Photoresist compositions and pattern formation methods

Abstract

To provide photoresist compositions and pattern formation methods.SOLUTION: A photoresist composition comprises a polymer, a photoacid generator, an additive comprising a tertiary carbon atom as a ring-forming atom of a lactone ring, and a solvent.SELECTED DRAWING: None

Description

[Technical field]

[0001] PHOTORESIST COMPOSITIONS AND PATTERNING METHODS USING SUCH PHOTORESIST COMPOSITIONS FIELD OF THEINVENTION The present invention relates to photoresist compositions and patterning methods using such photoresist compositions.The present invention finds particular applicability in lithography applications in the semiconductor manufacturing industry. [Background technology]

[0002] Photoresist materials are photosensitive compositions typically used to transfer images to one or more underlying layers, such as metal, semiconductor, or dielectric layers, disposed on a semiconductor substrate. To increase the integration density of semiconductor devices and enable the formation of structures having dimensions in the nanometer range, photoresists and photolithography processing tools with high resolution capabilities have been developed.

[0003] Current lithography techniques often do not allow for further scaling of critical dimensions at low manufacturing costs. For example, NAND flash manufacturers are looking at stacking multiple layers of memory cells to achieve higher storage capacity while maintaining a low manufacturing cost per bit. By shrinking critical features while maintaining low manufacturing costs, stacked 3D structures have been developed for NAND applications. These 3D NAND devices are denser, faster, and cheaper than traditional 2D planar NAND devices. 3D NAND architectures include vertical channel and vertical gate architectures, where step structures (known as "stairs") are used to form electrical connections between memory cells and bitlines or wordlines. When building 3D NAND flash memory, manufacturers increase the number of steps by using thicker resists that allow for multiple trim and etch cycles used to form the steps. As subsequent trim-etch variations in critical dimensions (CDs) are deposited across the wafer in stages, maintaining a good feature profile at each step is a challenge.

[0004] The process of "step" formation, which uses a single mask exposure of a thick KrF photoresist to form several sets of steps, is considered a relatively cost-effective approach. However, the use of thick films in KrF lithography to print micrometer-scale features comes with inherent technical challenges. Patterning a thick resist film requires sufficient film transparency at the exposure wavelength to allow the incident radiation to reach the bottom of the film. Furthermore, thick resist films used in 3D NAND applications are subjected to multiple resist thickness trim and dry etch cycles. Exposing a thick resist film to trim and etch processes can affect the uniformity of the film structure, resulting in rough film surfaces and unwanted voids within the film. A suitable thick resist film must be capable of maintaining the film's physical structure after each trim and etch process.

[0005] Thus, there is a continuing need for chemical compositions that can be suitable for thick photoresists with good transparency at the exposure wavelength, excellent retention of properties after thickness trimming and etching, and improved adhesion at the substrate-photoresist interface. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] U.S. Patent No. 8,431,325 [Patent Document 2] U.S. Pat. No. 4,189,323 Summary of the Invention [Means for solving the problem]

[0007] A photoresist composition is provided that includes a polymer, a photoacid generator, an additive that includes a tertiary carbon atom as a ring-forming atom of a lactone ring, and a solvent.

[0008] Also provided is a method of forming a pattern that includes applying a layer of a photoresist composition of the invention to a substrate to provide a photoresist composition layer, patternwise exposing the photoresist composition layer to activating radiation to provide an exposed photoresist composition layer, and developing the exposed photoresist composition layer to provide a pattern. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Reference will now be made in detail to the exemplary embodiments, examples of which are set forth herein. In this regard, the exemplary embodiments may have different forms and should not be construed as being limited to the description set forth herein. Thus, the exemplary embodiments are described below simply by referring to the figures to illustrate aspects of the present description. As used herein, the term "and / or" encompasses any and all combinations of one or more of the associated listed items. A phrase such as "at least one of," when preceding a list of elements, modifies the entire list of elements and does not modify each individual element of the list.

[0010] As used herein, the terms "a," "an," and "the" do not denote quantity limitations and should be construed to include both the singular and the plural unless otherwise indicated herein or clearly contradicted by context. "Or" means "and / or" unless otherwise indicated. The modifier "about," used in connection with a quantity, is inclusive of the stated value and has the meaning dictated by the context (e.g., including the degree of error associated with measurement of the particular quantity). All ranges disclosed herein are inclusive of the endpoints, and the endpoints are combinable independently of each other. The suffix "(s)" is intended to include both the singular and the plural of the term it modifies, thereby including at least one of that term. "Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances when the event occurs and instances when the event does not occur. The terms "first," "second," etc., as used herein do not denote an order, quantity, or importance, but rather 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 the other element, or intervening elements may be present therebetween. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present. It will be understood that the described components, elements, limitations, and / or features of the embodiments may be combined in any suitable manner in the various embodiments.

[0011] Unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as commonly understood by those skilled in the art to which the present invention belongs. Terms as defined in commonly used dictionaries should be interpreted to have a meaning consistent with their meaning in the context of the relevant technical field and this disclosure, and will be further understood not to be interpreted in an idealized or overly formal sense unless expressly defined in this specification.

[0012] As used herein, "actinic rays" or "radiation" refers to, for example, the emission spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, particle rays such as electron beams and ion beams, etc. Furthermore, in the present invention, "light" refers to actinic rays or radiation.

[0013] Krypton Fluoride Lasers (KrF lasers) are a specific type of excimer laser, sometimes called an exciplex laser. "Excimer" stands for "excimer dimer", while "exciplex" stands for "exciplex". Excimer lasers use a mixture of rare gases (argon, krypton, or xenon) and halogen gases (fluorine or chlorine) to emit coherent stimulated radiation (laser light) in the ultraviolet range under the right conditions of electrical stimulation and high voltage.

[0014] Furthermore, unless otherwise specified, "exposure" in this specification includes not only exposure to far ultraviolet light such as that provided by a mercury lamp or an excimer laser, X-rays, extreme ultraviolet light (EUV light), and the like, but also writing using particle beams such as electron beams and ion beams.

[0015] As used herein, the term "hydrocarbon" refers to an organic compound or group having at least one carbon atom and at least one hydrogen atom; "alkyl" refers to a straight or branched chain saturated hydrocarbon having the specified number of carbon atoms and a valence of one; "alkylene" refers to an alkyl group having a valence of two; "hydroxyalkyl" refers to an alkyl group substituted with at least one hydroxyl group (-OH); "alkoxy" refers to "alkyl-O-"; "carbonyl" and "carboxylic acid group" 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 two; "alkenyl" refers to a straight or branched chain monovalent hydrocarbon group having at least one carbon-carbon double bond; "alkenoxy" refers to "alkenyl-O-"; "alkenylene" refers to an alkenyl group having a valence of two; "cycloa "Alkenyl" refers to a non-aromatic cyclic divalent hydrocarbon group having at least three carbon atoms, including 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 contains carbon atoms in the ring, and optionally contains one or more heteroatoms selected from N, O, and S in place of carbons in the ring; "aryl" refers to a monovalent aromatic monocyclic or polycyclic ring system, which may contain groups whose ring members are all carbon and have an aromatic ring fused to at least one cycloalkyl or heterocycloalkyl ring; "arylene" refers to an aryl group having a valence of two; "alkylaryl" refers to an aryl group substituted with an alkyl group; "arylalkyl" refers to an alkyl group substituted with an aryl group; "aryloxy" refers to "aryl-O-"; and "arylthio" refers to "aryl-S-".

[0016] The prefix "hetero" means that the compound or group contains at least one component that is a heteroatom (e.g., 1, 2, 3, or more heteroatoms) in place of a carbon atom, where the heteroatoms are each independently N, O, S, Si, or P; "heteroatom-containing group" refers to a substituent that contains at least one heteroatom; "heteroalkyl" refers to an alkyl group having at least one heteroatom in place of carbon; "heterocycloalkyl" refers to a cycloalkyl group having at least one heteroatom as a ring member in place of carbon; and "heterocycloalkylene" refers to a divalent heterocycloalkyl group.

[0017] The term "heteroaryl" refers to an aromatic 4-8 membered monocyclic ring system, 8-12 membered bicyclic ring system, or 11-14 membered tricyclic ring system having 1-4 heteroatoms (in the case of a monocyclic ring), 1-6 heteroatoms (in the case of a bicyclic ring), or 1-9 heteroatoms (in the case of a tricyclic ring) each independently selected from N, O, S, Si, or P (e.g., carbon atoms and 1-3, 1-6, or 1-9 heteroatoms of N, O, or S in the case of a monocyclic, bicyclic, or tricyclic ring, respectively). Examples of heteroaryl groups include pyridyl, furyl (furyl or furanyl), imidazolyl, benzimidazolyl, pyrimidinyl, thiophenyl or thienyl, quinolinyl, indolyl, thiazolyl, and the like.

[0018] The term "halogen" refers to a monovalent substituent that is fluorine (fluoro), chlorine (chloro), bromine (bromo), or iodine (iodo). The prefix "halo" refers to a group that contains one or more of fluoro, chloro, bromo, or iodo substituents in place of a hydrogen atom. Combinations of halo groups (e.g., bromo and fluoro) or only fluoro groups may be present. For example, the term "haloalkyl" refers to an alkyl group substituted with at least one halogen. As used herein, "substituted C 1~8 "Haloalkyl" refers to a C alkyl group substituted with at least one halogen and further substituted with one or more other substituents that are not halogens. 1~8It refers to an alkyl group. It is understood that substitution of a group with a halogen atom should not be considered a heteroatom-containing group since the halogen atom does not replace a carbon atom.

[0019] "Fluorinated" shall be understood to mean having one or more fluorine atoms incorporated into the group. For example, C 1~18 When a fluoroalkyl group is indicated, the fluoroalkyl group can contain one or more fluorine atoms, for example, a single fluorine atom, two fluorine atoms (such as, for example, a 1,1-difluoroethyl group), three fluorine atoms (such as, for example, a 2,2,2-trifluoroethyl group), or a fluorine atom at each free valence of a carbon (such as, for example, a perfluoro group such as -CF3, -C2F5, -C3F7, or -C4F9). A "substituted fluoroalkyl group" shall be understood to mean a fluoroalkyl group that is further substituted by additional substituents that do not contain fluorine atoms.

[0020] Where appropriate, and unless expressly stated otherwise, each of the foregoing substituents may be optionally substituted. The term "optionally substituted" refers to substituted or unsubstituted. "Substituted" means that at least one hydrogen atom of the chemical structure is replaced with another terminal substituent, typically monovalent, provided that the normal valence of the designated atom is not exceeded. When a substituent is oxo (i.e., O), two geminal hydrogen atoms on a carbon atom are replaced by terminal oxo groups. Combinations of substituents or variables are permitted. Exemplary substituents that may be present at a "substituted" position include nitro (-NO2), cyano (-CN), hydroxy (-OH), oxo (O), amino (-NH2), mono- or di-(C 1~6 ) alkylamino, alkanoyl (e.g., acyl, etc. 2~6 alkanoyl group), formyl (-C(O)H), carboxylic acid or its alkali metal salt or ammonium salt;C 2~6 Alkyl esters (-C(O)O-alkyl or -OC(O)-alkyl) and C 7~13Esters (including acrylates, methacrylates, and lactones), such as aryl esters (-C(O)O-aryl or -OC(O)-aryl); amides (-C(O)NR, where R is hydrogen or C 1~6 alkyl), carboxamide (-CHC(O)NR, where R is hydrogen or C 1~6 Alkyl), halogen, thiol (-SH), C 1~6 Alkylthio (-S-alkyl), thiocyano (-SCN), C 1~6 Alkyl, C 2~6 Alkenyl, C 2~6 Alkynyl, C 1~6 Haloalkyl, C 1~9 Alkoxy, C 1~6 Haloalkoxy, C 3~12 Cycloalkyl, C 5~18 Cycloalkenyl, C 2~18 Heterocycloalkenyl, C having at least one aromatic ring 6~12 Aryl (e.g., phenyl, biphenyl, naphthyl, etc., where each ring is either substituted or unsubstituted aromatic) C having 1-3 separate or fused rings and 6-18 ring carbon atoms 7~19 Arylalkyl, arylalkoxy having 1-3 separate or fused rings and 6-18 ring carbon atoms, C 7~12 Alkylaryl, C 3~12 Heterocycloalkyl, C 3~12 Heteroaryl, C 1~6 Alkylsulfonyl (-S(O)2-alkyl), C 6~12 Examples of such radicals include, but are not limited to, arylsulfonyl (-S(O)2-aryl), or tosyl (CH3C6H4SO2-). If a group is substituted, the number of carbon atoms indicated is the total number of carbon atoms in the group, excluding the carbon atoms of any substituents. For example, the group -CH2CH2CN is a cyano-substituted C2 alkyl group.

[0021] As used herein, "acid labile group" refers to a group that is formed on a polymer and that can be cleaved by acid catalysis, optionally and typically with thermal treatment, resulting in the formation of a polar group, such as a carboxylic acid group or an alcohol group, on the polymer, and optionally and typically the moiety connected to the cleaved bond is cleaved. In other systems, the non-polymeric compound can include an acid labile group that can be cleaved by acid catalysis, resulting in the formation of a polar group, such as a carboxylic acid group or an alcohol group, on the cleaved moiety of the non-polymeric compound. Such acids are typically photogenerated acids that cause bond cleavage during post-exposure bake (PEB), however, embodiments are not limited thereto, for example, such acids can be thermally generated. Suitable acid labile groups include, for example, tertiary alkyl ester groups, secondary or tertiary aryl ester groups, secondary or tertiary ester groups with a combination of alkyl and aryl groups, tertiary alkoxy groups, acetal groups, or ketal groups. Acid labile groups are also commonly referred to in the art as "acid cleavable groups", "acid cleavable protecting groups", "acid labile protecting groups", "acid leaving groups", "acid cleavable groups", and "acid sensitive groups".

[0022] As used herein, unless otherwise defined, a "divalent linking group" is any of -O-, -S-, -Te-, -Se-, -C(O)-, -N(R 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 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 heteroarylene, heteroaryl, or a combination thereof, a 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 3~30Typically, the divalent linking group is -O-, -S-, -C(O)-, -N(R a )-, -S(O)-, -S(O)2-, substituted or unsubstituted C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 heteroarylene, heteroarylene, or combinations thereof, wherein R a 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 More typically, the divalent linking group is -O-, -C(O)-, -C(O)O-, -N(R a )-, -C(O)N(R a )-, substituted or unsubstituted C 1~10 Alkylene, substituted or unsubstituted C 3~10 Cycloalkylene, substituted or unsubstituted C 3~10 Heterocycloalkylene, substituted or unsubstituted C 6~10 Arylene, substituted or unsubstituted C 3~10 heteroarylene, or a combination thereof, wherein R a is hydrogen, substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C 1~10 Heteroalkyl, substituted or unsubstituted C 6~10 Aryl, or substituted or unsubstituted C 3~10 It is heteroaryl.

[0023] The thick film ("thick film photoresist") derived from the photoresist composition can be used as an etch mask to generate surface features such as staircase structure patterns for manufacturing 3D NAND electronic devices. The patterning methods used to create 3D NAND electronic devices typically require thick photoresist films having a thickness of 5 micrometers or more for use with 248 nm radiation exposure. As the photoresist film thickness increases, it suffers from the problem that the photospeed of the photoresist may be insufficient and the transmittance of 248 nm light may decrease. Furthermore, as the film thickness increases, the adhesion of the photoresist film to the substrate at the photoresist-substrate interface decreases, which may be caused by increased film stress.

[0024] The present invention relates to a photoresist composition comprising a polymer; a photoacid generator (PAG), an additive comprising a tertiary carbon atom as an atom forming a ring of a lactone ring, a solvent, and may further comprise optional components.The inventors have found that the specific photoresist composition of the present invention can be used to prepare photoresist films having improved lithographic properties, such as increased photospeed, improved adhesion at the photoresist-substrate interface, and reduced peeling from the substrate surface.

[0025] Lactone rings containing tertiary carbon atoms as ring-forming atoms of the lactone ring can undergo a ring-opening reaction to form alkenyl carboxylic acids in the presence of strong acid catalysts, such as heat or photogenerated acid. The resulting alkenyl carboxylic acids have improved solubility in basic developers compared to additives that do not undergo ring-opening reactions. The improved solubility can increase the dissolution rate of thick films derived from the photoresist composition of the present invention in basic developers, thereby resulting in fast photospeed.

[0026] Without being bound by theory, the additive may function as a plasticizer in the photoresist composition of the present invention. This is because the thick film obtained from the photoresist composition of the present invention contains a plasticizer, and subsequently the generated acid (e.g., photoacid) diffuses quickly into the film, thereby increasing the photospeed. Furthermore, when the additive plasticizes the film derived from the photoresist composition of the present invention, the resulting thick film has a lower stress, which reduces the amount of film peeling.

[0027] The additive to the photoresist composition of the present invention is a compound represented by the formula (1): [ka] In the formula, m is an integer of 1 to 5, typically 1 to 3, and preferably 1 or 2.

[0028] In formula (I), R 1 and R 2 are each independently 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 Heterocycloalkyl, substituted or unsubstituted C 6~20 Aryl, or substituted or unsubstituted C 3~20 Heteroaryl. Substituted or unsubstituted C 1~20 Alkyl groups and substituted or unsubstituted C 1~20 Each heteroalkyl group may be linear or branched. 3~20 Cycloalkyl groups, substituted or unsubstituted C 3~20 Heterocycloalkyl group, substituted or unsubstituted C 6~20 Aryl groups, and substituted or unsubstituted C 3~20 Each heteroaryl group may be monocyclic or polycyclic. In some embodiments, R 1 and R 2 each independently represents a substituted or unsubstituted C 1~6 Alkyl, preferably substituted or unsubstituted C1~3 Alkyl, and more preferably unsubstituted C 1~3 Alkyl, typically methyl. R 1 and R 2 Each of the groups may include, as part of their structure, -O-, -C(O)-, -S-, -S(O)2-, and -N(R 1a )-, wherein R 1a is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 3~20 It is a heterocycloalkyl.

[0029] In formula (1), each R 3 are independently 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 Heterocycloalkyl, substituted or unsubstituted C 6~20 Aryl, or substituted or unsubstituted C 3~20 Heteroaryl may be substituted or unsubstituted C 1~20 Alkyl and substituted or unsubstituted C 1~20 Heteroalkyl may be linear or branched. 3~20 Cycloalkyl, substituted or unsubstituted C 3~20 Heterocycloalkyl, substituted or unsubstituted C 6~20 Aryl, or substituted or unsubstituted C 3~20 Heteroaryl may be monocyclic or polycyclic. Each R 3 has -O-, -C(O)-, -S-, -S(O)2-, and -N(R 2a )-, wherein R 2a is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 3~20In some embodiments, each R 3 are independently substituted or unsubstituted C 1~6 Alkyl, preferably substituted or unsubstituted C 1~3 Alkyl, and more preferably unsubstituted C 1~3 It may be an alkyl, typically methyl.

[0030] In formula (1), R 1 , R 2 , or R 3 Any two of the groups R may be taken together, optionally via a single bond or a divalent linking group, to form a ring. In some embodiments, when n is 2 or greater, any two groups R 3 may together optionally form a ring via a divalent linking group.

[0031] In formula (1), n ​​is an integer of 0 to 2 (m+1). For example, n may be an integer of 0 to 12, typically 0 to 6, and preferably 0 to 4. The group R 3 It is understood that when is not present at a given position on the lactone ring of formula (1), a hydrogen atom is present.

[0032] In some embodiments, the additive has formula (1a) or (1b): [ka] The compound may be represented by one or more of the following:

[0033] In formulas (1a) and (1b), R 1 and R 2 is the same as defined in equation (1).

[0034] In formula (1a), R 3a , R 3b , R 4a , and R 4b are each independently hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 1~20 Heteroalkyl, substituted or unsubstituted C3~20 Cycloalkyl, substituted or unsubstituted C 3~20 Heterocycloalkyl, substituted or unsubstituted C 6~20 Aryl, or substituted or unsubstituted C 3~20 In some embodiments, R 3a , R 3b , R 4a , and R 4b In one embodiment, at least one of R 4a and R 4b At least one of the groups may be substituted or unsubstituted C 1~20 Alkyl and substituted C 1~20 Alkyl is -O-, -C(O)-, -N(R 1c )-, -S-, -S(O)2-, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted divalent C 7~30 Aryl alkyl, substituted or unsubstituted C 3~30 Heteroarylene, or substituted or unsubstituted divalent C 4~30 Heteroarylalkyl, wherein R 1c is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 3~20 It is a heterocycloalkyl.

[0035] In formula (1a), R 3a , R 3b , R 4a , and / or R 4b Any two or more of may be taken together, optionally via a single bond or a divalent linking group, to form a cyclic group, which is monocyclic, non-fused polycyclic, or fused polycyclic.

[0036] In formula (1b), R 3a , R 3b , R 4a , R 4b , R 5a , and R5b are each 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 Heterocycloalkyl, substituted or unsubstituted C 6~20 Aryl, or substituted or unsubstituted C 3~20 In some embodiments, R 3a , R 3b , R 4a , R 4b , R 5a , and R 5b In another embodiment, at least one of R 3a , R 3b , R 5a , and R 5b In one embodiment, at least one of R 5a and R 5b At least one of the groups may be substituted or unsubstituted C 1~20 Alkyl and substituted C 1~20 Alkyl is -O-, -C(O)-, -N(R 1d )-, -S-, -S(O)2-, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted divalent C 7~30 Aryl alkyl, substituted or unsubstituted C 3~30 Heteroarylene, or substituted or unsubstituted divalent C 3~30 Heteroarylalkyl, wherein R 1d is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 3~20 It is a heterocycloalkyl.

[0037] In formula (1b), R 3a , R 3b , R 4a , R4b , R 5a , and / or R 5b Any two or more of may be taken together, optionally via a single bond or a divalent linking group, to form a cyclic group, which is monocyclic, non-fused polycyclic, or fused polycyclic.

[0038] Exemplary additives include those having the formula: [ka] In the formula, R 4a is as defined in formula (1a), and R 1a , R 1b , R 2a , R 2b , R 4c , R 4d , and R n are each 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 Heterocycloalkyl, substituted or unsubstituted C 6~20 Aryl, or substituted or unsubstituted C 3~20 Heteroaryl. R 3aa , R 3bb , and / or R 4a Any two or more of may be taken together, optionally via a single bond or a divalent linking group, to form a ring group, which is monocyclic, non-fused polycyclic, or fused polycyclic. 3aa , R 3bb , and / or R 4aa Any two or more of may be taken together, optionally via a single bond or a divalent linking group, to form a cyclic group, which is monocyclic, non-fused polycyclic, or fused polycyclic.

[0039] Particularly useful additives include the following compounds: [ka] These may include, but are not limited to, one or more of:

[0040] In some embodiments, the additive may have a boiling point of 200° C. or higher, for example, when measured at ambient or atmospheric pressure. As used herein, "ambient pressure" is about 1 atmosphere. For example, the additive may have a boiling point of 200° C. to 260° C. at ambient pressure.

[0041] The additives are typically present in the photoresist composition in an amount of from 1 to 40 weight percent, typically from 5 to 35 weight percent, more typically from 10 to 30 weight percent, based on the total solids content of the photoresist composition, it being understood that "total solids" includes the polymer, PAG, additives, and other non-solvent components.

[0042] The additives of the present invention may be prepared using any method in the art or may be commercially available. For example, the additives may 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-furan carboxylic acid (terephthalic acid), 2-carboxytetrahydro-5-oxo-2-furan acetic 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)-valeric acid gamma lactone, camphanic acid, or 1-oxa-8-azaspiro(4.5)decan-2-one.

[0043] The photoresist composition includes a polymer. In some embodiments, the polymer may include repeat units that include an acid labile group, which can be cleaved by photogenerated acid during post-exposure bake conditions. The polymer of the photoresist composition may be represented by formula (2), (3), (4), (5), or (6): [ka] The compound may include acid labile repeat units derived from monomers represented by one or more of:

[0044] In formulas (2), (3), and (4), R a , R b , and R c are each independently hydrogen, fluorine, cyano, or substituted or unsubstituted C 1~10 Preferably, R a , R b , and R c are each independently hydrogen, fluorine, or substituted or unsubstituted C 1~5 It may be an alkyl, typically methyl.

[0045] In formula (2), L 1 is a divalent linking group. For example, L 1 may contain 1 to 10 carbon atoms and at least one heteroatom. 1 is -OCH2-, -OCH2CH2O-, or -N(R 2a )-, where R 2a is hydrogen or C 1~6 It is an alkyl.

[0046] In formulas (2) and (3), R 6 ~R 11 are each independently hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, substituted or unsubstituted C 3~20 Heterocycloalkyl, substituted or unsubstituted C 2~20 Alkenyl, substituted or unsubstituted C 3~20 Cycloalkenyl, substituted or unsubstituted C 3~20 Heterocycloalkenyl, substituted or unsubstituted C 6~20 Aryl, or substituted or unsubstituted C 3~20 Heteroaryl, with the proviso that R 6 ~R 8 may be hydrogen, and R 9 ~R 11may be hydrogen, with the proviso that R 6 ~R 8 If one of R is hydrogen, then the other R 6 ~R 8 At least one of the C 6~20 Aryl or substituted or unsubstituted C 3~20 Heteroaryl, and R 9 ~R 11 If one of R is hydrogen, then the other R 9 ~R 11 At least one of the groups is substituted or unsubstituted C 6~20 Aryl or substituted or unsubstituted C 3~20 Heteroaryl. Preferably, R 6 ~R 11 are each independently substituted or unsubstituted C 1~6 Alkyl or substituted or unsubstituted C 3~10 Cycloalkyl. R 6 ~R 11 may further optionally include a divalent linking group as part of their structure.

[0047] For example, R 6 ~R 11 Any one or more of the formula -CHC(O)CH (3~n) Y n , or -CH2C(O)OCH (3~n) Y n wherein each Y is independently a substituted or unsubstituted C 3~10 heterocycloalkyl, and n is 1 or 2. For example, each Y is independently a group of the formula -O(C a1 )(C a2 )O- group 3~10 Heterocycloalkyl, wherein C a1 and C a2 are each independently hydrogen or substituted or unsubstituted alkyl; C a1 and C a2 together optionally form a ring.

[0048] In formula (2), R6 ~R 8 Any two of may optionally together form a ring, which may further include a divalent linking group as part of its structure, and which ring may be substituted or unsubstituted.

[0049] In formula (3), R 9 ~R 11 Any two of may optionally be taken together to form a ring, which may further include a divalent linking group as part of its structure, and the ring group may be substituted or unsubstituted.

[0050] In equations (4) and (6), R 12 , R 13 , R 18 , and R 19 are each independently hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, substituted or unsubstituted C 3~20 Heterocycloalkyl, substituted or unsubstituted C 6~20 Aryl, or substituted or unsubstituted C 3~20 heteroaryl; and R 14 and R 20 are each independently substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 3~20 Heterocycloalkyl. Preferably, R 12 , R 13 , R 15 , and R 16 are each independently hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 3~20 R may be heterocycloalkyl. 12 , R 13 , R 18 , and R 19 may further optionally include a divalent linking group as part of their structure.

[0051] In formula (4), R 12 ~R 14 Any two of may optionally be taken together to form a ring, which may further include a divalent linking group as part of its structure, and the ring group may be substituted or unsubstituted.

[0052] In formula (5), R 15 ~R 17 are each independently substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, substituted or unsubstituted C 3~20 Heterocycloalkyl, substituted or unsubstituted C 6~20 Aryl, or substituted or unsubstituted C 3~20 Heteroaryl, provided that R 15 ~R 17 may be hydrogen, and R 15 ~R 17 If one of R is hydrogen, then the other R 15 ~R 17 At least one of the C 6~20 Aryl or substituted or unsubstituted C 3~20 Heteroaryl. R 15 ~R 17 Each of may further optionally include a divalent linking group as part of their structure.

[0053] For example, R 15 ~R 17 Any one or more of the formula -CHC(O)CH (3~n) Y n , or -CH2C(O)OCH (3~n) Y n wherein each Y is independently a substituted or unsubstituted C 3~10 heterocycloalkyl, and n is 1 or 2. For example, each Y is independently a group of the formula -O(C a1 )(C a2 )O- group 3~10 Heterocycloalkyl, wherein C a1 and C a2are each independently hydrogen or substituted or unsubstituted alkyl; C a1 and C a2 together optionally form a ring.

[0054] In formula (5), R 15 ~R 17 Any two of may optionally together form a ring, further comprising a divalent linking group as part of its structure, and the ring group may be substituted or unsubstituted.

[0055] In formulas (5) and (6), X a and X b are each independently a polymerizable group selected from vinyl and norbornyl.

[0056] In formulas (5) and (6), L 2 and L 3 are each independently a single bond or a divalent linking group, provided that X a If is vinyl, L 2 is not a single bond and X b If is vinyl, L 3 is not a single bond. 2 and L 3 are each independently substituted or unsubstituted C 6~30 Arylene or substituted or unsubstituted C 6~30 In formulas (5) and (6), n1 is 0 or 1, and n2 is 0 or 1. When n1 is 0, L 2 It is to be understood that the group is directly attached to the oxygen atom. When n2 is 0, L 3 It is understood that the group is attached directly to the oxygen atom.

[0057] In formula (6), R 18 ~R 20 Any two of may optionally be taken together to form a ring, which may further include a divalent linking group as part of its structure, and the ring group may be substituted or unsubstituted.

[0058] In some embodiments, R6 ~R 20 may optionally include as part of their structure one or more divalent linking groups selected from -O-, -C(O)-, -C(O)-O-, -S-, -S(O)2-, and N(R')-S(O)2-, where R' is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 3~20 It may be a heterocycloalkyl.

[0059] In some embodiments, in the repeat unit that includes an acid labile group, the acid labile group may be a tertiary alkyl ester. For example, the repeat unit that includes a tertiary alkyl ester group may be derived from one or more monomers of formula (2), (3), or (5), where R 6 ~R 11 is not hydrogen, and n1 is 1.

[0060] Exemplary monomers of formula (2) include the following: [ka] One or more of the following may be mentioned.

[0061] Exemplary monomers of formula (3) include the following: [ka] [ka] wherein R d is R in Eq. (3). b R′ and R″ are each independently substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, substituted or unsubstituted C 3~20 Heterocycloalkyl, substituted or unsubstituted C2~20 Alkenyl, substituted or unsubstituted C 3~20 Cycloalkenyl, substituted or unsubstituted C 3~20 Heterocycloalkenyl, substituted or unsubstituted C 6~20 Aryl, or substituted or unsubstituted C 3~20 It is heteroaryl.

[0062] Exemplary monomers of formula (4) include the following: [ka] wherein R d is R c As defined above with respect to

[0063] Exemplary monomers of formula (5) include the following: [ka] One or more of the following may be mentioned.

[0064] Exemplary monomers of formula (6) include the following: [ka] One or more of the following may be mentioned.

[0065] In yet another example, the polymer may have, for example, the following structure: [ka] wherein R d is R a As defined above with respect to

[0066] In some embodiments, the polymer comprises a tertiary alkoxy group, such as the following: [ka] The monomer may have a repeat unit having an acid labile group, the repeat unit containing one or more monomers of the formula:

[0067] The repeat units having acid labile groups are typically present in the polymer in an amount of from 5 to 80 mol %, more typically from 15 to 75 mol %, and even more typically from 20 to 60 mol %, based on all repeat units in the polymer.

[0068] The polymer may optionally include one or more additional repeat units. The additional repeat units may be, for example, one or more additional units for adjusting the properties of the photoresist composition, such as etch rate and solubility. Exemplary additional units may include those derived from one or more of (meth)acrylate monomers, vinyl aromatic monomers, vinyl ether monomers, vinyl ketone monomers, and / or vinyl ester monomers. When present in the polymer, the one or more additional repeat units may be used in an amount of up to 90 mol %, typically 3-50 mol %, based on the total repeat units of the polymer.

[0069] The polymer may have the formula (7) or (8): [ka] wherein R d and R f are each independently hydrogen, fluorine, cyano, or substituted or unsubstituted C 1~10 It is an alkyl.

[0070] In formula (7), L 4 is a single bond or a divalent linking group. 4 Exemplary divalent linking groups include substituted or unsubstituted C 1~20 Alkylene, substituted or unsubstituted C 3~20Cycloalkylene, or substituted or unsubstituted C 3~20 heterocycloalkylene.

[0071] In formula (7), L 5 is a divalent linking group. 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 Heterocycloalkylene, -O-, -C(O)-, -S-, -S(O)2-, and N(R 22a )-S(O)2, wherein R 22a is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 3~20 It may be a heterocycloalkyl.

[0072] In formula (7), q is 0 or 1.

[0073] L 4 is a single bond, R 22 -L 5 The - moiety is attached directly to the oxygen atom adjacent to the carbonyl group (i.e., -C(O)-OL 5 -R 22 ) Similarly, if q is 0, then R 22 - The part is a group L 4 (i.e., -C(O)-OL 4 -R 22 ) Please understand that. 4 is a single bond and q is 0, R 22 The moiety is directly attached to the oxygen atom adjacent to the carbonyl group (i.e., -C(O)-OR 22 ) Please understand that.

[0074] In formula (7), R 22is a substituted or unsubstituted organic group containing one or more heteroatoms. Exemplary organic groups containing one or more heteroatoms of the present invention include nitro (-NO), cyano (-CN), amino (-NR 22b R 22c wherein R 22b and R 22c are each independently 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, thiol (-SH), substituted or unsubstituted C 6~24 These include, but are not limited to, arylthiol, sulfonyl, or combinations thereof.

[0075] In some embodiments, the repeat unit derived from the monomer of formula (7) is a hydroxy-substituted C 1~30 Alkyl, hydroxy-substituted C 3~30 Cycloalkyl, Hydroxy-Substituted C 6~30 Aryl groups, hydroxy-substituted C 3~30 heteroaryl groups, or combinations thereof, each of which is further optionally substituted.

[0076] In equation (8), L 6 is a single bond or a divalent linking group. Exemplary divalent linking groups for L6 include substituted or unsubstituted C 1~30 Alkylene, substituted or unsubstituted C 1~30 Heteroalkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 Heteroarylene, -O-, -C(O)-, -S-, -S(O)2-, or -N(R 23a )-S(O)-, wherein R23a is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 3~20 It may be a heterocycloalkyl.

[0077] L 6 is a single bond, R 23 The - moiety is attached directly to the oxygen atom adjacent to the carbonyl group (i.e., -C(O)OR 23 ) Please understand that.

[0078] In formula (8), R 23 is a substituted or unsubstituted C 4~20 Lactone-containing group, or substituted or unsubstituted C 4~20 It is a sultone-containing group. 4~20 Lactone-containing groups and C 4~20 The sultone-containing group may be monocyclic, polycyclic, or fused polycyclic.

[0079] Exemplary monomers of formula (7) include the following: [ka] In one embodiment, the compound may include one or more of the following: d is as defined for equation (7).

[0080] Exemplary monomers of formula (8) include the following: [ka] In one embodiment, the compound may include one or more of the following: f is as defined for equation (8).

[0081] When present, the polymer typically contains repeat units derived from monomers of formula (7) and / or (8) in a combined amount of from 5 to 60 mol %, typically from 20 to 55 mol %, more typically from 25 to 50 mol %, based on all repeat units in the polymer.

[0082] In some embodiments, the polymer may further comprise a base-soluble repeat unit having a pKa of less than or equal to 12. For example, the base-soluble repeat unit may be represented by formula (9), (10), or (11): [ka] The monomers may be one or more of the monomers.

[0083] In formulas (9) to (11), each R g is hydrogen, fluorine, cyano, or substituted or unsubstituted C 1~10 Preferably, R g is hydrogen, fluorine, or substituted or unsubstituted C 1~5 It may be an alkyl, typically methyl.

[0084] In formula (9), R 24 is a substituted or unsubstituted C 1~100 Or C 1~20 Alkyl, typically C 1~12 Alkyl; substituted or unsubstituted C 3~30 Or C 3~20 cycloalkyl; or substituted or unsubstituted poly(C 1~3 alkylene oxide). Preferably, the substituted C 1~100 Or C 1~20 Alkyl, substituted C 3~30 Or C 3~20 Cycloalkyl and substituted poly(C 1~3 Alkylene oxide) is halogen, C 1~4 Fluoroalkyl groups, typically fluoroalkyl groups such as fluoromethyl, sulfonamide groups -NH-S(O)2-Y 1 (In the formula, Y 1 is F or C 1~4perfluoroalkyl (e.g., -NHSO2CF3) or fluoroalcohol groups (e.g., -C(CF3)2OH).

[0085] In formula (10), L 7 is, for example, optionally -O-, -S-, -C(O)-, and -NR 102 -(In the formula, R 102 is hydrogen and optionally substituted C 1~10 Optionally substituted C 1~6 Alkylene or C 3~20 represents a single bond or a polyvalent linking group selected from aliphatic hydrocarbons, such as cycloalkylene, and aromatic hydrocarbons, and combinations thereof. For example, the polymer may further comprise repeat units derived from one or more monomers of formula (10), where L 7 is a 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 is a single bond or a polyvalent linking group selected from arylene.

[0086] In formula (10), n3 is an integer from 1 to 5, typically 1. When n3 is 1, the group L 7 It is to be understood that is a divalent linking group. When n3 is 2, the group L 7 It should be understood that n3 is a trivalent linking group. Similarly, when n3 is 3, the group L 7 is a tetravalent linking group, and n3 is 4, the group L 7 is a pentavalent linking group and n3 is 5, the group L 7 It should be understood that is a hexavalent linking group. Thus, in the context of formula (10), the term "polyvalent linking group" refers to any of divalent, trivalent, tetravalent, pentavalent, and / or hexavalent linking groups. In some embodiments, when n is 2 or greater, the carboxylic acid group (-C(O)-OH) is linked to the linking group L 7In another embodiment, when n is 2 or more, the carboxylic acid group (-C(O)-OH) can be bonded to the same atom of the linking group L 7 The aryl group may be bonded to different atoms of the ring.

[0087] In formula (11), L 8 represents a single bond or a divalent linking group. 8 is a single bond, substituted or unsubstituted C 6~30 Arylene, or substituted or unsubstituted C 6~30 It may be a cycloalkylene.

[0088] In formula (11), n4 is 0 or 1. When n4 is 0, the moiety represented by -OC(O)- is L 8 It is to be understood that is a single bond such that it is attached directly to the alkenyl (vinyl) carbon atom.

[0089] In formula (11), Ar 1 is a substituted C optionally containing one or more aromatic ring heteroatoms selected from N, O, S, or combinations thereof; 5~60 is an aromatic group, which may be monocyclic, non-fused polycyclic, or fused polycyclic. 5~60 When the aromatic group is polycyclic, the rings or ring groups can be fused (such as naphthyl), non-fused, or combinations thereof. 5~60 When the aromatic group is non-fused, the rings or ring groups may be directly linked (such as biaryl, biphenyl) or bridged by a heteroatom (such as triphenylamino or diphenylene ether). 5~60 The aromatic groups can contain combinations of fused rings and directly linked rings (such as binaphthyl).

[0090] In formula (11), y may be an integer from 1 to 12, preferably from 1 to 6, typically from 1 to 3. x may independently be hydrogen or methyl.

[0091] Non-limiting examples of monomers that can be used to provide base-soluble repeat units to the polymer include the following: [ka] [ka] wherein Y 1 is as described above, and R i is expressed as R in equations (9) to (11). g As defined with respect to

[0092] When present, the polymer typically contains base-soluble repeat units in an amount of from 1 to 60 mol %, typically from 5 to 50 mol %, more typically from 5 to 40 mol %, based on total repeat units in the polymer.

[0093] Non-limiting exemplary polymers of the present invention include the following: [ka] where a, b, c, and d represent the mole fractions of the corresponding repeat units of the polymer.

[0094] The polymer typically has a weight average molecular weight (M) of 1,000 to 50,000 Daltons (Da), preferably 2,000 to 30,000 Da, more preferably 4,000 to 25,000 Da, and even more preferably 5,000 to 25,000 Da. w ) M w and number average molecular weight (M n The polydispersity index (PDI) of the first polymer, which is the ratio of the molecular weight (Mw) to the molecular weight (Cw), is typically from 1.1 to 3, more typically from 1.1 to 2. Molecular weight values ​​are determined by gel permeation chromatography (GPC) using polystyrene standards.

[0095] The polymer can be prepared by any suitable method in the art. For example, one or more monomers corresponding to the repeating units described herein can be combined or separately fed and polymerized in a reactor using a suitable solvent and initiator. For example, the polymer can be obtained by polymerizing each monomer under any suitable conditions, such as by heating at an effective temperature, irradiating with actinic radiation at an effective wavelength, or a combination thereof.

[0096] The photoresist composition further comprises a photoacid generator (PAG). Suitable PAGs can generate an acid during post-exposure bake (PEB) that causes cleavage of acid labile groups present on the polymer of the photoresist composition. The PAG can be in non-polymeric or polymeric form, for example, in the polymerized repeat unit of the polymer described above, or as part of another polymer. In some embodiments, the PAG can be included in the composition as a non-polymerizable PAG compound, as a repeat unit of a polymer having a PAG portion derived from a polymerizable PAG monomer, or a combination thereof.

[0097] Suitable non-polymeric PAG compounds have the formula G + A - wherein G + is an organic cation selected from an iodonium cation substituted with two alkyl groups, two aryl groups, or a combination of an alkyl group and an aryl group; and a sulfonium cation substituted with three alkyl groups, three aryl groups, or a combination of an alkyl group and an aryl group; - is a non-polymerizable organic anion. Particularly suitable non-polymeric organic anions include those in which the conjugate acid has a pKa of −15 to 1. Particularly preferred anions are the anions of fluorinated alkylsulfonates and fluorinated sulfonimides.

[0098] Useful non-polymeric PAG compounds are known in the chemically amplified photoresist art and include, for example, onium salts such as triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; di-t-butylphenyliodonium perfluorobutanesulfonate, and di-t-butylphenyliodonium camphorsulfonate. Nonionic sulfonate and sulfonyl compounds are also known to function as photoacid generators, such as nitrobenzyl derivatives, e.g., 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate, and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonic acid esters, e.g., 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives, e.g., bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diamine, and bis(p-toluenesulfonyl)diamine. (p-toluenesulfonyl)diazomethane; glyoxime 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, N-hydroxysuccinimide trifluoromethanesulfonate; and halogen-containing triazine compounds such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine and 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine. Suitable non-polymerizable photoacid generators are further described in (Patent Document 1) Hashimoto et al., column 37, lines 11-47 and columns 41-91.Other suitable sulfonate PAGs include sulfonated esters and sulfonyloxy ketones, nitrobenzyl esters, s-triazine derivatives, benzoin tosylate, t-butylphenyl α-(p-toluenesulfonyloxy)acetate, and t-butyl α-(p-toluenesulfonyloxy)acetate, as described in U.S. Pat. No. 5,399,233 and U.S. Pat. No. 5,499,233.

[0099] Typically, when the photoresist composition includes a non-polymeric photoacid generator, the non-polymeric photoacid generator is present in the photoresist composition in an amount from 0.3 to 65 weight percent, more typically from 1 to 20 weight percent, based on total solids of the photoresist composition.

[0100] In some embodiments, G + is a sulfonium cation of formula (13) or an iodonium cation of formula (14): [ka] It may be.

[0101] In formulas (13) and (14), each R aa are independently substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, substituted or unsubstituted C 2~20 Alkenyl, substituted or unsubstituted C 6~30 Aryl, substituted or unsubstituted C 3~30 Heteroaryl, substituted or unsubstituted C 7~20 Arylalkyl, or substituted or unsubstituted C 4~20 Heteroarylalkyl. Each R aa may be separate or may be connected to another group R via a single bond or a divalent linking group so as to form a ring. aa Each R aa may optionally include a divalent linking group as part of its structure. aamay optionally include acid labile groups independently selected from, for example, a tertiary alkyl ester group, a secondary or tertiary aryl ester group, a secondary or tertiary ester group having a combination of alkyl and aryl groups, a tertiary alkoxy group, an acetal group, or a ketal group.

[0102] Exemplary sulfonium cations of formula (13) include the following: [ka] [ka] One or more of the following may be mentioned.

[0103] Exemplary iodonium cations of formula (14) include the following: [ka] One or more of the following may be mentioned.

[0104] PAGs that are onium salts typically contain an organic anion having a sulfonate or non-sulfonate type group, such as a sulfonamidate group, a sulfonimidate group, a methide group, or a borate group.

[0105] Exemplary organic anions having a sulfonate group include the following: [ka] One or more of the following may be mentioned.

[0106] Exemplary non-sulfonated anions include the following: [ka] One or more of the following may be mentioned.

[0107] The photoresist composition may optionally include multiple PAGs. The multiple PAGs may be polymeric, non-polymeric, or may include both polymeric and non-polymeric PAGs. Preferably, each of the multiple PAGs is non-polymeric.

[0108] In one or more embodiments, the photoresist composition can include a first photoacid generator that includes a sulfonate group in its anion, and the photoresist composition can include a non-polymeric second photoacid generator, which can include an anion that does not include a sulfonate group.

[0109] In some embodiments, the polymer comprises a repeat unit that includes a PAG-containing moiety, such as a repeat unit of formula (15): [ka] The copolymer may further optionally contain repeat units derived from one or more monomers of the formula:

[0110] In formula (15), R m is hydrogen, fluorine, cyano, or substituted or unsubstituted C 1~10 Preferably, R m is hydrogen, fluorine, or substituted or unsubstituted C 1~5 Alkyl, typically methyl. 1 may be a single bond or a divalent linking group. 1 may contain 1 to 10 carbon atoms and at least one heteroatom, more preferably -C(O)-O-.

[0111] In equation (15), A 1 is a substituted or unsubstituted C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, or substituted or unsubstituted C 3~30Heteroarylene may be one or more of the following: 1 is an optionally substituted divalent C 1~30 It may be a perfluoroalkylene group.

[0112] In formula (15), Z - is an anionic moiety, the conjugate acid of which typically has a pKa between -15 and 1. For example, Z - may be a sulfonate, carboxylate, anion of a sulfonamide, anion of a sulfonimide, or a methide anion. Particularly preferred anionic moieties are the anions of fluorinated alkylsulfonates and fluorinated sulfonimides.

[0113] In formula (15), G + is an organic cation as defined above. In some embodiments, G + is an iodonium cation substituted with two alkyl groups, two aryl groups, or a combination of an alkyl group and an aryl group; or a sulfonium cation substituted with three alkyl groups, three aryl groups, or a combination of an alkyl group and an aryl group.

[0114] Exemplary monomers of formula (15) include the following: [ka] In one embodiment, the formula may include one or more of: + is an organic cation as defined herein.

[0115] When used, repeat units containing PAG moieties may be included in the polymer in an amount of from 1 to 15 mol %, typically from 1 to 8 mol %, and more typically from 2 to 6 mol %, based on the total repeat units in the polymer.

[0116] The photoresist composition further comprises a solvent to dissolve the components of the composition and facilitate its coating on a substrate. Preferably, the solvent is an organic solvent conventionally used in the manufacture of electronic devices. Suitable solvents include, for example, aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane and 1-chlorohexane; alcohols such as methanol, ethanol, 1-propanol, isopropanol, tert-butanol, 2-methyl-2-butanol, 4-methyl-2-pentanol, and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone); propylene glycol monomethyl ether (PGME); ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and anisole; acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanol, methyl ethyl ketone ... Examples of suitable solvents include ketones such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), hydroxyisobutyrate methyl ester (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 dimethylsulfoxide and dimethylformamide; water; and combinations thereof. Among these, preferred solvents are PGME, PGMEA, EL, GBL, HBM, CHO, and combinations thereof.

[0117] The total solvent content in the photoresist composition (i.e., the cumulative solvent content of all solvents) is typically 40 to 99 weight percent, such as 60 to 99 weight percent, or 85 to 99 weight percent, based on the total solids content of the photoresist composition. The desired solvent content depends, for example, on the desired thickness of the coated photoresist layer and the coating conditions.

[0118] The polymer is typically present in the photoresist composition in an amount of from 10 to 99.9 weight percent, typically from 25 to 99 weight percent, more typically from 40 to 95 weight percent, based on the total solids of the photoresist composition, it being understood that "total solids" includes the polymer, PAG, additives, and other non-solvent components.

[0119] In some embodiments, the photoresist composition may further comprise a material that comprises one or more base labile groups ("base labile material"). A base labile group as referred to herein is a functional group that can undergo a cleavage reaction to provide a polar group such as hydroxyl, carboxylic acid, or sulfonic acid in the presence of an aqueous alkaline developer after the exposure and post-exposure bake steps. The base labile group does not significantly react (e.g., does not undergo a bond scission reaction) before the development step of the photoresist composition that comprises the base labile group. Thus, for example, the base labile group is substantially inactive during the pre-exposure soft bake, exposure, and post-exposure bake steps. By "substantially inactive" it is meant that 5% or less, typically 1% or less of the base labile groups (or moieties) decompose, cleave, or react during the pre-exposure soft bake, exposure, and post-exposure bake steps. The base labile group is reactive under typical photoresist development conditions, for example, with an aqueous alkaline photoresist developer such as 0.26 normal (N) aqueous tetramethylammonium hydroxide (TMAH) solution. For example, a 0.26N aqueous TMAH solution may be used for single puddle development or dynamic development, where, for example, 0.26N TMAH developer is dispensed onto the imaged photoresist layer for a suitable time, such as 10 to 120 seconds (s). An exemplary base labile group is an ester group, typically a fluorinated ester group. Preferably, the base labile material is substantially immiscible with the polymer and other solid components of the photoresist composition, and has a lower surface energy than the polymer and other solid components of the photoresist composition. This allows the base labile material to be separated from the other solid components of the photoresist composition to the top surface of the formed photoresist layer when coated onto a substrate.

[0120] In some embodiments, the base labile material may be a polymeric material, also referred to herein as a base labile polymer, and may include one or more repeat units that include one or more base labile groups. For example, the base labile polymer may include repeat units that include two or more base labile groups, which may be the same or different. A preferred base labile polymer includes at least one repeat unit that includes two or more base labile groups, for example, a repeat unit that includes two or three base labile groups.

[0121] The base labile polymer has the formula (16): [ka] wherein X e is a polymerizable group selected from vinyl and (meth)acrylic; L 9 is a divalent linking group; and R n is a substituted or unsubstituted C 1~20 Fluoroalkyl, provided that the carbon atom bonded to the carbonyl (-C(O)-) of formula (16) is replaced with at least one fluorine atom.

[0122] Exemplary monomers of formula (16) include the following: [ka] One or more of the following may be mentioned.

[0123] The base labile polymer can include repeat units that include more than one base labile group. For example, the base labile polymer can have the formula (17): [ka] In one embodiment, the repeat unit may be derived from one or more monomers of the formula: f and R p are X e and R nis as defined in equation (16); L 10 is a substituted or unsubstituted C 1~20 Alkylene, substituted or unsubstituted C 3~20 is a polyvalent linking group that includes one or more of cycloalkylene, -C(O)-, or -C(O)O-; and n3 can be an integer of 2 or greater, for example, 2 or 3.

[0124] Exemplary monomers of formula (17) include the following: [ka] One or more of the following may be mentioned.

[0125] The base labile polymer can include repeat units that include one or more base labile groups. For example, the base labile polymer can be represented by the formula (18): [ka] In one embodiment, the repeat unit may be derived from one or more monomers of the formula: g and R q are X e and R n is as defined in equation (16); L 11 is a divalent linking group; and L 12 is a substituted or unsubstituted C 1~20 In the fluoroalkylene, the carbon atom bonded to the carbonyl (-C(O)-) of formula (18) is substituted with at least one fluorine atom.

[0126] Exemplary monomers of formula (18) include the following: [ka] One or more of the following may be mentioned.

[0127] In a further preferred embodiment of the invention, the base labile polymer may comprise one or more base labile groups and one or more acid labile groups, such as one or more acid labile ester moieties (e.g., t-butyl esters) or acid labile acetal groups. For example, the base labile polymer may comprise a repeat unit comprising a base labile group and an acid labile group, i.e., both the base labile group and the acid labile group are present in the same repeat unit. In another example, the base labile polymer may comprise a first repeat unit comprising a base labile group and a second repeat unit comprising an acid labile group. A preferred photoresist of the invention may reduce defects associated with resist relief images formed from a photoresist composition.

[0128] The base labile polymer can be prepared using any suitable method in the art, including those described herein for the first and second polymers.For example, the base labile polymer can be obtained by polymerizing the respective monomers under any suitable conditions, such as by heating at an effective temperature, irradiating with actinic radiation at an effective wavelength, or a combination thereof.In addition, or alternatively, one or more base labile groups can be grafted onto the backbone of the polymer using a suitable method.

[0129] In some embodiments, the base labile substance is a single molecule that contains one or more base labile ester groups, preferably one or more fluorinated ester groups. Single molecule base labile substances typically have an M in the range of 50 to 1,500 Da. W Exemplary base labile substances include the following: [ka] One or more of the following may be mentioned.

[0130] If present, the base labile polymer is typically present in a photoresist composition in an amount of from 0.01 to 10 weight percent, more typically from 1 to 5 weight percent, based on total solids of the photoresist composition.

[0131] In addition to or instead of the base labile polymer, the photoresist composition may further comprise one or more polymers different from the photoresist polymer described above.For example, the photoresist composition may comprise an additional polymer as described above but with a different composition, or a polymer similar to the one described above but without each of the essential repeat units.In addition to or instead of that, the one or more additional polymers may include those well known in the photoresist technology, such as those selected from polyacrylates, polyvinyl ethers, polyesters, polynorbornenes, polyacetals, polyethylene glycols, polyamides, polyacrylamides, polyphenols, novolacs, styrene-based polymers, polyvinyl alcohols, or combinations thereof.

[0132] The photoresist composition may further comprise one or more additional optional additives. For example, the optional additives may include actinic and contrast dyes, anti-striation agents, plasticizers, rate enhancers, sensitizers, photolytic quenchers (PDQs) (also known as photolytic bases), base quenchers, thermal acid generators, surfactants, and the like, or combinations thereof. When present, the optional additives are typically present in the photoresist composition in an amount of 0.01 to 10 wt %, based on the total solids content of the photoresist composition.

[0133] PDQ generates a weak acid upon irradiation. The acid generated from the photolabile quencher is not strong enough to react quickly with the acid labile groups present in the resist matrix. Exemplary photolabile quenchers include, for example, photolabile cations, preferably, for example, C 1~20 Carboxylic acid or C 1~20Also included are those useful for preparing strong acid generator compounds paired with anions of weak acids (pKa>1), such as anions of sulfonic acids. Exemplary carboxylic acids include formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexane carboxylic acid, benzoic acid, salicylic acid, and the like. Exemplary sulfonic acids include p-toluenesulfonic acid, camphorsulfonic acid, and the like. In a preferred embodiment, the photodegradable quencher is a photodegradable organic zwitterionic compound, such as diphenyliodonium-2-carboxylate.

[0134] The photodegradable quencher may be in a non-polymer form or in a polymer-bound form. In the case of a polymer form, the photodegradable quencher is present in the polymerized units of the first polymer or the second polymer. The polymerized units containing the photodegradable quencher are typically present in an amount of 0.1 to 30 mol %, preferably 1 to 10 mol %, more preferably 1 to 2 mol %, based on the total repeat units of the polymer.

[0135] Exemplary basic quenchers include, for example, straight chain aliphatic amines such as tributylamine, trioctylamine, triisopropanolamine, tetrakis(2-hydroxypropyl)ethylenediamine; n-tert-butyldiethanolamine, tris(2-acetoxy-ethyl)amine, 2,2',2'',2'''-(ethane-1,2-diylbis(azanetriyl))tetraethanol, 2-(dibutylamino)ethanol, and 2,2',2''-nitrilotriethanol; Cycloaliphatic amines such as N,N-bis(2-hydroxyethyl)pivalamide, N,N-diethylacetamide, N-(2-butoxycarbonyl)-4-hydroxypiperidine, tert-butyl 1-pyrrolidinecarboxylate, tert-butyl 2-ethyl-1H-imidazole-1-carboxylate, di-tert-butylpiperazine-1,4-dicarboxylate, and N-(2-acetoxyethyl)morpholine; aromatic amines such as pyridine, di-tert-butylpyridine, and pyridinium; 1 ,N 1 ,N 3 ,N3 linear and cyclic amides and derivatives thereof, such as tetrabutylmalonamide, 1-methylazepan-2-one, 1-allylazepan-2-one, and tert-butyl 1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylcarbamate; ammonium salts, such as quaternary ammonium salts of sulfonates, sulfamates, carboxylates, and phosphonates; imines, such as primary and secondary aldimines and ketimines; optionally substituted diazines, such as pyrazines, piperazines, and phenazines; optionally substituted diazoles, such as pyrazoles, thiadiazoles, and imidazoles; and optionally substituted pyrrolidones, such as 2-pyrrolidone and cyclohexylpyrrolidine.

[0136] The basic quencher may be in a non-polymeric form or in a polymer-bound form. When in a polymeric form, the quencher may be present in a repeat unit of the polymer. The repeat unit containing the quencher is typically present in an amount of 0.1 to 30 mol %, preferably 1 to 10 mol %, more preferably 1 to 2 mol %, based on the total repeat units of the polymer.

[0137] Exemplary surfactants include fluorinated and non-fluorinated surfactants, and may be ionic or non-ionic, with non-ionic surfactants being preferred.Exemplary fluorinated non-ionic surfactants include perfluoro C4 surfactants, such as FC-4430 and FC-4432 surfactants available from 3M Corporation; and fluorodiols, such as POLYFOX PF-636, PF-6320, PF-656, and PF-6520 fluorosurfactants from Omnova.In one embodiment, the photoresist composition further comprises a surfactant polymer that comprises a fluorine-containing repeat unit.

[0138] A method of forming a pattern using the photoresist composition of the present invention will now be described. Suitable substrates onto which the photoresist composition can be coated include electronic device substrates. A wide variety of electronic device substrates may be used in the present invention, such as semiconductor wafers; polycrystalline silicon substrates; packaging substrates such as multichip modules; flat panel display substrates; substrates for light emitting diodes (LEDs) such as organic light emitting diodes (OLEDs), and the like, with semiconductor wafers being typical. Such substrates are typically comprised of one or more of silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. Suitable substrates may be in the form of wafers such as those used in the manufacture of integrated circuits, optical sensors, flat panel displays, optical integrated circuits, and LEDs. Such substrates may be of any suitable size. A typical wafer substrate has a diameter of 200-300 millimeters (mm), although smaller and larger diameter wafers may be suitably used in accordance with the present invention. The substrate may include one or more layers or structures that may optionally include operating or operable portions of the device being formed.

[0139] Typically, one or more lithographic layers, such as a hardmask layer, e.g., a spin-on carbon (SOC), amorphous carbon, or metal hardmask layer, a CVD layer, e.g., a silicon nitride (SiN), silicon oxide (SiO), or silicon oxynitride (SiON) layer, an organic or inorganic underlayer, or a combination thereof, are provided on top of the substrate prior to coating the photoresist composition of the invention. Such layers, together with an overcoated photoresist layer, form a lithographic material stack.

[0140] Optionally, a layer of adhesion promoter can be applied to the substrate surface before coating with the photoresist composition.If adhesion promoter is desired, suitable adhesion promoter for any polymer film can be used, such as silane, typically organosilane such as trimethoxyvinylsilane, triethoxyvinylsilane, hexamethyldisilazane, or aminosilane coupling agent such as γ-aminopropyltriethoxysilane.Particularly suitable adhesion promoters include those sold under the names AP 3000, AP 8000, and AP 9000S, available from DuPont Electronics & Imaging (Marlborough, Massachusetts).

[0141] The photoresist composition may be coated on the substrate by any suitable method, including spin coating, spray coating, dip coating, doctor blading, and the like. For example, application of a layer of photoresist can be accomplished by spin coating the photoresist in a solvent using a coating track, in which the photoresist is dispensed onto a rotating wafer. During dispensing, the wafer is typically rotated at a speed of up to 4,000 revolutions per minute (rpm), such as 200 to 3,000 rpm, such as 1,000 to 2,500 rpm, for a period of 15 to 120 seconds to obtain a layer of the photoresist composition on the substrate. It will be understood by those skilled in the art that the thickness of the coated layer can be adjusted by varying the spin speed and / or the total solids content 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, more preferably 6 to 25 μm.

[0142] The photoresist composition is typically then soft baked to minimize the solvent content in the layer, thereby forming a tack-free coating and improving the adhesion of the layer to the substrate. The soft bake is performed, for example, on a hot plate or in an oven, with a hot plate being typical. The temperature and time of the soft bake depend, for example, on the photoresist composition and thickness. The soft bake temperature is typically 80 to 170°C, more typically 90 to 150°C. The soft bake time is typically 10 seconds to 20 minutes, more typically 1 minute to 10 minutes, and even more typically 1 minute to 2 minutes. The heating time can be readily determined by one of ordinary skill in the art based on the components of the composition.

[0143] The photoresist layer is then patternwise exposed to activating radiation to create a solubility differential between exposed and unexposed regions. Reference herein to exposing a photoresist composition to radiation that is activating for the composition indicates that the radiation can form a latent image in the photoresist composition. Exposure is typically performed through a patterned photomask having optically transparent and optically opaque regions that correspond, respectively, to exposed and unexposed regions of the resist layer. Alternatively, such exposure can be performed without a photomask in direct write processes typically used in electron beam lithography. Activating radiation typically has a sub-400 nm, sub-300 nm or sub-200 nm wavelength, with wavelengths of 248 nm (KrF), 193 nm (ArF), 13.5 nm (EUV) or electron beam lithography being preferred. The activating radiation is preferably 248 nm radiation. This method is utilized in immersion or dry (non-immersion) lithography techniques. Exposure energies are typically between 1 and 200 millijoules per square centimeter (mJ / cm 2 ), preferably 10 to 100 mJ / cm 2 , more preferably 20 to 50 mJ / cm 2 and depends on the exposure tool and the components of the photoresist composition.

[0144] After the photoresist layer is exposed, a post-exposure bake (PEB) of the exposed photoresist layer is performed. PEB can be performed, for example, on a hot plate or in an oven, with a hot plate being typical. The PEB conditions depend, for example, on the photoresist composition and the thickness of the layer. PEB is typically performed at a temperature of 70-150°C, preferably 75-120°C, for 30-120 seconds. A latent image is formed in the photoresist, defined by areas where polarity has been switched (exposed areas) and areas where polarity has not been switched (unexposed areas).

[0145] The exposed photoresist layer is then developed with a suitable developer, which selectively removes areas of the layer that are soluble in the developer, while the remaining insoluble areas form a relief image of the resulting photoresist pattern. In the case of a positive tone development (PTD) process, the exposed areas of the photoresist layer are removed during development, leaving behind the unexposed areas. Conversely, in a negative tone development (NTD) process, the exposed areas of the photoresist layer remain, while the unexposed areas are removed during development. Application of the developer can be accomplished by any suitable method, such as those described above with respect to application of the photoresist composition, and is typically spin-coating. The development time is effective to remove the soluble areas of the photoresist, typically 5 to 60 seconds. Development is typically performed at room temperature.

[0146] Suitable developers for the PTD process include aqueous base developers, such as quaternary ammonium hydroxide solutions, such as tetramethylammonium hydroxide (TMAH), preferably 0.26 normal (N) TMAH, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the like. Suitable developers for the NTD process are organic solvent-based, meaning that the cumulative content of organic solvent in the developer is 50% by weight or more, typically 95% by weight or more, 98% by weight or more, or 100% by weight, based on the total weight of the developer. Suitable organic solvents for NTD developers include, for example, those selected from ketones, esters, ethers, hydrocarbons, and mixtures thereof. The developer is typically 2-heptanone or n-butyl acetate.

[0147] A coated substrate can be formed from the photoresist composition of the invention. Such a coated substrate comprises (a) a substrate having one or more layers patterned on its surface; and (b) a layer of a photoresist composition on the patterned layer or layers.

[0148] The photoresist pattern may be used, for example, as an etch mask, which allows the pattern to be transferred to one or more successive underlying layers by known etching techniques, typically dry etching such as reactive ion etching. The photoresist pattern may be used, for example, to transfer the pattern to an underlying hard mask layer, which is then used as an etch mask to transfer the pattern to one or more layers below the hard mask layer. If the photoresist pattern is not consumed during pattern transfer, it may be removed from the substrate by known techniques, for example, oxygen plasma ashing. When the photoresist composition is used in one or more such patterning processes, it may be used to manufacture semiconductor devices such as memory devices, processor chips (CPUs), graphic chips, optoelectronic chips, LEDs, OLEDs, as well as other electronic devices.

[0149] The present invention is further illustrated by the following examples. EXAMPLES

[0150] Example 1 and Comparative Example 1 The photoresist compositions of Example 1 and Comparative Example 1 were prepared by combining the components shown in Table 1, in amounts expressed as weight percent (wt %) based on 100 wt % of all non-solvent components of the photoresist composition (i.e., 100 wt % of total solids). The photoresist compositions were prepared in a solvent mixture of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and gamma-butyrolactone (gBL) in a weight ratio of 75:20:5.

[0151] [Table 1]

[0152] The additive (A1) was γ-methyldecalactone. The surfactant (SLA) was POLYFOX PF-656 (Omnova Solutions Inc.).

[0153] The polymer (P1) has the following structure: [ka] where a is 64.2 mol%, b is 5.1 mol%, c is 24.3 mol%, and d is 24.3 mol%, based on 100 mol% total repeat units. Polymer 1 has an M w and had a PDI of 1.69.

[0154] The structures of the photoacid generator (PAG1), the quencher (Q1), and the quencher (Q2) are as follows: [ka]

[0155] Photospeed. KrF contrast and lithography evaluation was performed on 200 mm silicon wafers using a TEL Mark8 truck (Tokyo Electron Limited). Silicon wafers were primed with HMDS (125° C. for 60 seconds) and then spin-coated with the photoresist composition of Example 1 or Comparative Example 1. The coated wafers were baked at 150° C. for 200 seconds to obtain a photoresist layer with a thickness of about 15 μm. The photoresist-coated wafers were then exposed to KrF radiation (248 nm) without a mask using an ASML300 KrF stepper with a numerical aperture of 0.6NA / 0.65σ. The exposed wafers were post-exposure baked at 110° C. for 120 seconds and developed using a 0.26 N tetramethylammonium hydroxide (TMAH) solution (DuPont Electronics & Imaging) for 120 seconds to form resist patterns. Different exposure doses (mJ / cm 2 The thickness (μm) of the remaining photoresist layer at 100 nm was measured using an F50-UVX Film Mapping System (Filmetrics). The data was evaluated by plotting the remaining film thickness as a function of exposure dose to obtain a positive contrast curve for KrF. The contrast curve was used to determine the clearing dose (E0), which is the minimum dose required to completely clear the film.

[0156] The E0 values ​​for each formulation are shown in Table 2.

[0157] [Table 2]

[0158] As demonstrated by the data in Table 2, the additive of the present invention increased the E0 clearing dose of the photoresist composition of Example 1. Thus, Inventive Example 1 achieved a faster photospeed compared to the photospeed achieved with Comparative Example 1.

[0159] Stripping. 200 mm silicon wafers were primed with HMDS (125° C. for 60 seconds) and spin-coated with the photoresist composition of Example 1 or Comparative Example 1. The wafers were baked at 150° C. for 200 seconds to yield a film thickness of approximately 15 μm. The photoresist-coated wafers were then exposed to 248 nm radiation using an ES4 stepper (Canon Inc.) equipped with a binary mask using 0.6 NA / 0.65 σ. The exposed wafer was post-exposure baked at 110° C. for 120 seconds and then developed using 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. Overhead images revealed that the γ-methyl-decalactone additive of Example 1 improved the adhesion performance of thick photoresists for KrF patterning.

[0160] Example 2 and Comparative Example 2 The photoresist compositions of Example 2 and Comparative Example 2 were prepared by combining the components as shown in Table 3, where the amounts are expressed in weight percent (wt%) based on 100 wt% of all non-solvent components of the photoresist composition (i.e., 100 wt% of total solids). The photoresist compositions were prepared in a 60:40 weight ratio solvent mixture of PGMEA and PGME.

[0161] [Table 3]

[0162] The structures of P1, PAG1, Q1, Q2 and SLA are the same as defined above.

[0163] Additives (A2) and (A3) had the following structures: [ka]

[0164] Photospeed Evaluation. KrF comparison and lithographic evaluation of Example 2 and Comparative Example 2 were performed as described above for Example 1 and Comparative Example 1.

[0165] From these experiments, it was found that the E0 clearing dose in Example 2 was 14 mJ / cm 2 whereas the E0 clearing dose of Comparative Example 2 was 20 mJ / cm 2 As the data demonstrates, the substituted lactone additive having Formula A3 increased the photospeed of the photoresist composition of Example 2.

[0166] While the present disclosure has been described in terms of what are presently considered to be practical exemplary embodiments, it is to 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 polymer; A photoacid generator; The following formula (1c): 【Chemistry 1】 (In formula (1c), R １ and R ２ are each independently substituted or unsubstituted C １～３ Alkyl, substituted or unsubstituted C １～２０ Heteroalkyl, substituted or unsubstituted C ３～２０ Cycloalkyl, substituted or unsubstituted C ３～２０ Heterocycloalkyl, substituted or unsubstituted C ６～２０ Aryl, or substituted or unsubstituted C ３～２０ is heteroaryl; The substitution C １～３ The alkyl substituents are nitro; cyano; hydroxy; amino; mono- or di-(C １～６ ) alkylamino; ２～６ Alkanoyl group; formyl; carboxylic acid or its alkali metal salt or ammonium salt; C ２～６ Alkyl esters (-C(O)O-alkyl or -OC(O)-alkyl); ７～１３ Aryl esters (-C(O)O-aryl or -OC(O)-aryl); amides (-C(O)NR ２ (Wherein, R is hydrogen or C １～６ alkyl); carboxamide (-CH ２ C(O)NR ２ (Wherein, R is hydrogen or C １～６ alkyl); halogen; thiol; C １～６ Alkylthio; Thiocyano; C ２～６ Alkenyl; C ２～６ Alkynyl; C １～６ Haloalkyl; C １～９ Alkoxy; C １～６ Haloalkoxy; C ３～１２ Cycloalkyl; C ５～１８ Cycloalkenyl; C ２～１８ Heterocycloalkenyl; C having at least one aromatic ring ６～１２ Aryl; C having 1 to 3 separate or fused rings and 6 to 18 ring carbon atoms ７～１９ Arylalkyl; arylalkoxy having 1 to 3 separate or fused rings and 6 to 18 ring carbon atoms; C ７～１２ Alkylaryl; C ３～１２ Heterocycloalkyl; C ３～１２ Heteroaryl; C １～６ Alkylsulfonyl; C ６～１２ arylsulfonyl; or tosyl; R １ and R ２ Each of the groups may include, as part of their structure, -O-, -C(O)-, -S-, -S(O) ２ -, and -N(R １ａ )-(wherein, R １ａ is hydrogen, substituted or unsubstituted C １～２０ Alkyl, substituted or unsubstituted C ３～２０ Cycloalkyl, or substituted or unsubstituted C ３～２０ heterocycloalkyl); R ３ａ and R ３ｂ are each independently hydrogen, substituted or unsubstituted C １～２０ Alkyl, substituted or unsubstituted C ３～２０ Cycloalkyl, substituted or unsubstituted C １～２０ Heteroalkyl, substituted or unsubstituted C ３～２０ Heterocycloalkyl, substituted or unsubstituted C ６～２０ Aryl, or substituted or unsubstituted C ３～２０ Heteroaryl, wherein the substituted C １～２０ Alkyl is nitro, cyano, hydroxy, carboxylic acid or its alkali metal salt or its ammonium salt, halogen, thiol, C １～６ Alkylthio, C １～６ Alkyl, C ２～６ Alkenyl, C ２～６ Alkynyl, C １～６ Haloalkyl, C １～９ Alkoxy, C １～６ Haloalkoxy, C ３～１２ Cycloalkyl, C ５～１８ Cycloalkenyl, C ２～１８ Heterocycloalkenyl, C ６～１２ Aryl, C having 1 to 3 separate or fused rings and 6 to 18 ring carbon atoms ７～１９ Aryl alkyl, C ７～１２ Alkylaryl, C ３～１２ Heterocycloalkyl, C ３～１２ or a combination thereof, １～２０ Heteroalkyl and the C ３～２０ Heterocycloalkyls each have heteroatoms independently selected from O, S, Si, P, or combinations thereof; Each R ４ are each independently 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 Heterocycloalkyl, substituted or unsubstituted C ６～２０ Aryl, or substituted or unsubstituted C ３～２０ is heteroaryl; Each R ４ As part of their structure, -O-, -C(O)-, -S-, -S(O) ２ -, and -N(R ２ａ )-(wherein, R ２ａ is hydrogen, substituted or unsubstituted C １～２０ Alkyl, substituted or unsubstituted C ３～２０ Cycloalkyl, or substituted or unsubstituted C ３～２０ heterocycloalkyl); R １ and R ２ may optionally together form a ring via a single bond or a divalent linking group; R ３ａ , R ３ｂ , or R ４ any two of may together optionally form a ring via a single bond or a divalent linking group; When n is 2 or more, any two R ４ the groups may optionally together form a ring via a single bond or a divalent linking group; m is an integer from 1 to 5; and n is an integer from 0 to 2m. and and a solvent.

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

3. The polymer has formula (2), (3), (4), (5), or (6): 【Chemistry 2】 and comprising an acid labile repeat unit derived from a monomer represented by one or more of the following formula: In the formulas (2) to (6), R ａ and R ｃ are each independently hydrogen, fluorine, cyano, or substituted or unsubstituted C １～１０ is alkyl; L １ is a divalent linking group; R ６ ~R １１ are each independently hydrogen, substituted or unsubstituted C １～２０ Alkyl, substituted or unsubstituted C ３～２０ Cycloalkyl, substituted or unsubstituted C ３～２０ Heterocycloalkyl, substituted or unsubstituted C ２～２０ Alkenyl, substituted or unsubstituted C ３～２０ Cycloalkenyl, substituted or unsubstituted C ３～２０ Heterocycloalkenyl, substituted or unsubstituted C ６～２０ Aryl, or substituted or unsubstituted C ３～２０ Heteroaryl, R ６ ~R １１ each may further optionally include a divalent linking group as part of their structure; However, R ６ ~R ８ At most one of R ６ ~R ８ When one of R is hydrogen, the other R ６ ~R ８ At least one of the following is substituted or unsubstituted C ６～２０ Aryl or substituted or unsubstituted C ３～２０ heteroaryl; ９ ~R １１ At most one of R ９ ~R １１ When one of R is hydrogen, the other R ９ ~R １１ At least one of the following is substituted or unsubstituted C ６～２０ Aryl or substituted or unsubstituted C ３～２０ is heteroaryl; R ６ ~R ８ any two of may optionally together form a ring, said ring may further optionally include a divalent linking group as part of its structure, said ring being substituted or unsubstituted; R ９ ~R １１ any two of may optionally together form a ring, said ring may further optionally include a divalent linking group as part of its structure, said ring being substituted or unsubstituted; R １２ , R １３ , R １８ , and R １９ are each independently hydrogen, substituted or unsubstituted C １～２０ Alkyl, substituted or unsubstituted C ３～２０ Cycloalkyl, substituted or unsubstituted C ３～２０ Heterocycloalkyl, substituted or unsubstituted C ６～２０ Aryl, or substituted or unsubstituted C ３～２０ Heteroaryl, R １２ , R １３ , R １８ , and R １９ each may further optionally include a divalent linking group as part of their structure; R １４ is a substituted or unsubstituted C １～２０ Alkyl, substituted or unsubstituted C ３～２０ Cycloalkyl, or substituted or unsubstituted C ３～２０ Heterocycloalkyl, R １４ may optionally further include a divalent linking group as part of its structure; R １２ ~R １４ any two of may optionally together form a ring, said ring may further optionally include a divalent linking group as part of its structure, said ring being substituted or unsubstituted; R １５ ~R １７ are each independently substituted or unsubstituted C １～２０ Alkyl, substituted or unsubstituted C ３～２０ Cycloalkyl, substituted or unsubstituted C ３～２０ Heterocycloalkyl, substituted or unsubstituted C ６～２０ Aryl, or substituted or unsubstituted C ３～２０ Heteroaryl, R １５ ~R １７ each may further optionally include a divalent linking group as part of their structure; However, R １５ ~R １７ At most one of R １５ ~R １７ When one of R is hydrogen, the other R １５ ~R １７ At least one of the following is substituted or unsubstituted C ６～２０ Aryl or substituted or unsubstituted C ３～２０ is heteroaryl; Any two R １５ ~R １７ may optionally be taken together to form a ring, said ring may further optionally include a divalent linking group as part of its structure, said ring being substituted or unsubstituted; R ２０ is a substituted or unsubstituted C １～２０ Alkyl, substituted or unsubstituted C ３～２０ Cycloalkyl, or substituted or unsubstituted C ３～２０ Heterocycloalkyl, R ２０ may optionally further include a divalent linking group as part of its structure; Any two R １８ ~R ２０ may optionally be taken together to form a ring, said ring may further optionally include a divalent linking group as part of its structure, said ring being substituted or unsubstituted; X ａ and X ｂ are each independently a polymerizable group selected from norbornyl or vinyl; n1 and n2 are each independently 0 or 1; and L ２ and L ３ are each independently a single bond or a divalent linking group, provided that X ａ When is vinyl, L ２ is not a single bond, and X ｂ When is vinyl, L ３ The photoresist composition of claim 1 or 2, wherein is not a single bond.

4. 1. A method for forming a pattern, comprising: Applying a layer of a photoresist composition according to any one of claims 1 to 3 to a substrate to provide a photoresist composition layer; patternwise exposing the photoresist composition layer to activating radiation to provide an exposed photoresist composition layer; developing said exposed photoresist composition layer to provide said pattern.

5. The method of claim 4 , wherein the photoresist composition layer has a thickness greater than 5 micrometers.

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