Photoresist composition and pattern forming method

Abstract

A photoresist composition comprising a polymer, a photoacid generator, an additive comprising a tertiary carbon atom as a ring-forming atom of a lactone ring, and a solvent.

Description

Technical Field

[0001] This invention relates to photoresist compositions and methods for patterning using such photoresist compositions. The invention finds particular applicability in photolithography applications within the semiconductor manufacturing industry. Background Technology

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

[0003] Further miniaturization of critical dimensions is generally not achievable with current lithography techniques that offer low manufacturing costs. For example, NAND flash memory manufacturers have been investigating techniques for stacking multiple layers of memory cells to achieve greater storage capacity while maintaining lower manufacturing costs per bit. Miniaturizing critical features while keeping manufacturing costs low has led to the development of stacked 3D structures for NAND applications. Such 3D NAND devices are denser, faster, and cheaper than traditional 2D planar NAND devices. 3D NAND architectures include vertical channel and vertical gate architectures, and a stepped structure (called a “staircase”) is used to form the electrical connections between memory cells and bit lines or word lines. When constructing 3D NAND flash memory, manufacturers use a thick resist to increase the number of steps, which is used in multiple trimming and etch cycles for step formation. Maintaining a good feature profile at each step is challenging because subsequent trimming-etching variations on the critical dimension (CD) will be incremental and accumulate across the wafer.

[0004] The "staircase" formation process, which uses a single mask exposure to form several sets of steps using thick KrF photoresist, is considered a relatively cost-effective method. However, using thick films in KrF lithography for printing micrometer-scale features presents unique technical challenges. Patterning thick resist films requires sufficient film transparency at the exposure wavelength to allow incident radiation to reach the bottom of the film. Furthermore, subjecting thick resist films used in 3D NAND applications to multiple resist thickness trimming and dry-etch cycles is challenging. Exposing thick resist films to trimming and etching processes can affect film structure uniformity and may lead to the formation of rough film surfaces and unwanted voids within the film. A suitable thick resist film should be able to maintain its physical structure after each thickness trimming and etching process.

[0005] Therefore, there is a continued demand for chemical compositions that can be applied to thick photoresists, which have good transparency at the exposure wavelength, excellent property retention after thickness trimming and etching, and improved adhesion at the substrate-photoresist interface. Summary of the Invention

[0006] A photoresist composition is provided, comprising a polymer, a photoacid generator, an additive comprising a tertiary carbon atom as a cyclizing atom of an lactone ring, and a solvent.

[0007] A method for forming a pattern is also provided, the method comprising applying a layer of the photoresist composition of the present invention onto a substrate to provide a photoresist composition layer, exposing the photoresist composition layer in a patterned manner to activation radiation to provide an exposed photoresist composition layer, and developing the exposed photoresist composition layer to provide the pattern. Detailed Implementation

[0008] Reference will now be made in detail to exemplary embodiments, examples of which are shown in this specification. In this respect, these exemplary embodiments may take different forms and should not be construed as limited to the description shown herein. Therefore, exemplary embodiments are described below only by reference to the accompanying drawings to explain various aspects of this specification. As used herein, the term “and / or” includes any and all combinations of one or more of the associated listed items. When a statement such as “at least one of…” precedes the list of elements, it modifies the entire list of elements and does not modify any individual element in the list.

[0009] As used herein, the terms “a / an” and “the” do not indicate a limitation of quantity and are to be construed as including both the singular and plural unless otherwise indicated herein or clearly contradicted by the context. Unless otherwise explicitly stated, “or” means “and / or”. The modifier “about” used in conjunction with quantity includes the value and has the meaning specified by the context (e.g., including the degree of error associated with a particular quantity of measurement). The full scope disclosed herein includes endpoints, and these endpoints can be independently combined with each other. The suffix “(s)” is intended to include both the singular and plural of the term it modifies, thereby including at least one of the stated terms. “Optional” or “optionally” means that an event or situation subsequently described may or may not occur, and the description includes examples of the event occurring as well as examples of its non-occurrence. The terms “first,” “second,” and similar terms herein do not indicate order, quantity, or importance, but are used to distinguish one element from another. When an element is referred to as being “on” another element, it may be in direct contact with or interposed to the other element, or the element may exist therein. In contrast, when an element is referred to as being "directly on" another element, there is no inserting element. It should be understood that the components, elements, limitations, and / or features of the described aspects can be combined in any suitable manner within the aspects.

[0010] Unless otherwise defined, all terms used herein (including technical and scientific terms) shall have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. It will be further understood that terms (such as those defined in common dictionaries) shall be interpreted as having the same meaning as they have in the relevant field and in the context of this disclosure, and shall not be construed as having an idealized or overly formal meaning unless expressly defined herein.

[0011] As used herein, "photochemical rays" or "radiation" refers to, for example, the bright-line spectrum of a mercury lamp, far-ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, particle rays (such as electron beams and ion beams), etc. Furthermore, in this invention, "light" refers to photochemical rays or radiation.

[0012] Krypton fluoride lasers (KrF lasers) are a special type of excimer laser, sometimes called excimer complex lasers. "Excimer" is an abbreviation for "excited dimer," and "excimer complex" is an abbreviation for "excited complex." Excimer lasers use a mixture of rare gases (argon, krypton, or xenon) and halogen gases (fluorine or chlorine), which, under appropriate electrical stimulation and high voltage conditions, emit coherent stimulated emission (lasing) in the ultraviolet range.

[0013] Furthermore, unless otherwise stated, “exposure” in this specification includes not only exposure by a mercury lamp, far ultraviolet light represented by an excimer laser, X-rays, extreme ultraviolet light (EUV light), etc., but also writing with particle beams (such as electron beams and ion beams).

[0014] As used herein, the term "hydrocarbon" refers to an organic compound or group having at least one carbon atom and at least one hydrogen atom; "alkyl" refers to a straight-chain or branched saturated hydrocarbon group having a specified number of carbon atoms and a valence of 1; "alkylene" refers to an alkyl group having a valence of 2; "hydroxyalkyl" refers to an alkyl group substituted with at least one hydroxyl group (-OH); "alkoxy" refers to "alkyl-O-"; "carboxyl" and "carboxylic acid" refer to groups having the formula "-C(O)-OH"; "cycloalkyl" refers to a monovalent group having one or more saturated rings in which all ring members are carbon; "cycloalkylene" refers to a cycloalkyl group having a valence of 2; "alkenyl" refers to a straight-chain or branched monovalent hydrocarbon group having at least one carbon-carbon double bond; "alkenyloxy" refers to "alkenyl-O-"; "alkenylene" refers to an alkenyl group having a valence of 2; "Cycloalkenyl" refers to a non-aromatic cyclic divalent hydrocarbon group having at least three carbon atoms and at least one carbon-carbon double bond; "alkynyl" refers to a monovalent hydrocarbon group having at least one carbon-carbon triple bond; the term "aromatic group" refers to a monocyclic or polycyclic ring system that satisfies Hückel's rule and includes a carbon atom in the ring, and optionally may include one or more heteroatoms selected from N, O, and S that replace the carbon atoms in the ring; "aryl" refers to a monovalent aromatic monocyclic or polycyclic ring system in which each ring member is carbon, and may include a group having an aromatic ring fused to at least one cycloalkyl or heterocyclic alkyl ring; "arylene" refers to an aryl group having a valence of 2; "alkylaryl" refers to an aryl group that has been substituted with an alkyl group; "arylalkyl" refers to an alkyl group that has been substituted with an aryl group; "aryloxy" refers to "aryl-O-"; and "arylthio" refers to "aryl-S-".

[0015] The prefix "hetero" means that the compound or group includes at least one member (e.g., 1, 2, 3, or 4 or more heteroatoms) as a heteroatom in place of a carbon atom, wherein each of these heteroatoms is independently N, O, S, Si, or P; "heteroatom-containing group" refers to a substituent that includes at least one heteroatom; "heteroalkyl" refers to an alkyl group having at least one heteroatom in place of a carbon atom; "heterocyclic alkyl" refers to a cycloalkyl group having at least one heteroatom as a ring member in place of a carbon atom; "heterocyclic alkyl" refers to a heterocyclic alkyl group having a valence of 2.

[0016] The term "heteroaryl" refers to an aromatic 4-8 membered monocyclic, 8-12 membered bicyclic, or 11-14 membered tricyclic ring system having 1-4 heteroatoms (if monocyclic), 1-6 heteroatoms (if bicyclic), or 1-9 heteroatoms (if tricyclic), each heteroatom being independently selected from N, O, S, Si, or P (e.g., carbon atom and 1-3, 1-6, or 1-9 N, O, or S heteroatoms, respectively, if monocyclic, bicyclic, or tricyclic). Examples of heteroaryl groups include pyridyl, furanyl (furyl or furanyl), imidazole, benzimidazolyl, pyrimidinyl, thiophenyl or thienyl, quinolinyl, indole, thiazolyl, etc.

[0017] The term "halogen" refers to a monovalent substituent of fluorine (fluorinated), chlorine (chloroinated), bromine (brominated), or iodine (iodinated). The prefix "halogenated" indicates a group containing one or more of the fluorine, chlorine, bromine, or iodine substituents that replace a hydrogen atom. Combinations of halogen groups (e.g., bromine and fluorine) or only fluorine groups may be present. For example, the term "halogenated alkyl" refers to an alkyl group substituted with one or more halogens. As used herein, "substituted C" refers to an alkyl group substituted with one or more halogens. 1-8 "Halogenated alkyl" refers to a C that has been substituted with at least one halogen. 1-8 Alkyl groups, and further substituted by one or more other substituents that are not halogens. It should be understood that substitution of groups with halogen atoms should not be considered as heteroatom-containing groups, because halogen atoms do not substitute carbon atoms.

[0018] "Fluorinated" should be understood as indicating the presence of fluorine atoms in one or more incorporated groups. For example, when indicating C... 1-18 When fluoroalkyl is used, the fluoroalkyl group can include one or more fluorine atoms, such as a single fluorine atom, two fluorine atoms (e.g., 1,1-difluoroethyl), three fluorine atoms (e.g., 2,2,2-trifluoroethyl), or fluorine atoms at each free valence of carbon (e.g., perfluorinated groups such as -CF3, -C2F5, -C3F7, or -C4F9). "Substituted fluoroalkyl" should be understood to mean a fluoroalkyl group further substituted with additional substituents that do not contain fluorine atoms.

[0019] Where appropriate, unless otherwise expressly provided, each of the aforementioned substituents may be optionally substituted. The term “optionally substituted” means substituted or unsubstituted. “Substituted” means that at least one hydrogen atom of the chemical structure is substituted by another terminal substituent group, typically monovalent, provided that the valence of the specified atom is not exceeded. When the substituent is oxo (i.e., O), the two twin hydrogen atoms on the carbon atom are replaced by a terminal oxo group. Combinations of substituents or variations are permitted. Exemplary groups 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, alkylacyl (such as C 2-6 Alkyl groups (such as acyl groups), formyl groups (-C(O)H), carboxylic acids or their alkali metal or ammonium salts; esters (including acrylates, methacrylates and lactones) such as C 2-6 Alkyl esters (-C(O)O-alkyl or -OC(O)-alkyl) and C 7-13 Aryl esters (-C(O)O-aryl or -OC(O)-aryl); amide groups (-C(O)NR2, where R is hydrogen or C). 1-6 alkyl), formamido (-CH2C(O)NR2, where R is hydrogen or C 1-6 Alkyl groups, halogens, mercapto groups (-SH), C 1-6 Alkylthio (-S-alkyl), thiocyano (-SCN), C 1-6 Alkyl, C 2-6 alkenyl, C 2-6 alkynyl group, C 1-6 Haloalkyl, C 1-9 Alkoxy, C 1-6 Halogenated alkoxy groups, C 3-12 cycloalkyl, C 5-18 Cycloalkenyl, C 2-18 Heterocyclic alkenyl groups, C groups having at least one aromatic ring 6-12 Aryl (e.g., phenyl, biphenyl, naphthyl, etc., each ring being substituted or unsubstituted aromatic), having 1 to 3 single or fused rings and 6 to 18 ring carbon atoms, C 7-19 arylalkyl, arylalkoxy having 1 to 3 single or fused rings and 6 to 18 ring carbon atoms, C 7-12 alkylaryl, C 3-12 Heterocyclic alkyl, C 3-12 heteroaryl, C 1-6 alkylsulfonyl (-S(O)2-alkyl), C 6-12Arylsulfonyl (-S(O)2-aryl) or toluenesulfonyl (CH3C6H4SO2-). When the group is substituted, the indicated number of carbon atoms is the total number of carbon atoms in the group, excluding those with any substituents. For example, the group -CH2CH2CN is a cyano-substituted C2 alkyl.

[0020] As used herein, an "acid-indestructible group" refers to a group in which a bond is broken by the catalytic action of an acid (optionally and typically in conjunction with heat treatment), resulting in the formation of a polar group (such as a carboxylic acid or alcohol group, formed on the polymer) and a portion of the bond connected to the broken bond, optionally and typically disconnected from the polymer. In other systems, nonpolymeric compounds may include acid-indestructible groups that can be cleaved by the catalytic action of an acid, resulting in the formation of a polar group, such as a carboxylic acid or alcohol group, on the cleaved portion of the nonpolymeric compound. Such acids are typically photogenerated acids (PEBs) under conditions of bond cleavage during post-exposure baking; however, the examples are not limited thereto, and such acids may, for example, be thermally generated. Suitable acid-indestructible groups include, for example, tertiary alkyl ester groups, secondary or tertiary aryl ester groups, secondary or tertiary ester groups having a combination of alkyl and aryl groups, tertiary alkoxy groups, acetal groups, or ketal groups. Acid-indestructible groups are also commonly referred to in the art as "acid-cleavable groups," "acid-cleavable protecting groups," "acid-indestructible protecting groups," "acid-leaving groups," "acid-decomposable groups," and "acid-sensitive groups."

[0021] As used herein, unless otherwise defined, "divalent linker" refers to -O-, -S-, -Te-, -Se-, -C(O)-, -N(R)-, etc. a -, -S(O)-, -S(O)2-, -C(S)-, -C(Te)-, -C(Se)-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 A divalent group, or one or more of a heteroaryl group or a combination thereof, wherein R a It is hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Heteroaryl groups. Typically, the divalent linking groups include -O-, -S-, -C(O)-, and -N(R-). a -, -S(O)-, -S(O)2-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 Heteroaryl groups or combinations thereof, wherein R a It is hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Heteroaryl groups. More typically, the divalent linking groups include -O-, -C(O)-, -C(O)O-, and -N(R-). a )-、-C(O)N(R a -, substituted or unsubstituted C 1-10 Alkylene, substituted or unsubstituted C 3-10 Cycloalkylene, substituted or unsubstituted C 3-10 Heterocyclic alkyl, substituted or unsubstituted C 6-10 aryl, substituted or unsubstituted C 3-10 Heteroaryl groups or combinations thereof, wherein R a It is hydrogen, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted C 1-10 Heteroalkyl, substituted or unsubstituted C 6-10 aryl, or substituted or unsubstituted C 3-10 Mixed aromatic compounds.

[0022] Thick films derived from photoresist compositions (“thick-film photoresist”) can be used as etching masks for creating surface features, such as stepped patterning for 3D NAND electronic device fabrication. Patterning methods for fabricating 3D NAND electronic devices typically require thick photoresist films with a thickness of 5 micrometers or greater for 248 nm irradiation. With increasing photoresist film thickness, the photoresist’s photosensitivity decreases, likely due to reduced transmittance at 248 nm. Furthermore, the larger film thickness results in poorer adhesion of the photoresist film to the substrate at the photoresist-substrate interface, possibly due to increased film stress.

[0023] This invention relates to photoresist compositions comprising a polymer; a photoacid generator (PAG); an additive containing a tertiary carbon atom as a cyclizing atom of a lactone ring; a solvent; and may contain other optional components. The inventors have discovered that certain photoresist compositions of this invention can be used to prepare photolithography properties with improved photosensitivity, such as increased photosensitivity, improved adhesion at the photoresist-substrate interface, and reduced delamination from the substrate surface.

[0024] The lactone ring, containing a tertiary carbon atom as a cyclizing atom, can undergo a ring-opening reaction in the presence of a strong acid catalyst, such as an acid generated by heat or light, to form an alkenyl carboxylic acid. Compared to additives that do not undergo a ring-opening reaction, the resulting alkenyl carboxylic acid exhibits increased solubility in alkaline developers. This increased solubility can increase the dissolution rate of thick films derived from the photoresist composition of the present invention in alkaline developers, resulting in faster photosensitivity.

[0025] To avoid being bound by theory, additives can act as plasticizers in the photoresist compositions of the present invention. Because the thick film obtained from the photoresist compositions of the present invention contains plasticizers, subsequently generated acids (e.g., photoacids) can diffuse more quickly within the film, which increases the photosensitivity. Furthermore, when additives plasticize films derived from the photoresist compositions of the present invention, the resulting thick films have lower stress, which reduces the amount of film delamination.

[0026] The additive in the photoresist composition of the present invention can be a compound represented by formula (1):

[0027] (1)

[0028] Where m can be an integer from 1 to 5, typically from 1 to 3, preferably 1 or 2.

[0029] In equation (1), R 1 and R 2 Each is independently either substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 3-20 heteroaryl. Substituted or unsubstituted C 1-20 Alkyl and substituted or unsubstituted C 1-20 Each heteroalkyl group can be straight-chain or branched. Substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl, substituted or unsubstituted C 6-20 Aryl and substituted or unsubstituted C 3-20 Each heteroaryl group can be monocyclic or polycyclic. In some respects, R 1 and R 2 Each is independently either substituted or unsubstituted C 1-6 Alkyl, preferably substituted or unsubstituted C 1-3 Alkyl, and more preferably unsubstituted C 1-3Alkyl, typically methyl. R 1 and R 2 Each of these may optionally further include, as part of its structure, a selection from -O-, -C(O)-, -S-, -S(O)2-, and -N(R-). 1a One or more groups of )-, wherein R 1a It is hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl groups.

[0030] In equation (1), each R 3 C can be substituted or unsubstituted independently. 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 3-20 heteroaryl. Substituted or unsubstituted C 1-20 Alkyl and substituted or unsubstituted C 1-20 Heteroalkyl groups can be straight-chain or branched. Substituted or unsubstituted C24 groups. 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 3-20 Heteroaryl groups can be monocyclic or polycyclic. Each R 3 Optionally, it may further include, as part of its structure, elements selected from -O-, -C(O)-, -S-, -S(O)2-, and -N(R-). 2a One or more groups of )-, wherein R 2a It is hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl groups. In some respects, each R 3 C can be substituted or unsubstituted independently. 1-6 Alkyl, preferably substituted or unsubstituted C 1-3 Alkyl, and more preferably unsubstituted C 1-3 Alkyl, typically methyl.

[0031] In equation (1), R 1 R 2 or R 3Any two groups can optionally form a ring together via a single bond or a divalent linker. In some respects, when n is 2 or greater, any two groups R 3 They can optionally form a ring through a divalent linker.

[0032] In equation (1), n ​​is an integer from 0 to 2(m+1). For example, n can be an integer from 0 to 12, typically from 0 to 6, preferably 0 or 4. It should be understood that when group R 3 Hydrogen atoms are present when they are not present at a given position of the lactone ring in equation (1).

[0033] In some respects, the additive may be a compound represented by one or more of formulas (1a) or (1b):

[0034] (1a) (1b)

[0035] In equations (1a) and (1b), R 1 and R 2 Same as defined in equation (1).

[0036] In equation (1a), R 3a R 3b R 4a and R 4b Each can be independently hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 3-20 Mixed aromatics. In some respects, R 3a R 3b R 4a and R 4b At least one of them is not hydrogen. In the examples, R 4a and R 4b One or more of them are substituted or unsubstituted C 1-20 Alkyl (and substituted C) 1-20 Alkyl groups are prefixed with -O-, -C(O)-, or -N(R)-. 1c One or more of -, -S-, -S(O)2- are substituted, and C is substituted or unsubstituted. 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl groups, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted divalent C 7-30Aryl groups, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted divalent C 4-30 Heteroarylalkyl, wherein R 1c It is hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 3-20 Heterocyclic alkyl groups.

[0037] In equation (1a), R 3a R 3b R 4a and / or R 4b Any two or more of them may optionally form a cyclic group by a single bond or a divalent linker, wherein the cyclic group is a monocyclic, non-fused polycyclic, or fused polycyclic.

[0038] In equation (1b), R 3a R 3b R 4a R 4b R 5a and R 5b Each can be independently hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 3-20 Mixed aromatics. In some respects, R 3a R 3b R 4a R 4b R 5a and R 5b At least one of them is not hydrogen. In other respects, R 3a R 3b R 5a and R 5b At least one of them is not hydrogen. In the embodiments, R 5a and R 5b One or more of them are substituted or unsubstituted C 1-20 Alkyl (and substituted C) 1-20 Alkyl groups are prefixed with -O-, -C(O)-, or -N(R)-. 1d One or more of -, -S-, -S(O)2- are substituted, and C is substituted or unsubstituted. 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl groups, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted divalent C7-30 Aryl groups, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted divalent C 3-30 Heteroarylalkyl, wherein R 1d It is hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 3-20 Heterocyclic alkyl groups.

[0039] In equation (1b), R 3a R 3b R 4a R 4b R 5a and / or R 5b Any two or more of them may optionally form a cyclic group by a single bond or a divalent linker, wherein the cyclic group is monocyclic, non-fused polycyclic, or fused polycyclic.

[0040] Exemplary additives include those with the following formula:

[0041]

[0042] Where R 4a As defined in equation (1a), and R 1a R 1b R 2a R 2b R 4c R 4d and R n Each is independently a hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 3-20 Mixed aromatics. R 3aa R 3bb and / or R 4a Any two or more of them may optionally form a cyclic group by a single bond or a divalent linker, wherein the cyclic group is monocyclic, non-fused polycyclic, or fused polycyclic. R 3aa R 3bb and / or R 4aa Any two or more of them may optionally form a cyclic group by a single bond or a divalent linker, wherein the cyclic group is monocyclic, non-fused polycyclic, or fused polycyclic.

[0043] Particularly useful additives may include, but are not limited to, one or more of the following compounds:

[0044]

[0045]

[0046] In some respects, additives can have a boiling point greater than or equal to 200°C, for example, when measured at ambient pressure or atmospheric pressure. As used herein, “ambient pressure” is approximately one atmosphere. For example, additives can have a boiling point of 200°C to 260°C at ambient pressure.

[0047] Additives are typically present in the photoresist composition in an amount of 1 to 40 wt%, typically 5 to 35 wt%, and more typically 10 to 30 wt% of the total solids of the photoresist composition. It will be understood that “total solids” includes polymers, PAG, additives, and other non-solvent components.

[0048] The additives of the present invention can be prepared using any method in the art, or can be commercially available. For example, the additives can be prepared by chemically modifying commercially available lactone compounds to include one or more functional groups. For example, commercially available lactones include, but are not limited to, tetrahydro-2,2,-dimethyl-5-oxo-3-furanoic acid (rutin), 2-carboxytetrahydro-5-oxo-2-furanoic acid, 2-oxo-1-oxaspiro[4,4]nonane-4-carboxylic acid, 5-hexyldihydro-5-methyl-2(3H)-furanone, 4-hydroxy-4-methyl-3-(3-oxobutyl)-valerate γ-lactone, camphoric acid, or 1-oxa-8-azaspiro(4,5)decane-2-one.

[0049] The photoresist composition comprises a polymer. In some aspects, the polymer may include repeating units containing acid-labile groups that can be cleaved by photogenerated acids under post-exposure baking conditions. The polymer of the photoresist composition may include acid-labile repeating units of monomers represented by one or more of the following formulas: (2), (3), (4), (5), or (6).

[0050] (2) (3) (4) (5) (6)

[0051] In equations (2), (3), and (4), R a R b and R cEach can be independently hydrogen, fluorine, cyano, or substituted or unsubstituted C. 1-10 Alkyl group. Preferably, R a R b and R c Each can be independently hydrogen, fluorine, or substituted or unsubstituted C. 1-5 Alkyl, typically methyl.

[0052] In equation (2), L 1 It is a divalent linker. For example, L 1 It can include 1 to 10 carbon atoms and at least one heteroatom. In a typical example, L 1 It can be -OCH2-, -OCH2CH2O-, or -N(R) 2a )-, where R 2a Is it hydrogen or C? 1-6 alkyl.

[0053] In equations (2) and (3), R 6 To R 11 Each is independently a hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 3-20 Cycloalkenyl, substituted or unsubstituted C 3-20 Heterocyclic alkenyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 3-20 heteroaryl, which is based on R 6 To R 8 No more than one of them can be hydrogen and R 9 To R 11 No more than one of them can be hydrogen, provided that R 6 To R 8 One of them is hydrogen, then R 6 To R 8 At least one of the other Cs is either substituted or unsubstituted. 6-20 aryl or substituted or unsubstituted C 3-20 heteroaryl, and if R 9 To R 11 One of them is hydrogen, then R 9 To R 11 At least one of the other Cs is either substituted or unsubstituted. 6-20 aryl or substituted or unsubstituted C 3-20 heteroaryl. Preferably, R 6 To R 11 Each is independently either substituted or unsubstituted C1-6 Alkyl or substituted or unsubstituted C 3-10 Cycloalkyl. R 6 To R 11 Each of them may optionally further include a divalent linker group as part of its structure.

[0054] For example, R 6 To R 11 Any one or more of them can independently be of the formula -CH2C(O)CH (3-n) Y n or -CH2C(O)OCH (3-n) Y n The group, wherein each Y is independently a substituted or unsubstituted C. 3-10 Heterocyclic alkyl groups, and n is 1 or 2. For example, each Y can be independently substituted or unsubstituted, including the formula -O(C a1 (C) a2 The C of the O- group 3-10 Heterocyclic alkyl, wherein C a1 and C a2 Each is independently hydrogen or a substituted or unsubstituted alkyl group, and wherein C a1 and C a2 They can be arranged together to form a ring.

[0055] In equation (2), R 6 To R 8 Any two of them may optionally form a ring together, which may further include a divalent linking group as part of its structure, and wherein the ring may be substituted or unsubstituted.

[0056] In equation (3), R 9 To R 11 Any two of them may optionally form a ring, which may further include a divalent linking group as part of its structure, wherein the ring group may be substituted or unsubstituted.

[0057] In equations (4) and (6), R 12 R 13 R 18 and R 19 Each can be independently hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 3-20 heteroaryl; and R 14 and R 20 Each is independently either substituted or unsubstituted C1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 3-20 Heterocyclic alkyl groups. Preferably, R 12 R 13 R 15 and R 16 Each can be independently hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 3-20 Heterocyclic alkyl. R 12 R 13 R 18 and R 19 Each of them may optionally further include a divalent linker group as part of its structure.

[0058] In equation (4), R 12 To R 14 Any two of them may optionally form a ring together, wherein the ring may further include a divalent linking group as part of its structure, wherein the ring group may be substituted or unsubstituted.

[0059] In equation (5), R 15 To R 17 Each can be either substituted or unsubstituted C independently. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 3-20 heteroaryl, which is based on R 15 To R 17 No more than one of them can be hydrogen, provided that R 15 To R 17 One of them is hydrogen, then R 15 To R 17 At least one of the other Cs is either substituted or unsubstituted. 6-20 aryl or substituted or unsubstituted C 3-20 Mixed aromatics. R 15 To R 17 Each of them may optionally further include a divalent linker group as part of its structure.

[0060] For example, R 15 To R 17 Any one or more of them can independently be of the formula -CH2C(O)CH (3-n) Y n or -CH2C(O)OCH (3-n) Yn The group, wherein each Y is independently a substituted or unsubstituted C. 3-10 Heterocyclic alkyl groups, and n is 1 or 2. For example, each Y can be independently substituted or unsubstituted, including the formula -O(C a1 (C) a2 The C of the O- group 3-10 Heterocyclic alkyl, wherein C a1 and C a2 Each is independently hydrogen or a substituted or unsubstituted alkyl group, and wherein C a1 and C a2 They can be arranged together to form a ring.

[0061] In equation (5), R 15 To R 17 Any two of them may optionally form a ring together, wherein the ring may further include a divalent linking group as part of its structure, wherein the ring group may be substituted or unsubstituted.

[0062] In equations (5) and (6), X a and X b Each is independently a polymerizable group selected from vinyl and norborneol.

[0063] In equations (5) and (6), L 2 and L 3 Each is an independent single-bonded or divalent linker, provided that X is a single bond or a divalent linker. a When it is vinyl, L 2 It is not a single bond, and when X b When it is vinyl, L 3 It is not a single bond. Preferably, L 2 and L 3 Each is independently either substituted or unsubstituted C 6-30 aryl or substituted or unsubstituted C 6-30 Cycloalkylene. In formulas (5) and (6), n1 is 0 or 1, and n2 is 0 or 1. It should be understood that when n1 is 0, L 2 The group is directly attached to the oxygen atom. It should be understood that when n² is 0, L... 3 The group is directly attached to the oxygen atom.

[0064] In equation (6), R 18 To R 20 Any two of them may optionally form a ring, which may further include a divalent linking group as part of its structure, wherein the ring group may be substituted or unsubstituted.

[0065] In some respects, R 6 To R 20Each of these may optionally include, as part of its structure, a selection from -O-, -C(O)-, -C(O)-O-, -S-, -S(O)2-, and N(R). ’ One or more divalent linking groups of )-S(O)2-, wherein R ’ It can be hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 3-20 Heterocyclic alkyl groups.

[0066] In some respects, in repeating units containing acid-labile groups, the acid-labile group can be a tertiary alkyl ester. For example, repeating units containing tertiary alkyl ester groups can be derived from one or more monomers having formula (2), (3), or (5), wherein R 6 To R 11 Neither of them is hydrogen, and n1 is 1.

[0067] Exemplary monomers having formula (2) include one or more of the following:

[0068]

[0069]

[0070] Exemplary monomers having formula (3) include one or more of the following:

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078] Where R d As in this paper, R in equation (3) b Defined; and R ’ and R ’’ Each is independently either substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 3-20 Cycloalkenyl, substituted or unsubstituted C 3-20 Heterocyclic alkenyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 3-20 Mixed aromatic compounds.

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

[0080]

[0081] Where R d R is as defined above c .

[0082] Exemplary monomers having formula (5) include one or more of the following:

[0083]

[0084] Exemplary monomers having formula (6) include one or more of the following:

[0085]

[0086] In another example, the polymer may have an acid-instable repeating unit derived from one or more monomers having cyclic acetal or cyclic ketal groups, for example having one or more of the following structures:

[0087]

[0088]

[0089]

[0090]

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

[0092] In some respects, the polymer may have repeating units containing acid-labile groups (including tertiary alkoxy groups), such as one or more of the following monomers:

[0093]

[0094] Repeating units with acid-labile groups are typically present in polymers in amounts of 5 to 80 mol%, more typically 15 to 75 mol%, and even more typically 20 to 60 mol%, based on the total repeating units in the polymer.

[0095] The polymer may further optionally include one or more additional repeating units. These additional repeating units may be, for example, units used to modulate the properties of the photoresist composition, such as etching rate and solubility. Exemplary additional units may include those derived from one or more of (meth)acrylates, vinyl aromatic compounds, vinyl ethers, vinyl ketones, and / or vinyl ester monomers. These one or more additional repeating units (if present in the polymer) may be used in amounts up to 90 mol%, typically 3 to 50 mol%, based on the total repeating units of the polymer.

[0096] The polymer may further comprise repeating units derived from one or more monomers having formula (7) or (8):

[0097] (7) (8)

[0098] Where R d and R f Each is independently a hydrogen, fluorine, cyano group, or a substituted or unsubstituted C group. 1-10alkyl.

[0099] In equation (7), L 4 It is a single bond or a divalent linker. L 4 Exemplary divalent linking groups include substituted or unsubstituted C 1-20 Alkylene, substituted or unsubstituted C 3-20 Cycloalkylene, or substituted or unsubstituted C 3-20 One or more of heterocyclic alkyl groups.

[0100] In equation (7), L 5 It is a divalent linker. L 5 Exemplary divalent linking groups include substituted or unsubstituted C 1-20 Alkylene, substituted or unsubstituted C 3-20 Cycloalkylene, substituted or unsubstituted C 3-20 Heterocyclic alkyl groups, -O-, -C(O)-, -S-, -S(O)2- and N(R) 22a One or more of )-S(O)2, wherein R 22a It can be hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 3-20 Heterocyclic alkyl groups.

[0101] In equation (7), q is 0 or 1.

[0102] It should be understood that when L 4 When it is a single bond, part of R 22 -L 5 - Directly attached to the oxygen atom adjacent to the carbonyl group (i.e., -C(O)-OL) 5 -R 22 Similarly, it should be understood that when q is 0, part of R... 22 - Directly connected to group L 4 (i.e., -C(O)-OL) 4 -R 22 For L among them 4 This is the case of a single bond and q is 0. It should be understood that some R... 22 It is directly attached to the oxygen atom adjacent to the carbonyl group (i.e., -C(O)-OR). 22 ).

[0103] In equation (7), R 22 It is an organic group comprising one or more heteroatoms, whether substituted or unsubstituted. Exemplary organic groups comprising one or more heteroatoms in this invention include, but are not limited to, nitro (-NO2), cyano (-CN), and amino (-NR). 22b R 22c, where R 22b and R 22c Each is independently a hydrogen, substituted or unsubstituted C. 1-10 Alkyl, substituted or unsubstituted C 6-12 aryl, or substituted or unsubstituted C 3-12 heteroaryl), hydroxyl (-OH), carboxyl (-C(O)-OH), substituted or unsubstituted C 1-20 Alkoxy, substituted or unsubstituted C 6-24 aryloxy group, mercapto group (-SH), substituted or unsubstituted C 6-24 Aryl mercapto, sulfonyl, or combinations thereof.

[0104] In some respects, repeating units derived from monomers having formula (7) include hydroxyl-substituted C2. 1-30 Alkyl, hydroxyl substituted C 3-30 Cycloalkyl, hydroxyl-substituted C 6-30 Aryl and hydroxy substituted C 3-30 heteroaryl groups, or combinations thereof, each of which may be further substituted.

[0105] In equation (8), L 6 It is a single bond or a divalent linker. L 6 Exemplary divalent linking groups include substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 Heteroaryl, -O-, -C(O)-, -S-, -S(O)2- or -N(R 23a One or more of )-S(O)2-, wherein R 23a It can be hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 3-20 Heterocyclic alkyl groups.

[0106] It should be understood that when L 6 When it is a single bond, part of R 23 - Directly attached to the oxygen atom adjacent to the carbonyl group (i.e., -C(O)OR) 23 ).

[0107] In equation (8), R 23 It is C with or without substitution. 4-20 The lactone group may contain substituted or unsubstituted C groups. 4-20 The group of sulfonyl lactone. Contains C.4-20 lactone groups and C-containing groups 4-20 The groups of sulfonyl lactones can be monocyclic, polycyclic, or fused polycyclic.

[0108] An exemplary monomer having formula (7) may include one or more of the following:

[0109]

[0110] Where R d It is as defined for equation (7).

[0111] An exemplary monomer having formula (8) may include one or more of the following:

[0112]

[0113]

[0114]

[0115] Where R f It is as defined for equation (8).

[0116] When present, the polymer typically contains 5 to 60 mol%, typically 20 to 55 mol%, and more typically 25 to 50 mol% of the total repeating units in the polymer derived from repeating units having formula (7) and / or (8).

[0117] In some aspects, the polymer may further comprise alkali-soluble repeating units having a pKa of less than or equal to 12. For example, the alkali-soluble repeating units may be derived from one or more monomers having formula (9), (10), or (11):

[0118] (9) (10) (11)

[0119] In equations (9) to (11), each R g It can be hydrogen, fluorine, cyano, or substituted or unsubstituted C. 1-10 Alkyl group. Preferably, R g It can be hydrogen, fluorine, or substituted or unsubstituted C. 1-5 Alkyl groups, typically methyl groups.

[0120] In equation (9), R 24 C can be substituted or unsubstituted. 1-100 Or C 1-20 Alkyl, typically C 1-12Alkyl; substituted or unsubstituted C 3-30 Or C 3-20 cycloalkyl; or substituted or unsubstituted poly(C) 1-3 Epoxides). Preferably, substituted C 1-100 Or C 1-20 Alkyl, substituted C 3-30 Or C 3-20 cycloalkyl and substituted poly(C) 1-3 Epoxides are substituted with one or more of the following: halogens, fluoroalkyl groups such as C 1-4 Fluoroalkyl groups (typically desfluoromethyl), sulfonamide groups -NH-S(O)2-Y 1 , where Y 1 Is it F or C? 1-4 Perfluoroalkyl (e.g., -NHSO2CF3) or fluoroalcohol groups (e.g., -C(CF3)2OH).

[0121] In equation (10), L 7 Represents a single bond or a multivalent linker selected from: for example, optionally substituted aliphatic groups (such as C...). 1-6 Alkylene or C 3-20 Cycloalkylene hydrocarbons, aromatic hydrocarbons, and combinations thereof, optionally having one or more of the following selected from -O-, -S-, -C(O)-, and -NR-. 102 - the connection part, where R 102 Selected from hydrogen and optionally substituted C 1-10 Alkyl groups. For example, the polymer may further comprise repeating units derived from one or more monomers having formula (10), wherein L 7 It is a single bond or a polyvalent linker selected from the following: substituted or unsubstituted C 1-20 Alkylene, typically C 1-6 Alkylene; substituted or unsubstituted C 3-20 Cycloalkylene, typically C 3-10 Cycloalkylene; and substituted or unsubstituted C 6-24 Alpha-aryl.

[0122] In equation (10), n3 is an integer from 1 to 5, typically 1. It should be understood that when n3 is 1, the group L... 7 It is a divalent linker. It should be understood that when n3 is 2, the group L... 7 It is a trivalent linker. Similarly, it should be understood that when n3 is 3, the group L... 7 It is a tetravalent linker; when n3 is 4, the group L 7 It is a pentavalent linker; and when n3 is 5, the group L 7It is a hexavalent linker. Therefore, in the context of formula (10), the term "multivalent linker" refers to any of the divalent, trivalent, tetravalent, pentavalent, and / or hexavalent linkers. In some respects, when n is 2 or greater, the carboxylic acid group (-C(O)-OH) can be attached to the linker L. 7 On the same atom. In other respects, when n is 2 or greater, the carboxylic acid group (-C(O)-OH) can be attached to the linking group L. 7 On different atoms.

[0123] In equation (11), L 8 This indicates a single bond or a divalent linker. Preferably, L 8 It can be a single bond, substituted, or unsubstituted C. 6-30 aryl, or substituted or unsubstituted C 6-30 Cycloalkylene.

[0124] In equation (11), n4 is 0 or 1. It should be understood that when n4 is 0, the part represented by -OC(O)- is a single bond, such that L 8 It is directly attached to the alkenyl (vinyl) carbon atom.

[0125] In equation (11), Ar 1 It is the replacement of C 5-60 An aromatic group, optionally comprising one or more aromatic cyclic heteroatoms selected from N, O, S, or combinations thereof, wherein the aromatic group may be monocyclic, non-fused polycyclic, or fused polycyclic. When C 5-60 When the aromatic group is polycyclic, the one or more cyclic groups can be fused (such as naphthyl), non-fused, or a combination thereof. When the polycyclic C... 5-60 When aromatic groups are non-fused, the one or more cyclic groups can be directly linked (e.g., biaryl, biphenyl, etc.) or bridged by heteroatoms (e.g., triphenylamino or diphenylene ether). In some respects, polycyclic C 5-60 Aromatic groups can include combinations of fused rings and directly linked rings (such as binaphthyl groups).

[0126] In equation (11), y can be an integer from 1 to 12, preferably from 1 to 6, and typically from 1 to 3. Each R x It can be hydrogen or methyl independently.

[0127] Non-limiting examples of monomers that can be used to provide alkali-soluble repeating units in polymers include one or more of the following:

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137] Where Y 1 As described above, and R i For example, R in equations (9)-(11) g Defined.

[0138] When present, the polymer typically contains alkali-soluble repeating units in amounts of 1 to 60 mol%, typically 5 to 50 mol%, and more typically 5 to 40 mol%, based on the total repeating units in the polymer.

[0139] Non-limiting exemplary polymers of the present invention include one or more of the following:

[0140]

[0141]

[0142] Where a, b, c, and d represent the mole fraction of each repeating unit of the polymer.

[0143] The polymer typically has a weight-average molecular weight (Mn) of 1,000 to 50,000 Daltons (Da), preferably 2,000 to 30,000 Da, more preferably 4,000 to 25,000 Da, and still more preferably 5,000 to 25,000 Da. w The first polymer's polydispersity index (PDI) (which is M) w Number-average molecular weight (M n The ratio of 1 / 3 to 1 / 2 is typically 1.1 to 3, and more typically 1.1 to 2. Molecular weight values ​​are determined by gel permeation chromatography (GPC) using polystyrene standards.

[0144] Polymers can be prepared using any suitable method or one method in the art. For example, one or more monomers corresponding to the repeating units described herein can be fed together or separately using suitable solvents or initiators and polymerized in a reactor. For example, polymers can be obtained by polymerizing the respective monomers under any suitable conditions, such as by heating at an effective temperature, irradiation with photochemical radiation at an effective wavelength, or a combination thereof.

[0145] The photoresist composition also includes a photoacid generator (PAG). A suitable PAG generates an acid that causes the acid-indestructible groups present on the polymer of the photoresist composition to cleave during post-exposure baking (PEB). The PAG can be in a non-polymeric or polymeric form, for example, present in repeating units of polymers as described above, or as part of different polymers. In some embodiments, PAG may be included in the composition as a non-polymeric PAG compound, as a repeating unit of a polymer having a PAG moiety derived from a polymerizable PAG monomer, or as a combination thereof.

[0146] Suitable nonpolymeric PAG compounds can have the formula G + A - G + It is an organic cation selected from iodonium cations substituted with two alkyl groups, two aryl groups, or combinations of alkyl and aryl groups; and sulfonium cations substituted with three alkyl groups, three aryl groups, or combinations of alkyl and aryl groups; and A - It is a non-polymerizable organic anion. Particularly suitable non-polymerizable organic anions include those whose conjugate acid has a pKa of -15 to 1. Particularly preferred anions are fluorinated alkyl sulfonates and fluorinated sulfonamides.

[0147] Useful non-polymerized PAG compounds are known in the field of chemically enhanced photoresists and include, for example, onium salts such as triphenylsulfonium trifluoromethane sulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethane sulfonate, tri(p-tert-butoxyphenyl)sulfonium trifluoromethane sulfonate, triphenylsulfonium p-toluene sulfonate; di-tert-butylphenyliodomonium perfluorobutane sulfonate and di-tert-butylphenyliodomonium camphor sulfonate. It is also known that nonionic sulfonates and sulfonyl compounds act as photoacid generators, such as nitrobenzyl derivatives, such as 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate, and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonates, such as 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives, such as bis(benzenesulfonyl)diazomethane and bis(p-toluenesulfonyl)diazomethane; ethylene glycol Oxime derivatives, such as bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime and bis-O-(n-butanesulfonyl)-α-dimethylglyoxime; sulfonate derivatives of N-hydroxyimide compounds, such as N-hydroxysuccinimide methanesulfonate and N-hydroxysuccinimide trifluoromethanesulfonate; and halogen-containing triazine compounds, such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine and 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine. Suitable nonpolymeric photoacid generators are further described in U.S. Patent No. 8,431,325 to Hashimoto et al., in columns 37, lines 11-47 and 41-91. Other suitable sulfonate PAGs include sulfonated esters and sulfonyloxyketones, nitrobenzyl esters, s-triazine derivatives, benzoin toluenesulfonate, α-(p-toluenesulfonyloxy)acetic acid tert-butylphenyl ester, and α-(p-toluenesulfonyloxy)acetic acid tert-butyl ester; as described in U.S. Patent Nos. 4,189,323 and 8,431,325.

[0148] Typically, when the photoresist composition includes a nonpolymeric photoacid generator, it is present in the photoresist composition in an amount of 0.3 to 65 wt%, more typically 1 to 20 wt%, based on the total solids of the photoresist composition.

[0149] In some embodiments, G + It can be a sulfonium cation having formula (13) or an iodonium cation having formula (14):

[0150] (13) (14)

[0151] In equations (13) and (14), each R aaC is either substituted or unsubstituted independently. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 heteroaryl, substituted or unsubstituted C 7-20 arylalkyl, or substituted or unsubstituted C 4-20 Heteroarylalkyl. Each R aa It can be attached to another group R alone or via a single bond or a divalent linker. aa To form a loop. Each R aa Optionally, it may include a divalent linker group that is part of its structure. Each R aa It may optionally contain an acid-instable group selected from, for example, the following: tertiary alkyl ester group, secondary or tertiary aryl ester group, secondary or tertiary ester group having a combination of alkyl and aryl groups, tertiary alkoxy group, acetal group or ketal group.

[0152] An exemplary sulfonium cation having formula (13) may include one or more of the following:

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161] An exemplary iodonium cation having formula (14) may include one or more of the following:

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168] PAGs that are onium salts typically contain organic anions with sulfonate groups or non-sulfonate groups, such as sulfonamidate, sulfonimidate, methylation, or borate.

[0169] Exemplary organic anions having a sulfonate group include one or more of the following:

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177] Exemplary nonsulfonated anions include one or more of the following:

[0178]

[0179]

[0180]

[0181] The photoresist composition may optionally contain a variety of PAGs. The PAGs may be polymeric, non-polymeric, or may include both polymeric and non-polymeric PAGs. Preferably, each of the multiple PAGs is non-polymeric.

[0182] In one or more aspects, the photoresist composition may include a first photoacid generator comprising a sulfonate group on an anion, and the photoresist composition may include a non-polymerized second photoacid generator, wherein the second photoacid generator may include an anion without a sulfonate group.

[0183] In some respects, the polymer may optionally further comprise repeating units containing a PAG moiety, for example, repeating units derived from one or more monomers having formula (15):

[0184] (15)

[0185] In equation (15), R m It can be hydrogen, fluorine, cyano, or substituted or unsubstituted C. 1-10 Alkyl group. Preferably, R m It is hydrogen, fluorine, or substituted or unsubstituted C. 1-5 Alkyl group, typically methyl group. Q 1 It can be a single bond or a divalent linker. Preferably, Q 1 It may include 1 to 10 carbon atoms and at least one heteroatom, more preferably -C(O)-O-.

[0186] In equation (15), A 1 It can be one or more of the following: substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Hybrid aryl. Preferably, A 1 divalent C can be arbitrarily substituted 1-30 Perfluoroalkylene groups.

[0187] In equation (15), Z - It is the anionic moiety, and its conjugate acid typically has a pKa of -15 to 1. For example, Z - It can be a sulfonate, a carboxylate, an anion of a sulfonamide, an anion of a sulfonamide, or a methyl anion. Particularly preferred anionic moieties are fluorinated alkyl sulfonates and fluorinated sulfonamides.

[0188] In equation (15), G + It is an organic cation as defined above. In some embodiments, G + It is an iodonium cation substituted with two alkyl groups, two aryl groups, or a combination of alkyl and aryl groups; or a sulfonium cation substituted with three alkyl groups, three aryl groups, or a combination of alkyl and aryl groups.

[0189] An exemplary monomer having formula (15) may include one or more of the following:

[0190]

[0191]

[0192]

[0193]

[0194] Among them G + It is an organic cation as defined in this article.

[0195] When used, the repeating units containing the PAG portion may be included in the polymer in an amount of 1 to 15 mol%, typically 1 to 8 mol%, more typically 2 to 6 mol%, based on the total repeating units in the polymer.

[0196] The photoresist composition further comprises a solvent for dissolving the components of the composition and promoting its coating on a substrate. Preferably, the solvent is an organic solvent commonly used in the manufacture of electronic devices. Suitable solvents include, for example: aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, and 1-chlorohexane; alcohols such as methanol, ethanol, 1-propanol, isopropanol, tert-butanol, 2-methyl-2-butanol, 4-methyl-2-pentanol, and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone); propylene glycol monomethyl ether (PGME); ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and anisole; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, and cyclohexane. Ketones (CHO); esters, such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), methyl hydroxyisobutyrate (HBM), and ethyl acetoacetate; lactones, such as γ-butyrolactone (GBL) and ε-caprolactone; lactams, such as N-methylpyrrolidone; nitriles, such as acetonitrile and propionitrile; cyclic or acyclic carbonates, such as propylene carbonate, dimethyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, and propylene carbonate; polar aprotic solvents such as dimethyl sulfoxide and dimethylformamide; water; and combinations thereof. Among these, preferred solvents are PGME, PGMEA, EL, GBL, HBM, CHO, and combinations thereof.

[0197] The total solvent content (i.e., the cumulative solvent content of all solvents) in the photoresist composition is typically 40 to 99 wt%, for example 60 to 99 wt%, or 85 to 99 wt%, based on the total solids of the photoresist composition. The desired solvent content will depend, for example, on the desired thickness of the photoresist layer being coated and the coating conditions.

[0198] The polymer is typically present in the photoresist composition in an amount of 10 to 99.9 wt%, typically 25 to 99 wt%, and more typically 40 to 95 wt% of the total solids based on the photoresist composition. It will be understood that "total solids" includes the polymer, PAG, additives, and other non-solvent components.

[0199] In some aspects, the photoresist composition may further comprise a material containing one or more base-indestructible groups (“base-indestructible material”). As mentioned herein, a base-indestructible group is a functional group that can undergo a cleavage reaction in the presence of an aqueous base developer after the exposure and post-exposure baking steps to provide a polar group (such as hydroxyl, carboxylic acid, sulfonic acid, etc.). The base-indestructible group will not react significantly prior to the development step of the photoresist composition containing the base-indestructible group (e.g., will not undergo bond-breaking reactions). Therefore, for example, the base-indestructible group will be substantially inert during the pre-exposure soft bake step, the exposure step, and the post-exposure baking step. “Substantially inert” means that ≤ 5%, typically ≤ 1%, of the base-indestructible group (or portion) will decompose, cleave, or react during the pre-exposure soft bake, exposure, and post-exposure baking steps. The base-indestructible group is reactive under typical photoresist development conditions using, for example, an aqueous base photoresist developer (such as an aqueous solution of 0.26 standard (N) tetramethylammonium hydroxide (TMAH)). For example, a 0.26 N aqueous solution of TMAH can be used for single-immersion development or dynamic development, whereby a 0.26 N TMAH developer is dispensed onto the imaged photoresist layer for a suitable duration (e.g., 10 to 120 seconds). Exemplary base-insecure groups are ester groups, typically fluorinated ester groups. Preferably, the base-insecure material is substantially immiscible with the polymer and other solid components of the photoresist composition and has a lower surface energy than them. Thus, when coated onto a substrate, the base-insecure material can separate from the other solid components of the photoresist composition and reach the top surface of the formed photoresist layer.

[0200] In some aspects, alkali-insecure materials can be polymeric materials that may include one or more repeating units containing one or more alkali-insecure groups (also referred to herein as alkali-insecure polymers). For example, an alkali-insecure polymer may contain repeating units containing two or more identical or different alkali-insecure groups. Preferred alkali-insecure polymers include at least one repeating unit containing two or more alkali-insecure groups, such as repeating units containing two or three alkali-insecure groups.

[0201] Alkali-unstable polymers can be polymers comprising repeating units derived from one or more monomers having formula (16):

[0202] (16)

[0203] Where X e It is a polymerizable group selected from vinyl and (meth)acrylic acid, L 9 It is a divalent linker; and R n Is it substituted or unsubstituted C? 1-20Fluoroalkyl, provided that the carbon atom of the carbonyl group (-C(O)-) bonded to formula (16) is replaced by at least one fluorine atom.

[0204] An exemplary monomer having formula (16) may include one or more of the following:

[0205]

[0206] Alkali-insecure polymers may include repeating units comprising two or more alkali-insecure groups. For example, alkali-insecure polymers may include repeating units derived from one or more monomers having formula (17):

[0207] (17)

[0208] Where X f and R p For X, respectively, as in equation (16) e and R n Defined; L 10 It includes substituted or unsubstituted C 1-20 Alkylene, substituted or unsubstituted C 3-20 One or more of the following polyvalent linkages: cycloalkylene, -C(O)-, or -C(O)O-; and n3 can be an integer of 2 or greater, such as 2 or 3.

[0209] An exemplary monomer having formula (17) may include one or more of the following:

[0210]

[0211] Base-instable polymers may comprise repeating units including one or more base-instable groups. For example, a base-instable polymer may comprise repeating units derived from one or more monomers having formula (18):

[0212] (18)

[0213] Where X g and R q For X, respectively, as in equation (16) e and R n Defined; L 11 It is a divalent linker; and L 12 Is it substituted or unsubstituted C? 1-20 Fluoride, wherein the carbon atom of the carbonyl group (-C(O)-) bonded to formula (18) is replaced by at least one fluorine atom.

[0214] An exemplary monomer having formula (18) may include one or more of the following:

[0215]

[0216] In another preferred aspect of the invention, the alkali-instable polymer may comprise one or more alkali-instable groups and one or more acid-instable groups, such as one or more acid-instable ester moieties (e.g., tert-butyl ester) or acid-instable acetal groups. For example, the alkali-instable polymer may comprise repeating units including alkali-instable and acid-instable groups, i.e., wherein both alkali-instable and acid-instable groups are present on the same repeating unit. In another example, the alkali-instable polymer may comprise a first repeating unit containing alkali-instable groups and a second repeating unit containing acid-instable groups. Preferred photoresists of the present invention can exhibit reduced defects associated with resist relief images formed from photoresist compositions.

[0217] Base-instable polymers can be prepared using any suitable method in the art, including those described herein with respect to the first and second polymers. For example, base-instable polymers can be obtained by polymerization of the respective monomers under any suitable conditions, such as by heating at an effective temperature, irradiation with photochemical radiation at an effective wavelength, or a combination thereof. Furthermore or alternatively, suitable methods can be used to graft one or more base-instable groups onto the polymer backbone.

[0218] In some respects, alkali-instable materials are single molecules comprising one or more alkali-instable ester groups, preferably one or more fluorinated ester groups. Alkali-instable materials that are single molecules typically have an M value in the range of 50 to 1,500 Da. W Exemplary alkali-insecure materials include one or more of the following:

[0219]

[0220] When present, the alkali-unstable polymer is typically present in the photoresist composition in an amount of 0.01 to 10 wt%, more typically 1 to 5 wt%, based on the total solids of the photoresist composition.

[0221] Additionally, or alternatively, in addition to alkali-instable polymers, the photoresist composition may further comprise one or more polymers other than those described above. For example, the photoresist composition may contain additional polymers as described above but with different compositions, or polymers similar to those described above but not containing each of the required repeating units. Furthermore, or alternatively, the one or more additional polymers may include those well known in the field of photoresists, such as those selected from: polyacrylates, polyvinyl ethers, polyesters, polynorbornene, polyacetals, polyethylene glycol, polyamides, polyacrylamide, polyphenols, phenolic varnishes, styrene polymers, polyvinyl alcohol, or combinations thereof.

[0222] The photoresist composition may further include one or more additional optional additives. For example, optional additives may include photochemical dyes and contrast dyes, anti-stripping agents, plasticizers, accelerators, sensitizers, photodegradable quenchers (PDQ) (and also referred to as photodegradable bases), alkaline quenchers, hot acid generators, surfactants, etc., or combinations thereof. If present, optional additives are typically present in the photoresist composition in an amount of 0.01 to 10 wt% based on the total solids of the photoresist composition.

[0223] PDQ generates a weak acid upon irradiation. The acid generated by the photodegradable quencher is not strong enough to react rapidly with the acid-instable groups present in the resist matrix. Exemplary photodegradable quenchers include, for example, photodegradable cations, and are preferably also used to prepare strong acid generating compounds, which react with the anions of weak acids (pKa > 1) (e.g., C). 1-20 Carboxylic acid or C 1-20 Those that pair with the anion of sulfonic acid. Exemplary carboxylic acids include formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexanecarboxylic acid, benzoic acid, salicylic acid, etc. Exemplary carboxylic acids include p-toluenesulfonic acid, camphorsulfonic acid, etc. In a preferred embodiment, the photodegradable quencher is a photodegradable organic zwitterionic compound, such as diphenyliodonium-2-carboxylate.

[0224] Photodegradable quenchers can be in non-polymeric or polymerically bonded forms. When in polymeric form, the photodegradable quencher is present in polymeric units on a first or second polymer. Polymeric units containing the photodegradable quencher are typically present in an amount of 0.1 to 30 mol%, preferably 1 to 10 mol%, and more preferably 1 to 2 mol%, based on the total repeating units in the polymer.

[0225] Exemplary basic quenchers include, for example, straight-chain aliphatic amines such as tributylamine, trioctylamine, triisopropanolamine, tetra(2-hydroxypropyl)ethylenediamine, n-tert-butyldiethanolamine, tris(2-acetoxy-ethyl)amine, 2,2',2'',2'''-(ethane-1,2-diylbis(azanetriyl))tetraethanol, 2-(dibutylamino)ethanol, and 2,2',2''-nitrotriethanol; cyclic aliphatic amines, Examples include 1-(tert-butoxycarbonyl)-4-hydroxypiperidine, tert-butyl 1-pyrrolidinecarboxylate, tert-butyl 2-ethyl-1H-imidazolium-1-carboxylate, di-tert-butyl piperazine-1,4-dicarboxylate, and N-(2-acetoxy-ethyl)morpholine; aromatic amines such as pyridine, di-tert-butylpyridine, and pyridinium; linear and cyclic amides and their derivatives, such as N,N-bis(2-hydroxyethyl)palmitamide, N,N-diethylacetamide, and N... 1 N 1 N 3 N 3 -Tetrabutylmalonamide, 1-methylazacycloheptan-2-one, 1-allylazacycloheptan-2-one and tert-butyl 1,3-dihydroxy-2-(hydroxymethyl)propyl-2-ylcarbamate; ammonium salts, such as quaternary ammonium salts of sulfonates, aminosulfonates, carboxylates and phosphonates; imines, such as primary and secondary aldehyde imines and ketimines; diazines, such as optionally substituted pyrazines, piperazines and phenazines; diazoles, such as optionally substituted pyrazoles, thiadiazoles and imidazoles; and optionally substituted pyrrolidones, such as 2-pyrrolidone and cyclohexylpyrrolidine.

[0226] The alkaline quencher can be in non-polymeric or polymeric form. When in polymeric form, the quencher can be present in repeating units of the polymer. The repeating units containing the quencher are typically present in an amount of 0.1 to 30 mol%, preferably 1 to 10 mol%, and more preferably 1 to 2 mol%, based on the total repeating units in the polymer.

[0227] Exemplary surfactants include fluorinated and nonfluorinated surfactants and may be ionic or nonionic, with nonionic surfactants being preferred. Exemplary fluorinated nonionic surfactants include perfluorinated C4 surfactants, such as FC-4430 and FC-4432 surfactants available from 3M Corporation; and fluorinated glycols, such as POLYFOX PF-636, PF-6320, PF-656, and PF-6520 fluorinated surfactants from Omnova. In this aspect, the photoresist composition further comprises a surfactant polymer containing fluorinated repeating units.

[0228] A patterning method using the photoresist composition of the present invention will now be described. Suitable substrates on which the photoresist composition can be coated include electronic device substrates. A wide variety of electronic device substrates can be used in the present invention, such as: semiconductor wafers; polycrystalline silicon substrates; packaging substrates, such as multi-chip modules; flat panel display substrates; substrates for light-emitting diodes (LEDs) including organic light-emitting diodes (OLEDs); etc., wherein semiconductor wafers are typical. Such substrates are typically composed of one or more of silicon, polycrystalline silicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanide, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. Suitable substrates can be in the form of wafers, such as those used for manufacturing integrated circuits, optical sensors, flat panel displays, integrated optical circuits, and LEDs. Such substrates can be of any suitable size. Typical wafer substrate diameters are 200 to 300 millimeters (mm), although wafers with smaller and larger diameters can be suitably used according to the present invention. The substrate may include one or more layers or structures that may optionally include active or operable portions of the formed device.

[0229] Typically, prior to coating the photoresist composition of the present invention, one or more photolithographic layers, such as hard mask layers (e.g., spin-coated carbon (SOC), amorphous carbon, or metal hard mask layers), CVD layers (e.g., silicon nitride (SiN), silicon oxide (SiO), or silicon oxynitride (SiON) layers), organic or inorganic underlayers, or combinations thereof, are provided on the upper surface of the substrate. These layers, together with the externally coated photoresist layer, form a photolithographic material stack.

[0230] Optionally, an adhesion promoter layer may be applied to the substrate surface prior to coating the photoresist composition. If an adhesion promoter is desired, any suitable adhesion promoter for polymer films may be used, such as silanes, typically organosilanes like trimethoxyvinylsilane, triethoxyvinylsilane, hexamethyldisilazane, or aminosilane coupling agents like γ-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those sold from DuPont Electronics & Imaging (Marlborough, Massachusetts) under the names AP 3000, AP 8000, and AP 9000S.

[0231] Photoresist compositions can be coated onto a substrate by any suitable method, including spin coating, spraying, dip coating, blade coating, etc. For example, applying a photoresist layer can be accomplished by spin coating the photoresist in a solvent using a coating track, wherein the photoresist is dispensed onto a rotating wafer. During dispensing, the wafer is typically rotated at speeds up to 4,000 rpm, for example 200 to 3,000 rpm, or for example 1,000 to 2,500 rpm, for a period of 15 to 120 seconds to obtain a photoresist composition layer on the substrate. Those skilled in the art will understand that the thickness of the coated layer can be adjusted by varying the rotation speed and / or the total solids of the composition. Photoresist composition layers formed from the compositions of the present invention typically have a dry layer thickness of 3 to 30 micrometers (µm), preferably greater than 5 to 30 µm, and more preferably 6 to 25 µm.

[0232] Next, the photoresist composition is typically soft-baked to minimize the solvent content in the layer, thereby forming a non-stick coating and improving the layer's adhesion to the substrate. Soft baking is typically performed, for example, on a heated plate or in an oven, with a heated plate being typical. The soft baking temperature and time will depend, for example, on the photoresist composition and thickness. Soft baking temperatures are typically 80°C to 170°C, and more typically 90°C to 150°C. Soft baking times are typically 10 seconds to 20 minutes, more typically 1 minute to 10 minutes, and still more typically 1 minute to 2 minutes. Those skilled in the art can readily determine the heating time based on the composition's components.

[0233] Next, the photoresist layer is patterned and exposed to activating radiation to create a solubility difference between the exposed and unexposed areas. The exposure of the photoresist composition to radiation that activates the composition, as described herein, indicates that radiation can form a latent image in the photoresist composition. Exposure is typically performed using a patterned photomask with optically transparent and optically opaque regions corresponding to the areas of the photoresist layer to be exposed and the areas of the photoresist layer to be unexposed, respectively. Alternatively, this exposure can be performed without a photomask in a direct-write method, typically used in electron beam lithography. The activating radiation typically has a wavelength less than 400 nm, less than 300 nm, or less than 200 nm, with wavelengths of 248 nm (KrF), 193 nm (ArF), 13.5 nm (EUV), or electron beam lithography being preferred. Preferably, the activating radiation is 248 nm radiation. This method can be used in immersion or dry (non-immersion) lithography techniques. The energy exposed is typically 1 to 200 millijoules per square centimeter (mJ / cm²). 2 Preferably 10 to 100 mJ / cm 2And more preferably 20 to 50 mJ / cm 2 It depends on the composition of the exposed tool and the photoresist composition.

[0234] After the photoresist layer is exposed, post-exposure baking (PEB) of the exposed photoresist layer is performed. PEB can be performed, for example, on a heated plate or in an oven, with a heated plate being typical. The conditions of PEB will depend, for example, on the photoresist composition and the layer thickness. PEB is typically performed at a temperature of 70°C to 150°C, preferably 75°C to 120°C, for a time of 30 to 120 seconds. A latent image is formed in the photoresist, defined by polarity-converted regions (exposed regions) and polarity-unconverted regions (unexposed regions).

[0235] The exposed photoresist layer is then developed with a suitable developer to selectively remove areas of the layer that are soluble in the developer while retaining insoluble areas, forming the resulting photoresist pattern relief image. In the case of a positive development (PTD) process, the exposed areas of the photoresist layer are removed during development, while the unexposed areas are retained. Conversely, in a negative development (NTD) process, the exposed areas of the photoresist layer are retained during development, while the unexposed areas are removed. The application of the developer can be accomplished by any suitable method, as described above regarding the application of the photoresist composition, with spin coating being typical. The development time is the period of time during which the soluble areas of the photoresist are effectively removed, typically 5 to 60 seconds. Development is typically performed at room temperature.

[0236] Suitable developers for PTD processes include aqueous alkaline developers, such as quaternary ammonium hydroxide solutions, such as tetramethylammonium hydroxide (TMAH) (preferably 0.26 standard (N) TMAH), tetraethylammonium hydroxide, tetrabutylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. Suitable developers for NTD processes are based on organic solvents, meaning that the cumulative content of organic solvents in the developer is 50 wt% or more, typically 95 wt% or more, 98 wt% or more, or 100 wt% based on the total weight of the developer. Suitable organic solvents for NTD developers include, for example, those selected from ketones, esters, ethers, hydrocarbons, and mixtures thereof. Typical developers are 2-heptanone or n-butyl acetate.

[0237] The coated substrate can be formed from the photoresist composition of the present invention. Such a coated substrate comprises: (a) a substrate having one or more layers to be patterned on its surface; and (b) a photoresist composition layer on the one or more layers to be patterned.

[0238] Photoresist patterns can be used, for example, as an etching mask to transfer the pattern to one or more sequentially arranged underlying layers using known etching techniques, typically dry etching (such as reactive ion etching). Photoresist patterns can also be used, for example, to transfer a pattern to an underlying hard mask layer, which in turn serves as an etching mask for transferring the pattern to one or more layers below the hard mask layer. If the photoresist pattern is not lost during pattern transfer, it can be removed from the substrate using known techniques such as oxygen plasma ashing. When used in one or more such patterning processes, photoresist compositions can be used to manufacture semiconductor devices such as memory devices, processor chips (CPUs), graphics chips, optoelectronic chips, LEDs, OLEDs, and other electronic devices.

[0239] The invention is further illustrated by the following examples.

[0240] Example

[0241] Example 1 and Comparison Example 1

[0242] The photoresist compositions of Example 1 and Comparative Example 1 were prepared by combining the components shown in Table 1, wherein the amounts are expressed as a weight percentage (wt%) based on 100 wt% of the total non-solvent components of the photoresist composition (i.e., 100 wt% of the total solids). The photoresist compositions were prepared in a solvent mixture of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and γ-butyrolactone (gBL) in a weight ratio of 75:20:5.

[0243] Table 1

[0244]

[0245] The additive (A1) is γ-methyldecyl lactone. The surfactant (SLA) is POLYFOX PF-656 (Omnova Solutions Inc.).

[0246] Polymer (P1) has the following structure:

[0247]

[0248] Based on a total repeating unit of 100 mol%, a is 64.2 mol%, b is 5.1 mol%, c is 24.3 mol%, and d is 24.3 mol%. Polymer 1 has an M of 21 kDa. w And PDI of 1.69.

[0249] The structures of the photoacid generator (PAG1), quencher (Q1), and quencher (Q2) are as follows:

[0250] PAG1 Q1 Q2

[0251] Photosensitivity. KrF contrast and photolithography evaluation were performed on a 200 mm silicon wafer using a TEL Mark 8 track (Tokyo Electron). The silicon wafer was undercoated with HMDS (125°C for 60 seconds) and then spin-coated with the photoresist composition of Example 1 or Comparative Example 1. The coated wafer was baked at 150°C for 200 seconds to provide a photoresist layer with a film thickness of approximately 15 µm. The photoresist-coated wafer was then exposed to KrF radiation (248 nm) using an ASML 300 KrF stepper with a numerical aperture of 0.6 NA / 0.65σ and without a mask. The exposed wafer was then baked at 110°C for 120 seconds and developed with a 0.26 N tetramethylammonium hydroxide (TMAH) solution (DuPont Electronics & Imaging) for 120 seconds to form a resist pattern. Different exposure doses (mJ / cm²) were measured using the F50-UVX film mapping system (Filmetrics). 2 The remaining photoresist layer thickness (µm) under the exposure dose was determined. The data were evaluated by plotting the remaining film thickness as a function of exposure dose to obtain a KrF positive tone contrast profile. The contrast profile was used to determine the removal dose (E0), which is the minimum dose required to completely remove the film.

[0252] The E0 value for each preparation is shown in Table 2.

[0253] Table 2

[0254]

[0255] As demonstrated by the data shown in Table 2, the additives of the present invention increased the E0 clearance dose of the photoresist composition of Example 1. Therefore, Example 1 of the present invention achieved a faster photosensitivity compared to the photosensitivity when using Comparative Example 1.

[0256] Layering. A 200 mm silicon wafer was primed with HMDS (125°C for 60 seconds) and spin-coated with the photoresist composition of Example 1 or Comparative Example 1. The wafer was baked at 150°C for 200 seconds to provide a film with a thickness of 15 µm. The photoresist-coated wafer was then exposed to 248 nm radiation using an ES4 stepper lithography machine (Canon) with a binary mask using 0.6 NA / 0.65σ. The exposed wafer was baked at 110°C for 120 seconds and then developed with 0.26 N TMAH solution for 120 seconds. Cross-sectional images of the isolated line patterns were obtained using an AMRAY4200 scanning electron microscope (KLA-Tencor) operating at 15 kV. The top-down images show that the γ-methyl-decanolide additive of Example 1 improved the adhesion of the thick photoresist used for KrF patterning.

[0257] Example 2 and Comparison Example 2

[0258] The photoresist compositions of Example 2 and Comparative Example 2 were prepared by combining the components shown in Table 3, wherein the amounts are expressed as weight percentages (wt%) based on 100 wt% of the total non-solvent components of the photoresist composition (i.e., 100 wt% of the total solids). The photoresist compositions were prepared in a solvent mixture of PGMEA and PGME in a weight ratio of 60:40.

[0259] Table 3

[0260]

[0261] The structures of P1, PAG1, Q1, Q2, and SLA are the same as those defined above.

[0262] Additives (A2) and (A3) have the following structures:

[0263] A2

[0264] Light sensitivity evaluation. The KrF contrast and lithography evaluation of Example 2 and Comparative Example 2 were performed as described in Example 1 and Comparative Example 1 above.

[0265] These experiments revealed that the E0 clearance dose in Example 2 was 14 mJ / cm³. 2 The E0 clearance dose in Comparative Example 2 was 20 mJ / cm³. 2 As demonstrated by the data, the substituted lactone additive having formula A3 improved the photosensitivity of the photoresist composition of Example 2.

[0266] While this disclosure has been described in conjunction with exemplary embodiments now considered to be practical, it should be understood that the invention is not limited to the disclosed embodiments, but rather is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A photoresist composition comprising: polymer; Photoacid generator; Additives with the following chemical formulas (1a) or (1b); and Solvent, (1a) (1b), in, In chemical formulas (1a) and (1b), R 1 and R 2 Each is a substituted or unsubstituted C independently. 1-3 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 3-20 Mixed aromatics; R 1 and R 2 Each of these may optionally further include, as part of their structure, one or more groups selected from the group consisting of: -O-, -C(O)-, -S-, -S(O)2-, and -N(R-). 1a )-, where R 1a It is hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 3-20 Heterocyclic alkyl groups; R 3a R 3b R 4a R 4b R 5a and R 5b Each is independently a hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 3-20 heteroaryl, of which C 1-20 Heteroalkyl and C 3-20 Each heterocyclic alkyl group independently has a heteroatom selected from O, S, Si, P, or combinations thereof; and wherein the substituted C atoms... 1-20 Alkyl groups are substituted with the following groups: nitro, cyano, hydroxyl, carboxylic acid or its alkali metal or ammonium salt, halogen, mercapto, C 1-6 Alkylthio, C 1-6 Alkyl, C 2-6 alkenyl, C 2-6 alkynyl group, C 1-6 Haloalkyl, C 1-9 Alkoxy, C 1-6 Halogenated alkoxy groups, C 3-12 cycloalkyl, C 5-18 Cycloalkenyl, C 2-18 Heterocyclic alkenyl, C 6-12 Aryl, C 7-19 Arylalkyl, C 7-12 alkylaryl, C 3-12 Heterocyclic alkyl, C 3-12 heteroaryl groups or combinations thereof; R 1 and R 2 Together, they can optionally form a ring via single or divalent linking groups; and R 3a R 3b R 4a R 4b R 5a and / or R 5b Any two or more of them may optionally be linked together by a single bond or a divalent linker to form a cyclic group, wherein the cyclic group is monocyclic, non-fused polycyclic, or fused polycyclic.

2. The photoresist composition as claimed in claim 1, wherein, The additive has a boiling point of 200°C or higher.

3. The photoresist composition as described in claim 1, wherein, The polymer comprises an acid-labile repeating unit of a monomer represented by one or more of the derivatives of formulas (2), (3), (4), (5), or (6): (2) (3) (4) (5) (6) In equations (2) to (6), R a To R c Each is independently a hydrogen, fluorine, cyano group, or a substituted or unsubstituted C group. 1-10 alkyl; L 1 It is a divalent linker group; R 6 To R 11 Each is independently a hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 3-20 Cycloalkenyl, substituted or unsubstituted C 3-20 Heterocyclic alkenyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 3-20 heteroaryl, of which R 6 To R 11 Each of them optionally further includes a divalent linker group as part of its structure; The premise is R 6 To R 8 No more than one of them is hydrogen, and this is on the premise that R 6 To R 8 When one of them is hydrogen, R 6 To R 8 At least one of the other Cs is either substituted or unsubstituted. 6-20 aryl or substituted or unsubstituted C 3-20 heteroaryl; and the premise is R 9 To R 11 No more than one of them is hydrogen, and this is on the premise that R 9 To R 11 When one of them is hydrogen, R 9 To R 11 At least one of the other Cs is either substituted or unsubstituted. 6-20 aryl or substituted or unsubstituted C 3-20 Mixed aromatics; R 6 To R 8 Any two of them may optionally form a ring together, wherein the ring may optionally further include a divalent linking group as part of its structure, and wherein the ring may be substituted or unsubstituted; R 9 To R 11 Any two of them may optionally form a ring together, wherein the ring may optionally further include a divalent linking group as part of its structure, and wherein the ring may be substituted or unsubstituted; R 12 R 13 R 18 and R 19 Each is independently a hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 3-20 heteroaryl, of which R 12 R 13 R 18 and R 19 Each of them optionally further includes a divalent linker group as part of its structure; R 14 Is it substituted or unsubstituted C? 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 3-20 Heterocyclic alkyl groups, wherein R 14 Optionally, it may further include a divalent linker group as part of its structure; R 12 To R 14 Any two of them may optionally form a ring together, wherein the ring may optionally further include a divalent linking group as part of its structure, and wherein the ring may be substituted or unsubstituted; R 15 To R 17 Each is a substituted or unsubstituted C independently. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 3-20 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 3-20 heteroaryl, of which R 15 To R 17 Each of them optionally further includes a divalent linker group as part of its structure; The premise is R 15 To R 17 No more than one of them is hydrogen, and this is on the premise that R 15 To R 17 When one of them is hydrogen, R 15 To R 17 At least one of the other Cs is either substituted or unsubstituted. 6-20 aryl or substituted or unsubstituted C 3-20 Mixed aromatics; R 15 To R 17 Any two of them may optionally form a ring together, wherein the ring may optionally further include a divalent linking group as part of its structure, and wherein the ring may be substituted or unsubstituted; R 20 Is it substituted or unsubstituted C? 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 3-20 Heterocyclic alkyl groups, wherein R 20 Optionally, it may further include a divalent linker group as part of its structure; R 18 To R 20 Any two of them may optionally form a ring together, wherein the ring may optionally further include a divalent linking group as part of its structure, and wherein the ring may be substituted or unsubstituted; X a and X b Each is independently a polymerizable group selected from norbornel or vinyl groups; n1 and n2 are each independently 0 or 1; and L 2 and L 3 Each is an independent single-bonded or divalent linker, provided that X is a single bond or a divalent linker. a When it is vinyl, L 2 It is not a single bond, and its premise is that X b When it is vinyl, L 3 It's not a single key.

4. The photoresist composition of claim 1, wherein, The polymer comprises repeating units derived from one or more monomers having formula (7) or (8). (7) (8) In equations (7) and (8), R d and R f Each is independently a hydrogen, fluorine, cyano group, or a substituted or unsubstituted C group. 1-10 alkyl; L 4 and L 6 Each is independently a single bond or a divalent linker; L 5 It is a divalent linker group; q is 0 or 1; R 22 It is an organic group comprising one or more heteroatoms, whether substituted or unsubstituted; and R 23 It is C with or without substitution. 4-20 The lactone group may contain substituted or unsubstituted C groups. 4-20 The group of sulfonyl lactone.

5. The photoresist composition of claim 1, wherein, The polymer comprises repeating units containing a photoacid generator. The photoacid generator is a non-polymer compound, or The polymer comprises repeating units containing a first photoacid generator and a second photoacid generator, wherein the second photoacid generator is a non-polymeric compound.

6. The photoresist composition of claim 1, further comprising: a photodegradable quencher or an alkaline quencher.

7. A method for forming a pattern, the method comprising: A layer of the photoresist composition as described in any one of claims 1 to 6 is applied to a substrate to provide a photoresist composition layer; The photoresist composition layer is patterned and exposed to activated radiation to provide an exposed photoresist composition layer; as well as The exposed photoresist composition layer is developed to provide the pattern.

8. The method of claim 7, wherein, The activation radiation has a wavelength of 248 nm.

9. The method of claim 7, wherein, The photoresist composition layer has a thickness greater than 5 micrometers.

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