubstituted C 3~10 It is a cycloalkyl compound. Each R 8 ~R 13 It may optionally further include a divalent linking group as part of its structure.

[0078] For example, R 8 ~R 13 One or more of the following are independent of the formula -CH2C(O)CH (3-n) Y n or -CH2C(O)OCH (3-n) Y n It can be a base, and each Y is independently a substituted or unsubstituted C 3~10 It is a heterocycloalkyl group where n is 1 or 2. For example, each Y independently represents the formula -O(C a1 )(C a2 ) Substituted or unsubstituted C containing an O- group 3~10 It can be a heterocycloalkyl, where C a1 and C a2 Each is independently hydrogen or a substituted or unsubstituted alkyl, and C a1 and C a2 They optionally form a ring together.

[0079] In equation (6), R 8 ~R 10 Any two of them may optionally form a ring, which may further contain divalent linking groups as part of its structure, and this ring may be substituted or unsubstituted. In formula (7), R 11 ~R 13 Any two of these may optionally form a ring together, which may further contain a divalent linking group as part of its structure, and this ring may be substituted or unsubstituted.

[0080] In equations (8) and (10), R 14 , R 15 , R 20 , and R 21 These are, independently, hydrogen, substituted or unsubstituted C. 1~20 Alkyl, substituted, or unsubstituted C3~20 Cycloalkyl, substituted, or unsubstituted C 3~20 Heterocycloalkyl, substituted, or unsubstituted C 6~20 Aryl, or substituted or unsubstituted C 3~20 It is often a heteroaryl; R 16 and R 22 These are, independently, substitutional or non-substitutional C. 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 3~20 It may be a heterocycloalkyl group. Preferably, R 14 , R 15 , R 20 , and R 21 These are, independently, hydrogen, substituted or unsubstituted C. 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 3~20 It may be a heterocycloalkyl. 14 , R 15 , R 20 , and R 21 Each of these may optionally further include a divalent linking group as part of its structure.

[0081] In equation (8), R 14 ~R 16 Any two of these may optionally form a ring together, which may further contain a divalent linking group as part of its structure, and this ring group may be substituted or unsubstituted.

[0082] In equation (9), R 17 ~R 19 These are, independently, substitutional or non-substitutional C. 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, substituted, or unsubstituted C 3~20 Heterocycloalkyl, substituted, or unsubstituted C 6~20 Aryl, or substituted or unsubstituted C 3~20 It is a heteroaryl, but R 17 ~R 19The condition is that only one of them may be hydrogen, and R 17 ~R 19 If one of them is hydrogen, then R 17 ~R 19 At least one of the others is a substitution or non-substitution C 6~20 Aryl or substituted or unsubstituted C 3~20 The condition is that it is a heteroaryl compound. Each R 17 ~R 19 It may optionally further include a divalent linking group as part of its structure.

[0083] For example, R 17 ~R 19 One or more of the following are independent of the formula -CH2C(O)CH (3-n) Y n or -CH2C(O)OCH (3-n) Y n It may be a base of C, where each Y is independently substituted or unsubstituted. 3~10 It is a heterocycloalkyl group where n is 1 or 2. For example, each Y independently corresponds to formula -O(C a1 )(C a2 ) Substituted or unsubstituted C containing an O- group 3~10 It can be a heterocycloalkyl, where C a1 and C a2 Each is independently hydrogen or a substituted or unsubstituted alkyl, and C a1 and C a2 They optionally form a ring together.

[0084] In equation (9), R 17 ~R 19 Any two of these may optionally form a ring together, which may further contain a divalent linking group as part of its structure, and this ring may be substituted or unsubstituted.

[0085] In equations (9) and (10), X a and X b Each of these is independently a polymerizable group containing an ethylenically unsaturated double bond, preferably a (meth)acrylate or a C2 alkenyl.

[0086] In Formulas (9) and (10), L 5 and L 6 are each independently a single bond or a divalent linking group, provided that when Xa is C2 alkenyl, L 5 is not a single bond, and when Xb is C2 alkenyl, L6 is not a single bond. Preferably, L 5 and L 6 are each independently a substituted or unsubstituted C 6~30 arylene or a substituted or unsubstituted C 6~30 cycloalkylene. In Formulas (9) and (10), n1 is 0 or 1, and n2 is 0 or 1. When n1 is 0, it should be understood that the L 5 group is directly bonded to an oxygen atom. When n2 is 0, it should be understood that the L 6 group is directly bonded to an oxygen atom.

[0087] In Formula (10), any two of R 20 ~R 22 may combine together to optionally further contain a divalent linking group as part of its structure and may also form a ring which may be substituted or unsubstituted.

[0088] In some embodiments, each R 8 ~R 22 may optionally further contain one or more divalent linking groups selected from -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R’)-, or -C(O)N(R’)- as part of its structure, and R’ is hydrogen, a substituted or unsubstituted C 1~20 alkyl, a substituted or unsubstituted C 3~20 cycloalkyl, or a substituted or unsubstituted C 3~20 heterocycloalkyl.

[0089] Exemplary monomers of Formula (6) include one or more of the following.

Chemical Formula

[0090] The monomers of exemplary formula (7) include one or more of the following. [Chemical formula] [Chemical formula] In the formula, R d is as defined for formula R b in formula (7), and R ’ and R ’’ are each independently a substituted or unsubstituted C 1~20 alkyl, a substituted or unsubstituted C 3~20 cycloalkyl, a substituted or unsubstituted C 3~20 heterocycloalkyl, a substituted or unsubstituted C 2~20 alkenyl, a substituted or unsubstituted C 3~20 cycloalkenyl, a substituted or unsubstituted C 3~20 heterocycloalkenyl, a substituted or unsubstituted C 6~20 aryl, or a substituted or unsubstituted C 3~20 heteroaryl.

[0091] The monomers of exemplary formula (8) include one or more of the following. [Chemical formula] In the formula, R d is as defined above for R c .

[0092] The monomers of exemplary formula (9) include one or more of the following. [Chemical formula]

[0093] The monomers of exemplary formula (10) include one or more of the following. [Chemical formula]

[0094] In some embodiments, the polymer may have acid-unstable repeating units derived from one or more monomers having a cyclic acetal group or a cyclic ketal group. [ka] In the formula, R d R a This is as defined above.

[0095] In some embodiments, the polymer may have repeating units having acid-unstable groups including tertiary alkoxy groups, such as one or more monomers listed below. [ka]

[0096] If present, second repeating units containing acid-unstable groups and distinct from the first repeating units are typically present in the polymer in amounts of 25–65 mol%, more typically 30–50 mol%, and even more typically 30–45 mol%, based on the total number of repeating units in the polymer.

[0097] In some embodiments, the polymer may further comprise repeating units containing polar groups, which are pendant groups to the polymer's main chain. For example, the polar groups may be lactone groups, hydroxyaryl groups, carboxylic acid groups, or combinations thereof, but embodiments are not limited to these.

[0098] In one or more embodiments, the polymer may further comprise repeating units derived from one or more lactone-containing monomers of formula (11). [ka] In the formula, R a This is hydrogen, fluorine, cyano, or substituted or unsubstituted C 1~10 It is alkyl.

[0099] In formula (11), L 7 is a single bond or a divalent linking group. Examples of the divalent linking group of L 7 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 11a )-, or -C(O)N(R 11b )-, and one or more of R 11a and R 11b 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 heterocycloalkyl.

[0100] L 7 When L is a single bond, the moiety -R 23 is directly bonded to the oxygen atom adjacent to the carbonyl group (i.e., -C(O)O-R 23 ). It should be understood.

[0101] In formula (11), R 23 is a substituted or unsubstituted C 4~20 lactone-containing group or a substituted or unsubstituted C 4~20 sulfone-containing group. The C 4~20 lactone-containing group and the C 4~20 sulfone-containing group can be monocyclic, polycyclic or fused polycyclic.

[0102] Exemplary monomers of formula (11) can include one or more of the following.

Chemical formula

[0103] In some embodiments, the repeating unit containing the polar group may be a repeating unit that is base-soluble and / or has a pKa of 12 or less. For example, such a repeating unit can be derived from one or more of formulas (12), (13), or (14). [ka] In the formula, each R g This is hydrogen, fluorine, cyano, or substituted or unsubstituted C 1~10 It may be alkyl. Preferably, R g This is hydrogen, fluorine, or substituted or unsubstituted C 1~5 Alkyl, typically methyl.

[0104] In equation (12), R 24 is a substitution or non-substitution C 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 It may be an alkylene oxide. Preferably, a 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 a halogen, C 1~4 Fluoroalkyl groups such as fluoroalkyl groups (typically fluoromethyl), sulfonamide groups -NH-S(O)2-Y 1 (Here, Y 1 is F or C 1~4 It is substituted with one or more perfluoroalkyl groups (e.g., -NHSO2CF3) or fluoroalcohol groups (e.g., -C(CF3)2OH).

[0105] In equation (13), L 8 The bonds are single bonds, or optionally -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -NR 13a -, or -C(O)N(R) 13a )-(wherein, R 13a C is composed of hydrogen and optionally substituted C 1~10 Along with one or more linking sites selected from (selected from alkyl), for example C 1~6 Alkylene or C 3~20 This represents a polyvalent linking group selected from optionally substituted aliphatic hydrocarbons such as cycloalkylenes, aromatic hydrocarbons, and combinations thereof. For example, a polymer is represented by formula (12) (wherein L 8 C is a single bond, or a substituted or unsubstituted C. 1~20 Alkylene, typically C 1~6 Alkylene; substituted or unsubstituted C 3~20 Cycloalkylenes, typically C 3~10 Cycloalkylenes; and substituted or unsubstituted C 6~24 It may further contain repeating units derived from one or more monomers of a polyvalent linking group selected from arylene.

[0106] In equation (13), n3 is an integer from 1 to 5, typically 1. When n3 is 1, base L 8 It should be understood that this is a divalent linking group. When n3 is 2, the group L 8 It should be understood that this is a trivalent linking group. Similarly, if n3 is 3, then group L 8 It is a tetravalent linking group; if n3 is 4, then group L 8 is a pentavalent linking group; and when n3 is 5, group L 8 It should be understood that is a hexavalent linking group. Therefore, in relation to formula (13), the term “polyvalent linking group” refers to any of the divalent, trivalent, tetravalent, pentavalent and / or hexavalent linking groups. In some embodiments, when n is 2 or more, the carboxylic acid group (-C(O)OH) is a linking group L 8It can bond to the same atom. In other embodiments, when n is 2 or more, the carboxylic acid group (-C(O)OH) is a linking group L 8 It can bond to different atoms.

[0107] In equation (14), L 9 represents a single bond or a divalent linking group. Preferably, L 9 C is a single bond, substituted, or unsubstituted C 6~30 Arylene or substituted or unsubstituted C 6~30 It could be a cycloalkylene.

[0108] In equation (14), n4 is either 0 or 1. When n4 is 0, the part represented by -OC(O)- is L 9 It should be understood that this is a single bond, directly bonded to the alkenyl (vinyl) carbon atom.

[0109] In equation (14), Ar 3 This is a substituted carbon atom that optionally contains three or more aromatic ring heteroatoms selected from N, O, S, or combinations thereof. 5~60 It is an aromatic group, and the aromatic group can be monocyclic, non-condensed polycyclic, or condensed polycyclic. C 5~60 When an aromatic group is polycyclic, the ring or ring group can be condensed (e.g., naphthyl), uncondensed, or a combination thereof. Polycyclic C 5~60 When the aromatic group is uncondensed, the ring or ring group can be directly linked (e.g., biaryl or biphenyl) or bridged by a heteroatom (e.g., triphenylamino or diphenylene ether). In some embodiments, polycyclic C 5~60 Aromatic groups can include combinations of fused rings and directly bonded rings (such as binaphthyl rings).

[0110] In equation (14), y can be an integer between 1 and 12, preferably between 1 and 6, typically between 1 and 3. x These may independently be hydrogen or methyl.

[0111] Non-limiting examples of monomers of formula (12), (13), or (14) include one or more of the following: [ka] [ka] In the formula, Y 1 As stated above, R i In equations (12) to (14), R g This is as defined.

[0112] If present, the polymer typically contains repeating units with polar groups (pendant groups to the polymer's main chain) in amounts of 1 to 60 mol%, typically 5 to 50 mol%, and more typically 5 to 40 mol%, relative to the total repeating units in the polymer.

[0113] Non-exclusive exemplary polymers include one or more of the following: [ka] In the formula, a and b represent the mole fractions of each repeating unit of the polymer.

[0114] The polymer typically has a weight-average molecular weight (M) of 1,000 to 50,000 Datons (Da), preferably 2,000 to 30,000 Da, more preferably 4,000 to 25,000 Da, and even more preferably 5,000 to 25,000 Da. w ) has M w Logarithmic mean molecular weight (M n The polydispersity index (PDI) of the polymer, which is the ratio of ), is typically 1.1–3, more typically 1.1–2. The molecular weight is determined by gel permeation chromatography (GPC) using a polystyrene standard.

[0115] Polymers can be prepared using any suitable method in the art. For example, one or more monomers corresponding to the repeating units described herein may be combined using a suitable solvent and initiator, or supplied separately, and polymerized in a reactor. For example, polymers can be obtained by polymerization of each monomer under any suitable conditions, such as heating at an effective temperature, irradiation with chemical rays of an effective wavelength, or a combination thereof.

[0116] A photoresist composition comprising the polymer of the present invention and a photoacid generator (PAG) and a solvent is also provided.

[0117] A suitable PAG can generate an acid that causes cleavage of acid-unstable groups present on the polymer of the photoresist composition during post-exposure baking (PEB). The PAG may be in non-polymeric or polymeric form and may exist, for example, in polymerized repeating units of the polymer described above or as part of another polymer. In some embodiments, the PAG may be included in the composition as a non-polymerizable PAG compound, as repeating units of a polymer having a PAG moiety derived from a polymerizable PAG monomer, or as a combination thereof.

[0118] Suitable nonpolymer PAG compounds include those of formula G + A - It may have, in the formula, G + A 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. - These are nonpolymerizable organic anions. Particularly suitable nonpolymerized organic anions include those with a conjugate acid having a pKa of -15 to 1. Particularly preferred anions are fluorinated alkyl sulfonates and fluorinated sulfonimides.

[0119] Useful nonpolymeric 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-t-butylphenyliodonium perfluorobutanesulfonate and di-t-butylphenyliodonium camphorsulfonate. Nonionic sulfonates and sulfonyl compounds, e.g., nitrobenzyl derivatives, e.g., 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonic acid esters, e.g., 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene and 1,2,3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives, e.g., bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane; glyoxime derivatives, e.g. Bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime and bis-O-(n-butanesulfonyl)-α-dimethylglyoxime; sulfonic acid ester derivatives of N-hydroxyimide compounds, such as N-hydroxysuccinimodomethanesulfonic acid and N-hydroxysuccinimodomifluoromethanesulfonic acid; and halogen-containing triazine compounds, such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine and 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, are also known to function as photoacid generators. Suitable non-polymerizable acid generators are further described in Hashimoto et al. (Patent Document 1), column 37, rows 11-47 and columns 41-91.Other suitable sulfonate PAGs include sulfonated esters and sulfonyloxy ketones, nitrobenzyl esters, s-triazine derivatives, benzointosylates, t-butylphenyl α-(p-toluenesulfonyloxy)acetate, and t-butyl α-(p-toluenesulfonyloxy)acetate, as described in (Patent Document 2) and (Patent Document 1).

[0120] Typically, if the photoresist composition contains a nonpolymeric photoacid generator, it is present in the photoresist composition in an amount of 0.3 to 65% by weight, more typically 1 to 20% by weight, based on the total solids content of the photoresist.

[0121] In some embodiments, G + This may be a sulfonium cation of formula (15) or an iodonium cation of formula (16). [ka]

[0122] In equations (15) and (16), each R aa These 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 It is a heteroarylalkyl. Each R aa These are either individual or connected to another group R via a single bond or divalent linking group. aa They may be connected to each other to form a ring. Each R aa It may optionally include a divalent linking group as part of its structure. Each R aaThis can independently contain, optionally, an acid-unstable 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 an alkyl group and an aryl group, a tertiary alkoxy group, an acetal group, or a ketal group.

[0123] The exemplary sulfonium cation of formula (15) may include one or more of the following: [ka] [ka]

[0124] The exemplary iodonium cation of formula (16) may include one or more of the following: [ka]

[0125] PAGs, which are onium salts, typically contain organic anions having a sulfonate group or a non-sulfonate type group (such as sulfonamide, sulfonimidate, methide, or borate).

[0126] Exemplary organic anions having a sulfonate group may include one or more of the following: [ka]

[0127] Exemplary non-sulfonated anions include one or more of the following: [ka]

[0128] The photoresist composition may optionally contain a plurality of PAGs. The plurality of PAGs may be polymer-based, non-polymer-based, or may contain both polymer-based and non-polymer-based PAGs. Preferably, each of the plurality of PAGs is non-polymer-based.

[0129] In one or more embodiments, the photoresist composition may include a first photoacid generator having a sulfonate group on an anion, the photoresist composition may include a second photoacid generator which is a nonpolymer, and the second photoacid generator may include an anion which does not have a sulfonate group.

[0130] In some embodiments, the polymer may optionally further include repeating units containing PAG-containing moieties, for example, repeating units derived from one or more monomers of formula (17). [ka] In the formula, R m C is hydrogen, fluorine, cyano, or substituted or unsubstituted C 1~10 It may be alkyl. Preferably, R m C is hydrogen, fluorine, or substituted or unsubstituted C 1~5 It is alkyl, and typically methyl.

[0131] In equation (17), Q 1 Q may be a single bond or a divalent linking group. Preferably, 1 It may contain 1 to 10 carbon atoms and at least one heteroatom, more preferably -C(O)-O-. 1 is a substitution or non-substitution C 1~30 Alkylene, substituted, or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene or substituted or unsubstituted C 3~30 It may be one or more heteroarylenes. Preferably, A 1 This is a divalent C that is optionally substituted. 1~30 It may be a perfluoroalkylene group.- The anionic moiety is the anionic site, and its conjugate acid typically has a pKa of -15 to 1. For example, Z - The anionic moiety may be a sulfonate, carboxylate, sulfonamide anion, sulfonimide anion, or methide anion. Particularly preferred anionic moieties are fluorinated alkyl sulfonates and fluorinated sulfonimides. + is the organic cation defined above. In some embodiments, G + This refers to an iodonium cation substituted with two alkyl groups, two aryl groups, or a combination of an alkyl group and an aryl group; or a sulfonium cation substituted with three alkyl groups, three aryl groups, or a combination of an alkyl group and an aryl group.

[0132] The exemplary monomers of formula (17) may include one or more of the following: [ka] In the formula, G + is an organic cation as defined herein.

[0133] When used, the repeating units containing the PAG portion may be present in the polymer in amounts of 1–15 mol%, typically 1–8 mol%, and more typically 2–6 mol%, relative to the total repeating units in the polymer.

[0134] The photoresist composition further comprises a solvent for dissolving the components of the composition and facilitating its coating on a substrate. Preferably, the solvent is an organic solvent conventionally used in the manufacture of electronic devices. Suitable solvents include, for example, aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane and 1-chlorohexane; alcohols such as methanol, ethanol, 1-propanol, isopropanol, tert-butanol, 2-methyl-2-butanol, 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; acetone, methyl ethyl ketone, methyl isobutyl ketone, Examples of solvents include ketones such as 2-heptanone and cyclohexanone (CHO); esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), hydroxyisobutyrate methyl ester (HBM), and acetate acetate; lactones such as γ-butyrolactone (GBL) and ε-caprolactone; lactams such as N-methylpyrrolidone; nitriles such as acetonitrile and propionitrile; cyclic or acyclic carbonate esters such as dimethyl carbonate, ethylene carbonate, diphenyl carbonate, and propylene carbonate; polar aprotic solvents such as dimethyl sulfoxide and dimethylformamide; water; and combinations thereof. Of these, preferred solvents are PGME, PGMEA, EL, GBL, HBM, CHO, and combinations thereof.

[0135] The total solvent content in a photoresist composition (i.e., the cumulative solvent content for all solvents) is typically 40–99% by weight, for example, 60–99% by weight or 85–99% by weight, based on the total solids content of the photoresist composition. The desired solvent content will depend, for example, on the desired thickness of the photoresist layer to be coated and the coating conditions.

[0136] The polymer is typically present in the photoresist composition in amounts of 0.1–99.9% by weight, typically 0.1–20% by weight, and more typically 1–15% by weight, based on the total solids content of the photoresist composition. “Total solids content” is understood to include the polymer, PAG, additives, and other non-solvent components.

[0137] In some embodiments, the photoresist composition may further comprise a second polymer comprising repeating units containing an acid-unstable group, the second polymer being structurally different from the polymer of the present invention. Such acid-unstable groups are as described herein.

[0138] For example, a photoresist composition may include additional (second) polymers with different compositions as described above, or polymers similar to those described above but without each of the essential repeating units. In addition or alternatively, one or more additional (second) polymers may include those well known in photoresist technology, such as polyacrylates, polyvinyl ethers, polyesters, polynorbornene, polyacetals, polyethylene glycols, polyamides, polyacrylamides, polyphenols, novolacs, styrene polymers, polyvinyl alcohols, or combinations thereof.

[0139] The second polymer is typically M with a density of 1,000 to 50,000 Da, preferably 2,000 to 30,000 Da, more preferably 4,000 to 25,000 Da, and even more preferably 5,000 to 25,000 Da. w It has the following properties. The PDI of the second polymer is typically 1.1–3, and more typically 1.1–2. The molecular weight is determined by GPC using a polystyrene standard.

[0140] The second polymer is typically present in the photoresist composition in an amount of 0.1 to 99.9% by weight, typically 25 to 90% by weight, and more typically 45 to 85% by weight, based on the total solids content of the photoresist composition.

[0141] The photoresist composition may further contain one or more additional optional additives. For example, optional additives may include chemical laser dyes and contrast agents, striation inhibitors, plasticizers, rate accelerators, sensitizers, photodegradable deactivators (PDQ) (also known as photodegradable bases), basic deactivators, thermoacid generators, surfactants, etc., or combinations thereof. If present, optional additives are typically present in the photoresist composition in an amount of 0.01 to 10% by weight based on the total solids content of the photoresist composition.

[0142] PDQ generates a weak acid when irradiated. The acid generated from the photodegradable inactivator is not strong enough to react rapidly with acid-unstable groups present in the resist matrix. Exemplary photodegradable inactivators include, for example, photodegradable cations, preferably, for example, C 1~20 Carboxylic acid or C 1~20 This includes compounds useful for preparing strong acid-generating compounds paired with anions of weak acids (pKa>1), such as sulfonic acid anions. Exemplary carboxylic acids include formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexanecarboxylic acid, benzoic acid, salicylic acid, etc. Exemplary sulfonic acids include p-toluenesulfonic acid, camphorsulfonic acid, etc. In preferred embodiments, the photodegradable deactivator is a photodegradable organic zwitterionic compound such as diphenyliodonium-2-carboxylate.

[0143] The photodegradable inactivator may be in a non-polymeric or polymer-bound form. In the polymeric form, the photodegradable inactivator is present in polymerization units on the first or second polymer. Polymerization units containing the photodegradable inactivator 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 of the polymer.

[0144] Examples of basic deactivators include 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-diyrbis(azanetriyl))tetraethanol, 2-(dibutylamino)ethanol and 2,2',2''-nitrilotriethanol; 1-(tert-butylamine; Cyclic aliphatic amines such as toxiccarbonyl)-4-hydroxypiperidine, tert-butyl1-pyrrolidine carboxylate, tert-butyl2-ethyl-1H-imidazole-1-carboxylate, di-tert-butylpiperazine-1,4-dicarboxylate and N-(2-acetoxyethyl)morpholine; aromatic amines such as pyridine, di-tert-butylpyridine and pyridinium; N,N-bis(2-hydroxyethyl)pivalamide, N,N-diethylacetamide, N 1 , N 1 , N 3 , N 3 Examples include linear and cyclic amides and their derivatives such as tetrabutylmalonamide, 1-methylazepan-2-one, 1-allylazepan-2-one, and tert-butyl1,3-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.

[0145] Basic deactivators may be in a non-polymeric or polymer-bound form. If in a polymeric form, the deactivator may be present within the repeating units of the polymer. Repeating units containing the deactivator are typically present in an amount of 0.1 to 30 mol%, preferably 1 to 10 mol%, and more preferably 1 to 2 mol%, relative to the total repeating units of the polymer.

[0146] Exemplary surfactants include fluorinated and non-fluorinated surfactants, and may be ionic or nonionic, with nonionic surfactants being preferred. Exemplary fluorinated nonionic surfactants include perfluoro C4 surfactants such as FC-4430 and FC-4432 surfactants available from 3M Corporation, and fluorodiols such as Omnova's POLYFOX PF-636, PF-6320, PF-656, and PF-6520 fluorosurfactants. In one embodiment, the photoresist composition further comprises a surfactant polymer containing fluorine-containing repeating units.

[0147] This invention describes a pattern formation method using the photoresist composition of the present invention. Suitable substrates to which the photoresist composition can be coated include electronic device substrates. Various electronic device substrates, such as semiconductor wafers, polycrystalline silicon substrates, packaging substrates such as multi-chip modules, flat panel display substrates, and substrates for light-emitting diodes (LEDs) such as organic light-emitting diodes (OLEDs), can be used in the present invention, with semiconductor wafers being typical. Such substrates are typically composed of one or more of silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. Suitable substrates may be in the form of wafers used in the manufacture of integrated circuits, optical sensors, flat panel displays, optical integrated circuits, and LEDs. Such substrates may be of any suitable size. Typical wafer substrate diameters are 200 to 300 millimeters (mm), but wafers with smaller and larger diameters can be suitably used according to the present invention. The substrate may include one or more layers or structures that optionally contain the effective or operable portion of the device to be formed.

[0148] Typically, one or more lithography layers, such as a hard mask layer (e.g., spin-on carbon (SOC), amorphous carbon, or metallic hard mask layer), a CVD layer (e.g., 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 before coating with the photoresist composition of the present invention. Such layers, together with the overcoated photoresist layer, form a lithography material stack.

[0149] Optionally, a layer of adhesion promoter may be applied to the substrate surface before coating the photoresist composition. If an adhesion promoter is desired, any suitable adhesion promoter for the polymer film may be used, such as silanes, typically organosilanes such as trimethoxyvinylsilane, triethoxyvinylsilane, and hexamethyldisilazane, and aminosilane coupling agents such as gamma-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those available from DuPont Electronics & Industrial (Marlborough, Massachusetts), marketed under the names AP 3000, AP 8000, and AP 9000S.

[0150] The photoresist composition can be coated onto a substrate by any suitable method, such as spin coating, spray coating, dip coating, doctor blading, etc. For example, the application of a photoresist layer can be achieved by spin coating the photoresist in a solvent using a coating track, in which case the photoresist is distributed onto a rotating wafer. During distribution, the wafer is typically rotated for a period of 15 to 120 seconds at a speed of up to 4,000 revolutions per minute (rpm), e.g., 200 to 3,000 rpm, e.g., 1,000 to 2,500 rpm, to obtain a layer of the photoresist composition on the substrate. It will be understood by those skilled in the art that the thickness of the coated layer can be adjusted by changing the spin speed and / or the total solid content of the composition. The photoresist composition layer formed from the composition of the present invention typically has a dry layer thickness of 3 to 30 micrometers (μm), preferably more than 5 to 30 μm, and more preferably 6 to 25 μm.

[0151] Photoresist compositions are typically then soft-baked to minimize the solvent content in the layer, thereby forming a non-stick coating and improving the adhesion of the layer to the substrate. Soft baking is performed, for example, on a hot plate or in an oven, with a hot plate being typical. The soft-bake temperature and time will depend, for example, on the photoresist composition and thickness. Soft-bake temperatures are typically 80–170°C, more typically 90–150°C. Soft-bake times are typically 10 seconds–20 minutes, more typically 1 minute–10 minutes, and even more typically 1 minute–2 minutes. The heating time can be easily determined by those skilled in the art based on the composition's components.

[0152] The photoresist layer is then pattern-exposed to activation radiation to create a difference in solubility between exposed and unexposed areas. The herein reference to exposure of a photoresist composition to radiation that activates the composition indicates that the radiation can form a latent image in the photoresist composition. Exposure is typically performed through a patterned photomask having optically transparent and optically opaque regions, respectively, corresponding to the exposed and unexposed regions of the resist layer. Such exposure may instead be performed without a photomask using direct writing methods, which are typically used for e-beam lithography. The activation radiation typically has wavelengths less than 400 nm, less than 300 nm, or less than 200 nm, with 248 nm (KrF), 193 nm (ArF), 13.5 nm (EUV) wavelengths or electron beam lithography being preferred. Preferably, the activation radiation is 248 nm radiation. This method is utilized in immersion or dry (non-immersion) lithography techniques. The exposure energy depends on the components of the exposure tool and photoresist composition, and is typically 1 to 200 millijoules (mJ / cm²) per square centimeter. 2 ), preferably 10 to 100 mJ / cm² 2 More preferably 20-50 mJ / cm² 2 That is the case.

[0153] After exposure of the photoresist layer, post-exposure baking (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 layer thickness. PEB is typically performed at a temperature of 70-150°C, preferably 75-120°C, for a period of 30-120 seconds. A latent image is formed in the photoresist, defined by polarity switching regions (exposed regions) and non-switching regions (unexposed regions).

[0154] The exposed photoresist layer is then developed with a developer suitable for selectively removing the soluble regions of the layer, while the remaining insoluble regions form the resulting photoresist pattern relief image. In a positive development (PTD) process, the exposed regions of the photoresist layer are removed during development, leaving the unexposed regions. Conversely, in a negative development (NTD) process, the exposed regions of the photoresist layer remain, and the unexposed regions are removed during development. The application of the developer can be achieved by any suitable method as described above for the application of the photoresist composition, with spin coating being a typical example. The development time is an effective time for removing the soluble regions of the photoresist, typically 5 to 60 seconds. Development is typically carried out at room temperature.

[0155] Suitable developers for the PTD process include aqueous base developers, such as tetramethylammonium hydroxide (TMAH), preferably 0.26 N (N) TMAH, quaternary ammonium hydroxide solutions such as tetraethylammonium hydroxide and tetrabutylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. Suitable developers for the NTD process are organic solvent systems, meaning that the cumulative content of organic solvents in the developer is 50% by weight or more, typically 95% by weight or more, 98% by weight or more, or 100% by weight, based on the total weight of the developer. Suitable organic solvents for NTD developers include, for example, those selected from ketones, esters, ethers, hydrocarbons and mixtures thereof. The developer is typically 2-heptanone or n-butyl acetate.

[0156] A coated substrate may be formed from the photoresist composition of the present invention. Such a coated substrate comprises (a) a substrate having one or more layers patterned on its surface; and (b) a layer of the photoresist composition on one or more patterned layers.

[0157] A photoresist pattern can be used, for example, as an etching mask, thereby enabling the transfer of the pattern to one or more consecutive underlying layers by known etching techniques, typically dry etching such as reactive ion etching. A photoresist pattern can be used, for example, for pattern transfer to a lower hard mask layer, and it can subsequently be used as an etching mask for pattern transfer to one or more layers below the hard mask layer. If the photoresist pattern is not consumed during pattern transfer, it can be removed from the substrate by known techniques, such as oxygen plasma ashing. When used in one or more such patterning processes, photoresist compositions can be used to manufacture semiconductor devices and other electronic devices such as memory devices, processor chips (CPUs), graphics chips, optoelectronic chips, LEDs, OLEDs, etc.

[0158] This subject is further illustrated by the following non-limiting embodiments. [Examples]

[0159] List of monomers used in synthesis examples [ka]

[0160] Synthesis Example 1 The synthesis scheme for the monomer represented by M2 is shown in Scheme 1. [ka] A condenser, temperature probe, and septum were attached to a 500 ml (mL) multi-necked round-bottom flask. An N2 line was connected to the top of the condenser. Vinyl salicylic acid (44.0 g) was added to the flask, followed by dimethylformamide (DMF) (200 ml (mL)). Then, 1,1-carbonyldiimidazole (43.46 g) was added gradually while stirring under N2. After all bubbles generated during the reaction had disappeared, the reaction was heated at 55°C for 1 hour. Next, 1-ethylcyclopentanol (33.67 g) was added to the reaction mixture at 55°C, followed by 1,8-diazabicyclo[5.4.0]undec-7-ene (40.81 g). The reaction was then heated at 55°C for 16 hours under N2. A portion of the reaction was removed, quenched with deionized (DI) water, and extracted to heptane. 1 ¹H-NMR analysis confirmed the absence of vinyl salicylic acid. Therefore, the reaction was quenched by adding DI water (500 mL). The product was extracted with heptane (3 × 150 mL). The organic layers were combined, washed with saturated NaCl / water, and dried on pleated filter paper. Heptane was removed under reduced pressure. The product was obtained as a pale yellow solid (46.0 g, yield 66%). 1H NMR(500MHz,DMSO-d6)δ:7.73(s,1H),7.66(s,1H),6.94(d,J=8.6Hz,1H),6.69(s,1H),5.6 5(s,1H),5.16(s,1H),2.21(s,2H),2.05(s,2H),1.73(s,6H),0.86(td,J=7.4,2.2Hz,3H).

[0161] Synthesis Example 2 The synthesis scheme for the monomer represented by M7 is shown in Scheme 2. [ka]

[0162] 3,5-Diiodohydroxystyrene (30.00 g) was placed in a 500 mL round-bottom flask, followed by the addition of tetrahydrofuran (THF) (200 mL). Ethyl diisopropylaminocarbodiimide hydrochloride (EDC) (24.74 g) was added to the flask along with 4-pyrrolidinopyridine (0.60 g), and the reaction was cooled to 0°C. 3,3,3-Trifluoropropanoic acid (14.46 g) dissolved in THF (20 mL) was added to the reaction, and the reaction temperature was raised to room temperature (rt). The reaction was stirred at room temperature under an N2 atmosphere for 4 hours. The reaction mixture was cooled to 0°C and quenched with MilliQ water (500 mL). The reaction mixture was transferred to a separatory funnel, and the product was extracted with ethyl acetate (200 mL x 3). The organic layer was washed with MilliQ water (300 mL) and dried by passing it through pleated filter paper. The ethyl acetate was then removed under reduced pressure. The obtained product was purified by passing it through a silica gel plug containing heptane / ethyl acetate (8 / 2 v / v) to obtain monomers as a white powder. (33.5 g, yield = 86%) 1 H NMR(500MHz,DMSO-d6)δ 8.04(s,1H),6.66(dd,J=17.6,11.0Hz,1H),5.98(d,J=17.6Hz,1H),5.37(d,J=11.0Hz,1H),4.18(q,J=10.6Hz,1H). 19 F NMR (470 MHz, DMSO) δ-61.63.

[0163] Synthesis Example 3 The synthesis scheme for the polymer represented by AP-6 is shown in Scheme 3. [ka] 10.0 g of PGMEA was placed in the reactor and purged with N2 for 30 minutes while heating to 85°C. A monomer-initiator solution was prepared by dissolving M5 (14.13 g), M1 (0.89 g), and the azo initiator dimethyl 2,2'-azobis(2-methylpropionate) (obtained from Wako Pure Chemical Industries, Ltd. as V-601) (1.15 g) in PGMEA (18.00 g). This was filled into a syringe. The syringe was covered with a cooling agent to maintain the solution temperature below room temperature. After the reactor temperature stabilized at 85°C, the monomer-initiator solution was supplied to the reactor over 3 hours. After the addition was complete, the reactor was held at 85°C for a further 3 hours, and then cooled to 25°C. The product was precipitated in methanol and decanted. The obtained precipitate (11.0 g) was washed with methanol and dissolved in PGMEA (51.0 g). By removing PGMEA under reduced pressure, a final polymer solution of 49.4 g with a solid polymer content of 18.8 wt% was obtained. Mw = 11.4 kDa, Mn = 8.07 kDa, PDI = 1.47, composition = M5 / M1 (mol%): 89.1% / 10.9%.

[0164] Synthesis Example 4 The polymer represented by AP-5 was prepared as shown in Scheme 4. [ka] 7.34 g of PGMEA was placed in the reactor and purged with N2 for 30 minutes while heating to 85°C. A monomer-initiator solution was prepared by dissolving M5 (12.74 g), M1 (1.26 g), and initiator V601 (0.74 g) in PGMEA (15.86 g), and this solution was filled into a syringe. The syringe was covered with a cooling agent to maintain the solution temperature below room temperature. After the reactor temperature stabilized at 85°C, the monomer-initiator solution was supplied to the reactor over 3 hours. After the addition was complete, the reactor was held at 85°C for a further 3 hours, and then cooled to 25°C to obtain 36.7 g of polymer solution with a solids content of 40.0 wt%. This polymer solution was diluted with PGMEA (36.7 g) to obtain a polymer with a solids content of 20.0 wt% in the PGMEA solution. Mw=10.0kDa, Mn=4.72kDa, PDI=2.12, composition=M5 / M1 (mol%): 86.5% / 13.5%.

[0165] Synthesis Example 5 The polymer represented by AP-3 was prepared as shown in Scheme 5. [ka] 7.37 g of PGMEA was placed in the reactor and purged with N2 for 30 minutes while heating to 85°C. A monomer-initiator solution was prepared by dissolving M5 (13.16 g), M2 (0.84 g), and initiator V601 (0.74 g) in PGMEA (15.92 g), and this solution was filled into a syringe. The syringe was covered with a cooling agent to maintain the solution temperature below room temperature. After the reactor temperature stabilized at 85°C, the monomer-initiator solution was supplied to the reactor over 3 hours. After the addition was complete, the reactor was held at 85°C for a further 3 hours, and then cooled to 25°C to obtain 36.8 g of polymer solution with a solid content of 40.0 wt%. This polymer solution was diluted with PGMEA (36.8 g) to obtain a polymer with a solid content of 20.0 wt% in the PGMEA solution. Mw=10.2kDa, Mn=4.73kDa, PDI=2.16, composition=M5 / M2 (mol%): 93.6% / 6.4%.

[0166] Synthesis Example 6 The polymer represented by AP-4 was prepared as shown in Scheme 6. [ka] 7.39 g of PGMEA was placed in the reactor and purged with N2 for 30 minutes while heating to 85°C. A monomer-initiator solution was prepared by dissolving M5 (12.24 g), M2 (1.76 g), and initiator V601 (0.77 g) in PGMEA (15.95 g), and this was filled into a syringe. The syringe was covered with a cooling agent to maintain the solution temperature below room temperature. After the reactor temperature stabilized at 85°C, the monomer-initiator solution was supplied to the reactor over 3 hours. After the addition was complete, the reactor was held at 85°C for a further 3 hours, and then cooled to 25°C to obtain 36.9 g of polymer solution with a solid content of 40.0 wt%. This polymer solution was diluted with PGMEA (36.9 g) to obtain a polymer with a solid content of 20.0 wt% in the PGMEA solution. Mw=9.51kDa, Mn=4.68kDa, PDI=2.03, composition=M5 / M2 (mol%): 86.7% / 13.3%.

[0167] Synthesis Example 7 The polymer represented by AP-1 was prepared as shown in Scheme 7. [ka] 7.37 g of PGMEA was placed in the reactor and purged with N2 for 30 minutes while heating to 85°C. A monomer-initiator solution was prepared by dissolving M5 (13.09 g), M3 (0.91 g), and initiator V601 (0.73 g) in PGMEA (15.86 g), and this solution was filled into a syringe. The syringe was covered with a cooling agent to maintain the solution temperature below room temperature. After the reactor temperature stabilized at 85°C, the monomer-initiator solution was supplied to the reactor over 3 hours. After the addition was complete, the reactor was held at 85°C for a further 3 hours, and then cooled to 25°C to obtain 36.8 g of polymer solution with a solid content of 40.0 wt%. This polymer solution was diluted with PGMEA (36.8 g) to obtain a polymer with a solid content of 20.0 wt% in the PGMEA solution. Mw=10.2kDa, Mn=5.24kDa, PDI=1.95, composition=M5 / M3 (mol%): 92.4% / 7.6%.

[0168] Synthesis Example 8 The polymer represented by AP-2 was prepared as shown in Scheme 8. [ka] 7.35 g of PGMEA was placed in the reactor and purged with N2 for 30 minutes while heating to 85°C. A monomer-initiator solution was prepared by dissolving M5 (12.11 g), M3 (1.89 g), and initiator V601 (0.71 g) in PGMEA (15.89 g), and this solution was filled into a syringe. The syringe was covered with a cooling agent to maintain the solution temperature below room temperature. After the reactor temperature stabilized at 85°C, the monomer-initiator solution was supplied to the reactor over 3 hours. After the addition was complete, the reactor was held at 85°C for a further 3 hours, and then cooled to 25°C to obtain 36.7 g of polymer solution with a solid content of 40.0 wt%. This polymer solution was diluted with PGMEA (36.7 g) to obtain a polymer with a solid content of 20.0 wt% in the PGMEA solution. Mw=10.2kDa, Mn=5.00kDa, PDI=2.03, composition=M5 / M3 (mol%): 84.5% / 15.5%.

[0169] Synthesis Example 9 The polymer represented by AP-7 was prepared using the same procedure as in Synthesis Examples 3-8, except that the monomers were M6 and M2. Mw = 8.14 kDa, Mn = 4.26 kDa, PDI = 1.91, composition = M6 / M2 (mol%): 91.5% / 8.5%.

[0170] Synthesis Example 10 The polymer represented by AP-8 was prepared using the same procedure as in Synthesis Examples 3-8, except that the monomers were M6 and M1. Mw = 9.66 kDa, Mn = 5.12 kDa, PDI = 1.89, composition = M6 / M1 (mol%): 91.8% / 8.2%.

[0171] Synthesis Example 11 The polymer represented by AP-9 was prepared using the same procedure as in Synthesis Examples 3-8, except that the monomers were M6 and M3. Mw = 12.37 kDa, Mn = 5.75 kDa, PDI = 2.15, composition = M6 / M3 (mol%): 87.2% / 12.8%.

[0172] Synthesis Example 12 The polymer represented by AP-10 was prepared using the same procedure as in Synthesis Examples 3-8, except that the monomers were M6 and M2. Mw = 9.70 kDa, Mn = 5.01 kDa, PDI = 1.94, composition = M6 / M2 (mol%): 80.2% / 19.8%.

[0173] Synthesis Example 13 The polymer represented by AP-11 was prepared using the same procedure as in Synthesis Examples 3-8, except that the monomers were M6, M7, and M2. Mw = 10.6 kDa, Mn = 5.52 kDa, PDI = 1.93, composition = M6 / M7 / M2 (mol%): 79.9% / 11.8% / 8.3%.

[0174] Synthesis Example 14 The comparative polymer represented by AP-12 was prepared as shown in Scheme 9. [ka] 12.50 g of PGMEA was placed in the reactor and purged with N2 for 30 minutes while heating to 85°C. A monomer-initiator solution was prepared by dissolving M5 (27.44 g), M4 (2.57 g), and initiator V601 (1.70 g) in PGMEA (32.5 g), and this was filled into a syringe. The syringe was covered with a cooling agent to maintain the solution temperature below room temperature. After the reactor temperature stabilized at 85°C, the monomer-initiator solution was supplied to the reactor over 3 hours. After the addition was complete, the reactor was held at 85°C for a further 3 hours, and then cooled to 25°C. The product was precipitated in methanol, collected, and washed twice with methanol while stirring. The product was dried under high vacuum for 48 hours to obtain a polymer (20.0 g). This polymer solution was dissolved in PGMEA to obtain a 20% by weight solution. Mw=13.1kDa, Mn=9.1kDa, PDI=1.30, composition=M5 / M4 (mol%): 89.5% / 10.5%.

[0175] Dissolution rate (DR) evaluation An 8-inch silicon wafer was primed with HMDS at 120°C for 30 seconds on a TEL ACT-8 wafer track, coated with a 5 wt% polymer solution in PGMEA, and soft-baked at 110°C for 60 seconds to obtain a film layer approximately 100–120 nm thick. The initial film thickness was measured and is shown in Table 1. Subsequently, the wafer was treated with MF(trademark) CD26 tetramethylammonium hydroxide (TMAH) developer (DuPont Electronics & Industrial) for 60 seconds, rinsed with DI water, and dried. The film thickness after development was measured and is shown in Table 1. The dissolution rate of the polymer is determined by Equation 1. The change in film thickness (ΔFT) is determined by subtracting the FT after development from the film thickness before development (FT) according to Equation 2. The dissolution rate (DR) is reported in angstroms per second (Å / s). Dissolution rate (DR)=ΔFT / / Development time (sec) Equation 1 ΔFT = FT before development - FT after development (Equation 2)

[0176] [Table 1]

[0177] As shown in Table 1, polymers AP-1 to AP-6 and AP-7 to AP-11 of the present invention achieved improved (higher) developer dissolution rates compared to comparative polymer AP12, which possessed the desired base solubility.

[0178] Evaluation of contact angle An 8-inch silicon wafer was primed with HMDS at 120°C for 30 seconds on a TEL ACT-8 wafer track, coated with a 5 wt% polymer solution in PGMEA, and soft-baked at 110°C for 60 seconds to obtain a film layer approximately 100-120 nm thick. The contact angle of each polymer solution was measured using a Kruss contact angle goniometer with deionized Millipore filtered water. Subsequently, the receding angle in the soft-baked coated state was measured at the start of lateral fall motion before rapid acceleration. The receding angle after development / DI water rinsing was measured on a wafer treated with MF(trademark) CD26 TMAH developer (DuPont Electronics & Industrial) for 60 seconds, rinsed with DI water, and dried. The contact angle results for samples before and after exposure to the developer are shown in Tables 2 and 3. In Tables 2 and 3, Comparative Example AP-12 was tested on separate days. The first test was conducted using polymers AP-1 to AP-6 shown in Table 2, and the second test was conducted using polymers AP-7 to AP-11 shown in Table 3.

[0179] [Table 2]

[0180] [Table 3]

[0181] As shown in Table 2, polymers AP-1 to AP-6 achieved lower receding angles (contact angles in the soft-bake coated state) than the comparative polymer AP-12. After development, all samples showed a reduced receding angle compared to before development.

[0182] As shown in Table 3, polymers AP-7 to AP-11 of the present invention achieved higher receding angles (contact angles in the soft-bake coated state) than the comparative polymer AP-12. After development, all samples showed a reduced receding angle compared to before development.

[0183] Photoresist composition and evaluation The photoresist compositions were prepared by dissolving the solid components in a solvent using the materials and quantities shown in Table 4. The quantities are expressed as weight percent based on 100% of the total weight of the solids. The total solid content of the photoresist composition was 2.2% by weight. The solvent system contained PGMEA (50% by weight) and methyl-2-hydroxyisobutyric acid (50% by weight). Each mixture was shaken using a mechanical shaker and then filtered through a PTFE disc filter with a pore size of 0.2 microns.

[0184] Lithography was performed using the CLEAN TRACK ACT8 (TEL, Tokyo Electron Co.) wafer track. A 200nm wafer for photolithography testing was coated with AR(trademark)3 BARC (DuPont Electronics & Industrial) and soft-baked at 205°C for 60 seconds to obtain a 70nm film. Next, a coating of AR(trademark)40A BARC (DuPont Electronics & Industrial) was placed on top of the AR(trademark)3 layer and soft-baked at 215°C for 60 seconds to form a second BARC layer with a thickness of approximately 80nm. Then, a photoresist composition was coated onto the dual BARC stack and soft-baked at 110°C for 60 seconds to obtain a photoresist film layer with a thickness of approximately 70nm.

[0185] Using a mask with selected features, the wafer was exposed to 248 nm radiation using a Canon FPA-5000 ES4 scanner (NA=0.8, outer sigma=0.85, inner sigma=0.57). After exposure, the wafer was baked at 90°C for 60 seconds, developed with MF(trademark) CD26 TMAH developer (DuPont Electronics & Industrial) for 60 seconds, rinsed with DI water, and dried. Limiting dimension (CD) linewidth measurements of the formed pattern were performed using a Hitachi S-9380 CD-SEM. The LWR value was determined by top-down SEM with an acceleration voltage of 800 volts (V), probe current of 8.0 picoamperes (pA), digital zoom 1.0, magnification of 200Kx, and frame rate set to 64. The LWR was measured over a line length of 2 μm in a 40 nm process and reported as the average LWR of the measured area. Sizing energy (E) size The line width roughness (LWR) and line width roughness were determined based on CD measurements. The pseudo-Z factor is reported below. This was determined according to Equation 3. Pseudo Z-factor = (E size )×(LWR) 2 formula 3 In the formula, E size This is millijoules per square centimeter (mJ / cm²). 2 The values ​​are reported in units of ) and LWR is reported in nanometers (nm), and the pseudo-Z factor is mJ × 10⁻⁶. -11 It is reported in units. The pseudo-Z factor (Z'-factor) is a modified measure of photoresist performance based on the Z factor, which is an indicator of known parameters of RLS (Resolution, Line Edge Roughness, Sensitivity) photoresist performance (see, for example, Non-Patent Literature 1). The pseudo-Z factor is calculated at a constant resolution (CD size).

[0186] Structures of polymer P1, PAG-1, and deactivator Q1: [ka]

[0187] [Table 4]

[0188] As shown in Table 4, photoresist compositions PR-1 to PR-6 achieved improved LWR (reduction in LWR value) and improved pseudo-Z factor (reduction in pseudo-Z factor value) in L / S patterning under KrF exposure compared to the comparative photoresist composition PR-11. Photoresist compositions PR-7 to PR-10 achieved faster photospeed (E) in L / S patterning under KrF exposure compared to the comparative photoresist composition PR-11. size A reduction in the value was achieved.

Claims

1. A polymer comprising a first repeating unit derived from a polymerizable compound containing an aromatic group, and a second repeating unit containing a base-unstable group, The aforementioned aromatic group, A first substituent containing an ethylenically unsaturated double bond, The second substituent is a hydroxyl group, A third substituent containing a carbonyl group, It has been replaced with, The carbonyl groups of the first substituent, the second substituent, and the third substituent are bonded to different carbon atoms of the aromatic group, A polymer in which the first repeating unit and the second repeating unit are structurally different.

2. The first repeating unit is given by equation (1): 【Chemistry 1】 (In the formula, P １ It contains a group containing an ethylenically unsaturated double bond, P １ Ar is optional. １ They may also form a ring; Ar １ is a substitution or non-substitution C ６～６０ Aryl, substituted, or unsubstituted C ３～６０ It is a heteroaryl; Each L １ These are independently single bonds or divalent linking groups; Each R １ is, independently, substituted or unsubstituted C １～３０ alkyl, substituted or unsubstituted C ３～３０ cycloalkyl, substituted or unsubstituted C １～３０ heteroalkyl, substituted or unsubstituted C ２～３０ heterocycloalkyl, substituted or unsubstituted C ６～６０ aryl, or substituted or unsubstituted C ３～６０ heteroaryl; Each a is an integer greater than or equal to 1, and each b is an integer greater than or equal to 1, provided that a + b is an integer less than or equal to 10; (r is an integer greater than or equal to 1) The polymer according to claim 1, derived from a polymerizable compound.

3. Said part -C(O)-L １ -R １ The polymer according to claim 2, wherein the polymer contains an acid-unstable group.

4. The polymer according to any one of claims 1 to 3, wherein the base-unstable group comprises a fluorinated alkyl ester group, a fluorinated aryl ester group, or a hexafluoroalcohol group.

5. The second repeating unit is, Polymerizable groups containing ethylenically unsaturated double bonds; and Formula (4): 【Chemistry 2】 (In the formula, X １ is O, S, or -N (R ｃ ) - and; R ｃ is hydrogen or C １～６ It is alkyl; R ｆ (This refers to a substituted or unsubstituted fluoroalkyl group containing a fluorine atom bonded to the carbon atom at the α-position of the carbonyl group, or a fluoroalkyl group.) Base-unstable groups containing the structure represented by A polymer according to any one of claims 1 to 3, derived from one or more polymerizable compounds containing the above.

6. The second repeating unit is given by equation (5): 【Transformation 3】 (In equation (5), P ２ P is a group containing an ethylenically unsaturated double bond, ２ L is optional. ２ It may also form a ring, L ２ is a single bond or linking group; Each X １ These are independently O, S, or -N(R) ｃ ) - and R ｃ is hydrogen or C １～６ It is alkyl; Each R ｆ This is a substituted or unsubstituted fluoroalkyl group that independently contains a fluorine atom bonded to the carbon atom at the α-position relative to the carbonyl group, or a fluoroalkyl group; Each d is an integer greater than or equal to 1; e is an integer greater than or equal to 1. A polymer according to any one of claims 1 to 3, derived from one or more polymerizable compounds.

7. L ２ The polymer according to claim 6, wherein the group comprises an aromatic group substituted with at least one halogen.

8. A polymer according to any one of claims 1 to 7; Photoacid generator and; solvent and A photoresist composition containing [a specific substance].

9. The photoresist composition according to claim 8, further comprising a second polymer containing repeating units containing acid-unstable groups, wherein the second polymer is structurally different from the polymer.

10. A method for forming a pattern, A photoresist composition layer is obtained by coating a substrate with a layer of the photoresist composition described in claim 8 or 9; To provide the exposed photoresist composition layer by pattern-like exposure of the photoresist composition layer with activating radiation; and The exposed photoresist composition layer is developed to provide a photoresist pattern. Methods that include...

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