Electroactive compounds, compositions comprising the compounds, and methods of pattern forming

Abstract

The present application relates to an electroactive compound, a composition comprising the same, and a pattern forming method, and more particularly, to a composition comprising an acid-sensitive polymer comprising a first repeating unit derived from a monomer containing an acid-decomposable group; a photoacid generator compound; a non-polymeric electron acceptor compound, the non-polymeric electron acceptor compound having an electron affinity greater than that of the photoacid generator compound, where the non-polymeric electron acceptor compound does not generate a photoacid, and where the non-polymeric electron acceptor compound does not include a plurality of diazonaphthoquinone (DNQ) groups; and a solvent, where the solvent is present in the composition in an amount greater than 50% by weight, based on the total weight of the composition, where the composition is a positive EUV photoresist or an electron beam photoresist.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority and all benefits to U.S. Provisional Patent Application Serial No. 63 / 699,950, filed on September 27, 2024, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This invention relates to electroactive compounds for use in compositions (including photoresist compositions) and methods for forming patterns using the compositions. This invention is applicable to photolithography applications in the semiconductor manufacturing industry. Background Technology

[0004] Photoresist materials are photosensitive compositions typically used to transfer patterns onto 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 allow for the formation of nanoscale structures, photoresists and photolithography tools with high-resolution capabilities have been and will continue to be developed.

[0005] Chemically magnified photoresists are commonly used for high-resolution processing. These photoresists typically employ polymers with acid-indestabilized groups, photoacid generators, and acid quenchers. Exposure to activating radiation through a photomask in a pattern-wise manner causes the acid generator to form acid, which, during post-exposure baking, breaks down the acid-indestabilized groups in the exposed regions of the polymer. Acid quenchers are often added to the photoresist composition to control acid diffusion into unexposed areas, thereby improving contrast. The result of the photolithography process is a difference in the solubility characteristics of the exposed and unexposed regions of the photoresist in the developer solution. In positive development (PTD) processes, the exposed regions of the photoresist layer are soluble in the developer and removed from the substrate surface, while the unexposed regions, insoluble in the developer, remain after development, forming a positive image. The resulting relief image allows for selective processing of the substrate.

[0006] Extreme ultraviolet lithography (EUVL) is an optical lithography technique that images the most critical tiny feature patterns used in advanced integrated circuits. The semiconductor industry has adopted EUVL as the preferred patterning technique for printing critical features on contact layers, via layers, wire layers, and dicing layers in devices at 7nm and smaller nodes. For example, dicing can be applied to FinFETs, nanosheet FETs, or wires. Single-exposure EUV enables chipmakers to pattern the most challenging features at the 5nm node. Significant advancements in EUV technology over the past few years have enabled acceptable throughput using scanners such as ASML's EUV NXE:3400C (including a 0.33 NA scanner). Extending 0.33 NA EUV single-exposure patterning to 3nm and smaller nodes requires continued advancements in photoresist technology. For the continuation of advanced patterning techniques, the development of lithographic patterning solutions that support high NA EUV is crucial. As the industry anticipates the realization of high NA (0.55 NA) EUV, the demand for new materials is further increasing. These key materials, including photoresists, underlayers, and rinsing materials, will help the industry surpass current requirements for resolution, linewidth roughness, and sensitivity in modern photoresists, while also meeting targets for random and non-random defects and etched pattern transfer. Balancing these properties is a challenge for the entire industry. Developing new chemical materials, new formulation strategies, and understanding their fundamentals are crucial to breaking this trade-off and extending Moore's Law to next-generation devices. Summary of the Invention

[0007] One aspect provides a composition comprising an acid-sensitive polymer comprising a first repeating unit derived from a monomer containing an acid-degradable group; a photoacid-generating compound; a non-polymeric electron acceptor compound having a greater electron affinity than the photoacid-generating compound, wherein the non-polymeric electron acceptor compound does not generate photoacids, and wherein the non-polymeric electron acceptor compound does not contain a plurality of diazonaphthoquinone (DNQ) groups; and a solvent, wherein the solvent is present in the composition in an amount greater than 50% by weight based on the total weight of the composition, wherein the composition is a positive EUV photoresist or an electron beam photoresist.

[0008] On the other hand, a pattern forming method is provided, comprising (a) applying a composition layer on a substrate; soft baking the composition layer; exposing the soft-baked composition layer to EUV or electron beam activation radiation; post-baking the composition layer; and developing the post-baked composition layer to provide a photoresist relief image. Detailed Implementation

[0009] Reference will now be made in detail to exemplary embodiments, examples of which are illustrated in this specification. In this regard, exemplary embodiments of this disclosure may take different forms and should not be construed as limiting to the description presented herein. Therefore, only exemplary embodiments are described below to explain aspects of this specification. The term “and / or” as used herein includes any combination of one or more of the listed related entries, as well as all combinations thereof. When a statement such as “at least one of…” follows a series of elements, the statement modifies the series of elements rather than a single element within the series.

[0010] As used herein, the terms “a,” “an,” and “the / described” do not indicate a limitation of quantity and should be interpreted to encompass both the singular and plural unless otherwise stated herein or clearly contradicted by the context. Unless otherwise expressly stated, “or” means “and / or.” The quantity-related modifier “about” includes a prescribed value and has a meaning determined by the context (e.g., including the degree of error associated with a particular quantity of measurement). All scopes disclosed herein include endpoints, and endpoints may be combined independently with each other. The suffix “(a plurality)(s)” is intended to include both the singular and plural forms of the terms it modifies, thereby including at least one of those terms. “Optional” or “optionally” means that an event or situation subsequently described may or may not occur, and the description includes both the occurrence and non-occurrence of the event. Terms such as “first,” “second,” etc., used herein do not indicate order, quantity, or importance, but are used to distinguish individual elements. When an element is mentioned as being “above” another element, it may be in direct contact with the other element or there may be an intermediate element between them. Conversely, when an element is mentioned as being “directly above…(another element)”, there is no intermediate element. It should be understood that the components, elements, limitations and / or features of the described aspects can be combined in any suitable manner in the aspects.

[0011] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. It should also be understood that terms (e.g., those defined in common dictionaries) should be interpreted as having the same meaning as they have in the relevant field and in the context of this disclosure, and should not be interpreted in an idealized or overly formal sense unless expressly defined herein.

[0012] As used herein, "actinic ray" or "radiation" refers to, for example, the bright-line spectrum of a mercury lamp, far-ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and particle rays such as electron beams and ion beams. Furthermore, in this invention, "light" refers to actinic ray or radiation. A krypton fluoride laser (KrF laser) is a special type of excimer laser, sometimes also called an exciplex laser. "Excimer" is an abbreviation for "excited dimer," and "exciplex" is an abbreviation for "excited complex." Excimer lasers use a mixture of rare gases (argon, krypton, or xenon) and halogen gases (fluorine or chlorine) to emit coherent stimulated emission (laser) in the ultraviolet range under appropriate electrical stimulation and high-voltage conditions. In addition, unless otherwise specified, “exposure” in this instruction manual includes not only exposure using mercury lamps, far-ultraviolet light (represented by excimer lasers), X-rays, and extreme ultraviolet light (EUV light), but also writing using particle rays such as electron beams and ion beams.

[0013] As used herein, an "organic group" includes one or more carbon atoms, for example, 1 to 60 carbon atoms. The term "hydrocarbon" refers to an organic compound or organic group having at least one carbon atom and at least one hydrogen atom. The term "alkyl" refers to a straight-chain or branched saturated hydrocarbon group having a specified number of carbon atoms and being monovalent; "alkylene" refers to a divalent alkyl group; "hydroxyalkyl" refers to an alkyl group substituted with at least one hydroxyl group (-OH); "alkoxy" refers to "alkyl-O-"; "carboxyl" 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, all of which are carbon atoms; "cycloalkylene" refers to a divalent cycloalkyl group; "alkenyl" refers to a straight-chain or branched monovalent hydrocarbon group having at least one carbon-carbon double bond; "alkenoxy" refers to "alkenyl-O-"; "alkenyl" refers to a divalent alkenyl group; "cycloalkenyl" refers to a group having at least three carbon atoms and at least one carbon atom. A non-aromatic cyclic divalent hydrocarbon group with a 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 system that satisfies Hückel's rule and contains a carbon atom in the ring, and may optionally contain one or more heteroatoms selected from N, O, and S replacing the carbon atom in the ring; "aryl" refers to a monovalent aromatic monocyclic or polycyclic system in which each ring member is carbon, and may include a group in which the aromatic ring is fused with at least one cycloalkyl or heterocyclic alkyl ring; "arylene" refers to a divalent aryl; "alkanearyl" refers to an aryl group substituted with an alkyl group; "aranealkyl" refers to an alkyl group substituted with an aryl group; "aryloxy" refers to "aryl-O-"; "arylthio" refers to "aryl-S-".

[0014] The prefix "hetero" indicates that a compound or group contains at least one heteroatom (e.g., 1, 2, 3, or 4 or more heteroatoms) replacing a carbon atom, wherein each heteroatom is independently N, O, S, Si, or P; "heteroatom-containing group" refers to a substituent containing at least one heteroatom; "heteroalkyl" refers to an alkyl group having 1 to 4 or more heteroatoms replacing carbon; "heterocyclic alkyl" refers to a cycloalkyl group having 1 to 4 or more heteroatoms replacing carbon as ring members; "heterocyclic alkylene" refers to a divalent heterocyclic alkyl group; "heteroaryl" refers to an aryl group having 1 to 4 or more heteroatoms replacing carbon as ring members; "heteroarylene" refers to a divalent heteroaryl group.

[0015] Unless otherwise expressly stated, each of the above substituents may optionally be substituted. For example, when referring to a group, if it is not specified whether it is substituted, the group includes both unsubstituented groups and substituented groups. The term "optionally substituted" means substituted or unsubstituted.

[0016] "Substitution" refers to the substitution of at least one hydrogen atom in a chemical structure by another terminal substituent, usually monovalent, provided that the normal valence state of the specified atom is not exceeded. When the substituent is oxo (i.e., =O), the two host hydrogen atoms on the carbon atom are replaced by a terminal oxo group. Combinations of substituents or variations are permitted. Exemplary substituents that may appear at the "substitution" position include, but are not limited to, nitro (-NO2), cyano (-CN), hydroxyl (-OH), oxo (=O), amino (-NH2), mono- or di-(C) 1-6 )alkylamino, alkanoyl (e.g., C 2-6 Alkyl groups, such as acyl groups, formyl groups (-C(=O)H), carboxylic acids or their alkali metal or ammonium salts; esters (including acrylates, methacrylates and lactones), such as C 2-6 Alkyl esters (-C(=O)O-alkyl or -OC(=O)-alkyl) and C 7-13 Aryl esters (-C(=O)O-aryl or -OC(=O)-aryl), amide groups (-C(=O)NR2, where R is hydrogen or C... 1-6 alkyl), formamido (-CH2C(=O)NR2, where R is hydrogen or C 1-6 Alkyl groups, halogens, thiols (-SH), C 1-6 Alkylthio (-S-alkyl), thiocyano (-SCN), C 1-6 Alkyl, C 2-6 alkenyl, C 2-6 alkynyl group, C 1-6 Haloalkyl, C 1-9 Alkoxy, C 1-6 Halogenated alkoxy groups, C 3-12 cycloalkyl, C 5-18Cycloalkenyl, C 2-18 Heterocyclic alkenyl groups, having at least one aromatic ring, C 6-12 Aryl groups (e.g., phenyl, biphenyl, naphthyl, etc., each ring being a substituted or unsubstituted aromatic ring), having 1 to 3 independent or fused rings and containing 6 to 18 ring carbon atoms, are C14 groups. 7-19 Aryl alkyl groups, arylalkoxy groups having 1 to 3 free or fused rings and containing 6 to 18 ring carbon atoms, C 7-12 Alkyl, C 3-12 Heterocyclic alkyl, C 3-12 heteroaryl, C 1-6 alkylsulfonyl (-S(=O)2-alkyl), C 6-12 Arylsulfonyl (-S(=O)2-aryl) or toluenesulfonyl (CH3C6H4SO2-).

[0017] The term "halogen" refers to a monovalent substituent, namely fluorine (fluorinated), chlorine (chloroinated), bromine (brominated), or iodine (iodinated). The prefix "halo" refers to a group containing one or more fluorine, chlorine, bromine, or iodine substituents that replace a hydrogen atom. Halogenated groups can exist in combination (e.g., bromine and fluorine) or only as fluorine groups. For example, the term "haloalkyl" refers to an alkyl group substituted with one or more halogens. As used herein, "substituted C" refers to an alkyl group substituted with one or more halogens. 1-8 "Haloalkyl" refers to a C18 alkyl group that is substituted with at least one halogen and also with one or more other non-halogen substituents. 1-8 alkyl.

[0018] As used herein, an "acid-indestructible group" refers to a group whose bond breaks under the influence of an acid, optionally and usually by means of heat treatment, resulting in the formation of a polar group, such as a carboxylic acid or alcohol group, on the polymer, optionally and usually, the portion connected to the broken bond detaches from the polymer. As used herein, the term "acid-degradable group" is synonymous with an acid-indestructible group. In other systems, nonpolymeric compounds may contain acid-indestructible groups that break under the influence of an acid, resulting in the formation of a polar group, such as a carboxylic acid or alcohol group, on the broken portion of the nonpolymeric compound. Such acids are typically photoacidogenic, with bond breaking occurring during post-exposure baking (PEB); however, implementation is not limited to this, for example, the acid may also be thermally acidogenic. Suitable acid-indestructible groups include, for example: tertiary alkyl esters, secondary aryl esters or tertiary aryl esters, secondary or tertiary esters having an alkyl and aryl combination, tertiary alkoxy groups, tertiary carbonate groups, acetal groups or ketal groups. In this field, acid-instable groups are also commonly referred to as "acid-crackable groups", "acid-crackable protecting groups", "acid-instable protecting groups", "acid-leaving groups", "acid-decomposable groups" and "acid-sensitive groups".

[0019] As used herein, unless otherwise defined, "divalent linker" means a divalent group comprising one or more of the following: -O-, -S-, -Te-, -Se-, -C(O)-, -C(O)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 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 heteroaryl, or combinations thereof, wherein R a C is hydrogen, substituted or unsubstituted 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Heteroaryl groups. Typically, the divalent linking group comprises one or more of the following: -O-, -S-, -C(O)-, -C(O)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 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 heteroaryl, or combinations thereof, wherein R a C is hydrogen, deuterium, substituted or unsubstituted. 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Heteroaryl groups. More typically, the divalent linking group comprises at least one of the following: -O-, -C(O)-, -C(O)O-, -N(R a )-、-C(O)N(R a -, substituted or unsubstituted C 1-10 Alkylene, substituted or unsubstituted C 3-10 Cycloalkylene, substituted or unsubstituted C 3-10 Heterocyclic alkyl, substituted or unsubstituted C 6-10 aryl, substituted or unsubstituted C 3-10 heteroaryl, or combinations thereof, wherein R a C is hydrogen, deuterium, substituted or unsubstituted. 1-10 Alkyl, substituted or unsubstituted C1-10 Heteroalkyl, substituted or unsubstituted C 6-10 aryl, or substituted or unsubstituted C 3-10 Mixed aromatic compounds.

[0020] As mentioned above, chemically amplified photoresists have been a key technology (workhouse) for high-resolution patterning in semiconductors for many years. This method uses photoacids generated by radiation exposure to remove the protection of leaving groups on polymer chains, and regenerates them in multiple cycles to further remove the protection of other leaving groups. This creates a solubility transition between exposed and unexposed areas of the substrate coating. Traditionally, chemically amplified photoresists operate based on the principle of acid diffusion to significantly improve the sensitivity of the photoresist. Deep UV photoresist products and low-NA EUV photoresists still use chemical materials based on chemically amplified photoresists. Controlling the photoacid diffusion length is crucial for performance, as excessive acid diffusion can lead to blurred images or patterns and reduce their roughness and resolution.

[0021] EUV patterning presents additional challenges due to its unique photochemical mechanism. During EUV exposure, when 92 eV photons (13.5 nm) are initially absorbed by the photoresist composition, they primarily cause ionization of the polymer matrix, subsequently generating primary electrons. These primary electrons are high-energy and can further excite the matrix, generating further secondary electrons, including thermally heated low-energy secondary electrons. These thermally heated low-energy secondary electrons essentially undergo an irreversible reaction with the photoacid-producing agent (PAG) component, leading to PAG decomposition and the release of photoacid. Therefore, to improve the sensitivity of EUV photoresists, PAG components with higher electron affinity (or higher reduction potential) can be selected to facilitate the addition of secondary electrons. Furthermore, the high energy of EUV radiation means that the number of EUV photons is scarce at typical photoresist exposure doses. Therefore, a high EUV absorption cross-section of the photoresist composition is a useful factor in photoresist design and component selection.

[0022] In EUV chemically amplified photoresists, the involvement of secondary electrons in the acid generation pathway presents additional challenges. Electron blurring can be significant because the electron thermal distance (the total distance an electron travels in a random-walk model after generation and before quenching or reaction with PAG) in EUV photoresists averages 3–7 nm in organic polymer matrices. It can also be expressed as secondary electron diffusion, referring to the scattering and movement of secondary electrons generated when EUV photons interact with the photoresist material. Because these secondary electrons can diffuse beyond the intended exposure area, they blur feature edges, significantly impacting the accuracy of the final pattern. Increasing photoresist film density (e.g., metal oxide photoresists) can help suppress secondary electron blurring. However, low-density films made from chemically amplified photoresist materials are considered to have higher electron blurring, which is necessary to match the roughness levels required for high-resolution features in EUV patterning.

[0023] This invention addresses the challenge of electron blurring by providing electron blur control additives. These additives are non-polymeric electron acceptor compounds used in EUV photoresists or electron beam compositions (including organic, inorganic, and metallic photoresists). By using electron acceptor compounds to control the randomness of electron blurring, the resolution and roughness of printed features are inherently improved. In chemically amplified EUV photoresists or electron beam photoresists, the disclosed non-polymeric electron acceptor compound additives have higher electron affinity (or higher reduction sites) than existing photoacid-generating compounds. Therefore, they preferentially quench secondary electrons before reacting with PAG compounds, effectively improving deprotection contrast and thus enhancing lithography performance.

[0024] Unrestricted by theory, the mechanism of secondary electron acceptors or quenchers mimics the photoacid diffusion control of alkaline quencher additives in traditional chemically amplified photoresist systems used for deep UV lithography. Conceptually, introducing secondary electron quencher components into the formulation to annihilate rapidly diffusing electrons can essentially control electron blurring, thereby improving contrast and ultimately enhancing resolution and roughness.

[0025] As used in this article, "reduction potential" represents the affinity of a material for accepting electrons. It can be measured using cyclic voltammetry (Ereduction potential). o’The reduction potential is estimated using cyclic voltammetry with the acceptor compound, via the cathode peak potential. In typical cyclic voltammetry measurements, each material is dissolved in a distilled and dried solvent (e.g., anhydrous acetonitrile) to prepare a 1 mM redox molecular solution for measurement. An electrolyte solution (e.g., 0.1 M tetrabutylammonium perchlorate solution) is used as the supporting electrolyte. For electrodes, a 4 mm Pt disk, wound Pt wire, and an Ag / AgCl electrode can be used as the working electrode, counter electrode, and reference electrode, respectively. Before electrochemical measurements, the solution is purged with N2 gas for 5–10 minutes to displace dissolved O2. Measurements are typically performed at room temperature at the desired scan rate.

[0026] As used herein, “electron affinity” refers to the affinity of a material for accepting electrons. Electron affinity can be calculated by forming a sample layer on a quartz substrate. Subsequently, the absorption spectrum of the prepared sample can be measured using a spectrophotometer, and the optical band gap can be calculated based on the absorption edge of the resulting absorption spectrum. Electron affinity can be estimated by the difference between the obtained ionization potential and the calculated optical band gap.

[0027] The ionization potential can be measured as follows: A sample is formed on a glass substrate with an ITO film. Subsequently, the number of photoelectrons is measured in air using photoelectron emission spectroscopy. The energy of ultraviolet radiation is varied, and the energy position at which the first photoelectron is detected is assumed to be the ionization potential.

[0028] Quantum chemical calculations were used to estimate the key electronic properties of the molecules used in the compositions described herein. These calculations utilize the laws of quantum mechanics to accurately predict the properties of the molecules. Those skilled in the art can use quantum chemical calculations to gain a detailed understanding of the electronic structure of the molecules and how that structure affects their overall properties. Quantum chemical calculations were used to calculate the lowest unoccupied molecular orbital (LUMO) energies. Density functional theory (DFT) calculations were performed at the B3LYP level using the 6-31+G(d,p) basis set, based on the Gaussian 16 software package. Using DFT, the molecular geometry was first optimized and confirmed. Typically, vibrational frequency analysis is used to determine the lowest energy geometry. After optimization, a DFT output file containing the molecular orbital energies was obtained.

[0029] Quantum chemical calculations can also be used to estimate the reduction potential of molecules. The calculation method specified in J. Phys. Chem. C 2014, 118, 12, 6046–6051 is well-suited for calculating the reduction potential of organic compounds. Using this method, density functional theory (DFT) calculations were performed to confirm the overall minimum energy structure. Each molecule in solution was modeled using a polarizable continuum (PC) model and a solvent (e.g., propylene carbonate). The DFT calculations were used to calculate the energies before and after electron addition (reduction). These calculated energies were then used to calculate the reduction reaction free energy ΔG. The formal potential E of the molecule was calculated from the reaction free energy difference ΔG using ΔG = nFE, where n is the number of electrons transferred and F is the Faraday constant. This calculation yielded E as a function of vacuum, which was then converted to a reference value for Ag / AgCl.

[0030] Quantum chemical calculations can also be used to estimate the electron affinity of PAG cations and electron acceptor additive compounds. Electron affinity is defined as the energy released when an electron is added to a molecule. Typically, vibrational frequency analysis is used to determine the overall lowest-energy geometry. The energy calculated from the optimized structure is used to calculate the adiabatic electron affinity. In cases where the geometry cannot be optimized (e.g., for unstable radicals), the vertical electron affinity is calculated. For neutral molecules, the electron affinity is calculated as the energy difference between the neutral form and the form produced after adding an electron (i.e., the corresponding anionic radical form). For positively charged substances (e.g., a +1 sulfonium cation), its vertical electron affinity is calculated as the energy difference between the +1 cation and the radical form produced after adding an electron.

[0031] In this paper, materials that donate electrons to another molecule or chemical substance during a chemical reaction are called electron donor materials, and materials that accept electrons from another molecule or chemical substance during a chemical reaction are called electron acceptor materials. When using two different types of organic materials, the relative positions of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels at the interface between the two organic materials are usually used to determine which material acts as the donor and which material acts as the acceptor. The energy difference between the vacuum level (0 eV) and the LUMO level is related to the electron affinity. Generally, the lower the LUMO level, the stronger the electron acceptance ability. In addition, the energy difference between the vacuum level and the HOMO level is related to the ionization potential; the higher the HOMO energy, the stronger the electron donation ability.

[0032] The inventors have discovered that EUV and electron beam photoresist compositions exhibit excellent photolithographic properties when highly efficient non-polymerized secondary electron acceptor compounds with electron affinity higher than those of photoacid-producing compounds are added to the composition. The inventors have also discovered that "rapidly diffused" secondary electrons diffusing into unexposed areas can be annihilated (or quenched) before reacting with PAG cations to generate photoacids, leading to undesirable deprotection of the photoresist leaving groups. Materials with lower LUMO levels (i.e., higher electron affinity and reduction potential) are used as electron acceptor materials.

[0033] This document provides a composition comprising an acid-sensitive polymer, said acid-sensitive polymer comprising a first repeating unit derived from a monomer containing an acid-degradable group. The composition comprises a photoacid-generating compound. The composition comprises a non-polymeric electron acceptor compound having a greater electron affinity than the photoacid-generating compound, wherein said non-polymeric electron acceptor compound does not generate photoacids, and wherein said non-polymeric electron acceptor compound does not contain a plurality of diazonoquinone (DNQ) groups. The composition further comprises a solvent, said solvent being present in the composition in an amount greater than 50 weight percent (wt%) based on the total weight of the composition. The composition is a positive EUV photoresist or an electron beam photoresist.

[0034] Non-polymeric electron acceptor compounds have a greater electron affinity than photoacid-producing agents (or, in the case of ionic photoacid-producing agents, a greater electron affinity than the cation of the photoacid-producing agent). Furthermore, non-polymeric electron acceptor compounds do not produce photoacids upon exposure to EUV radiation or electron beams, and do not contain multiple DNQ groups. The electron affinity of PAG compounds can be determined based on the structure of the PAG compound. For example, a non-polymeric electron acceptor compound may have a greater electron affinity than the cation of the photoacid-producing agent compound, or a greater electron affinity than the zwitterionic portion of the photoacid-producing agent compound, or a greater electron affinity than the overall structure of the non-ionic photoacid-producing agent compound. As used herein, photoacid-producing compounds may have multiple active sites, such as multiple electronically reactive cations. Photoacid-producing compounds can be small molecule compounds or polymeric compounds.

[0035] In some embodiments, the non-polymeric electron acceptor compound has a greater electron affinity than triphenylsulfonium, such as substituted triphenylsulfonium. In some embodiments, the non-polymeric electron acceptor compound has a greater electron affinity than diphenyliodonium, such as substituted diphenyliodonium.

[0036] Nonpolymeric electron acceptor compounds contain conjugated organic groups and can be substituted by conjugation with one or more electron-withdrawing groups. Conjugated organic compounds or structures are a class of organic molecular structures in which alternating single and double bonds exist between carbon atoms and / or other atoms. In some embodiments, nonpolymeric electron acceptor compounds contain conjugated organic groups but do not further contain electron-withdrawing groups. Exemplary conjugated organic groups include vinyl, 1,3-butadienyl, ethynyl, carbonyl, 1,3-butadienyl, and combinations thereof. Other exemplary conjugated organic groups include aromatic and heteroaromatic groups, such as those having five-membered or six-membered rings or combinations thereof. Examples of suitable groups include five-membered or six-membered rings, or combinations of rings, with or without heteroatoms. Another class of conjugated organic groups that can be used in this invention are aromatic quinones, particularly substituted or unsubstituted benzoquinones or naphthoquinones. Quinones can be alkyl, alkoxy, hydroxyl, halogen, nitro, or cyano-substituted benzoquinones or naphthoquinones or combinations thereof. Other examples of quinone groups include dichlorocyanobenzoquinone, cyanoquinone, chloroquinone, bromoquinone, and tetracyanobenzoquinone dimethane. Examples of other conjugated organic groups include, but are not limited to, groups derived from: tetracyanoethylene, fluorenones or fluorenones substituted with electron-withdrawing groups (e.g., 2-nitrofluorenone, 2,7-dinitrofluorenone, 2,4,7-trinitrofluorenone), fullerenes and their derivatives, porphyrins and their derivatives, phthalocyanines and their derivatives, pyridinium salts, etc. Exemplary electron-withdrawing groups include, but are not limited to, cyano (including C(CN)2 and N-CN), pyridinium, oxo, nitro, halogen, haloalkyl, ester, sulfone, sulfonamide, sulfonylimide, phthalimide, and naphthalimide. Combinations of one or more different electron-withdrawing groups may be used. In some embodiments, the structure of the conjugated organic group may include an electron-withdrawing group. In some embodiments, the conjugated organic group may contain a cationic atom, such as a nitrogen cation, which is considered to be an electron-withdrawing group in the conjugated organic group.

[0037] Other examples of nonpolymeric electron acceptor compounds include ammonium salts (substituted or unsubstituted) that have a greater electron affinity than photoacidogens.

[0038] In some embodiments, the nonpolymeric electron acceptor compound may comprise one or more compounds represented by formulas (1) to (5):

[0039]

[0040] In equations (1) to (5), R 1 To R 25 R 20a and R 21a Each is independently hydrogen, deuterium, halogen, nitro, amino, cyano, pyridinium, substituted or unsubstituted C.1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 1-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 Aryl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 2-30 heteroaryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 3-30 Alkyl heteroaryl. In some embodiments, R 1 To R 25 R 20a and R 21a Each can be independently hydrogen, deuterium, or carbon. 1-4 Alkyl, cyano, pyridinium, nitro or C 1-4 Fluoroalkyl groups. Typically, R... 1 To R 25 R 20a and R 21a Each is independently hydrogen, substituted or unsubstituted C 1-4 Alkyl, or substituted or unsubstituted C 1-4 Fluoroalkyl groups.

[0041] In equations (1) to (5), R 1 To R 25 R 20a and R 21a Optionally, it also includes one or more divalent linking groups as part of its structure. Exemplary divalent linking groups may be selected from the following group: -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R ’ -, -C(O)N(R')-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 heteroaryl, or combinations thereof, wherein R ’ C is hydrogen, deuterium, substituted or unsubstituted. 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Mixed aromatic compounds.

[0042] In equation (1), two or more adjacent R 1 To R 10 Optionally, rings are formed between each other by divalent linking groups, wherein each of one or more divalent linking groups is substituted or unsubstituted, and wherein the rings are substituted or unsubstituted.

[0043] In equation (1), L 1 It can be a single bond or a divalent linker. Exemplary divalent linkers can be selected from the following group: -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R ’ -, -C(O)N(R')-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 heteroaryl, or combinations thereof, wherein R ’ It can be hydrogen, deuterium, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 heteroaryl. For example, L 1 C can be a single bond, substituted, or unsubstituted. 6-30 aryl or substituted or unsubstituted C 3-30 Hybrid aryl.

[0044] In equation (2), two or more adjacent R 11 To R 19 Optionally, rings are formed between each other by divalent linking groups, wherein each of one or more divalent linking groups is substituted or unsubstituted, and wherein the rings are substituted or unsubstituted.

[0045] In equation (2), L 2 It can be a single bond or a multivalent linker. Exemplary divalent linkers can be selected from the following group: -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R ’ -, -C(O)N(R')-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 heteroaryl, or combinations thereof, wherein R’ It can be hydrogen, deuterium, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Heteroaryl groups. When the group is polyvalent, it is divalent or higher. For example, L... 2 Can be a single bond, substituted or unsubstituted polyvalent C 6-30 aryl or substituted or unsubstituted polyvalent C 3-30 Hybrid aryl.

[0046] In equation (2), p is an integer from 2 to 6. p is an integer from 2 to 4.

[0047] In equations (1) and (2), A - and B - Each is an organic anion independently, of which A - and B - Optional linkages are made to form divalent organic anions. Exemplary organic anions include those whose conjugate acid typically has a pKa of -15 to 10. For example, A - and B - They can be sulfonate, carboxylate, sulfonamide anion, sulfonamide anion, or methyl anion, each independently.

[0048] In equation (3), two or more adjacent R 20 Optionally, rings are formed between each other by divalent linking groups, wherein each of one or more divalent linking groups is substituted or unsubstituted, and wherein the rings are substituted or unsubstituted.

[0049] In equation (3), n1 is an integer from 0 to 4. Preferably, n1 is 0 or 1.

[0050] In equation (3), X is a single bond or one or more divalent linking groups. Each of the one or more divalent linking groups may be substituted or unsubstituted. Exemplary divalent linking groups may be independently selected from the group consisting of: -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -S(O)2-, -N(R ’ -, -C(O)N(R')-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 heteroaryl, or combinations thereof, wherein R ’ It can be hydrogen, deuterium, substituted or unsubstituted C1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 heteroaryl. Typically, X can be a single bond or a substituted or unsubstituted C. 1-20 Alkylene, preferably with a single bond or substituted or unsubstituted C. 1-10 Alkylene.

[0051] In equation (4), A - These are organic anions. Exemplary organic anions include those whose conjugate acid has a pKa typically between -15 and 10. For example, A - It can be a sulfonate, carboxylate, sulfonamide anion, sulfonamide anion, or methyl anion.

[0052] In equation (4), n2 is an integer from 0 to 5. Usually, n2 is 0 or 1.

[0053] In equation (4), two or more adjacent R 21 Optionally, rings are formed between each other by divalent linking groups, wherein each of one or more divalent linking groups is substituted or unsubstituted, and wherein the rings are substituted or unsubstituted.

[0054] In equation (5), two or more R 22 To R 25 Optionally, they form rings with each other via divalent linking groups, wherein the divalent linking groups are substituted or unsubstituted, and wherein the rings are substituted or unsubstituted.

[0055] In equation (5), A - These are organic anions. Exemplary organic anions include those whose conjugate acid has a pKa typically between -15 and 10. For example, A - It can be a sulfonate, carboxylate, sulfonamide anion, sulfonamide anion, or methyl anion.

[0056] In some embodiments, the nonpolymeric electron acceptor compound may comprise one or more compounds of formulas (6) to (26):

[0057]

[0058]

[0059]

[0060] In equations (6) to (26), R 26 To R 81 Each is independently hydrogen, deuterium, halogen, nitro, amino, cyano, pyridinium, substituted or unsubstituted C.1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 1-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 Aryl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 2-30 heteroaryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 3-30 Alkyl heteroaryl. Typically, R... 26 To R 81 Each is independently hydrogen, deuterium, halogen, 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 1-20 Heterocyclic alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 Alkyne, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 Aryl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 2-30 heteroaryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 3-30 Alkyl heteroaryl.

[0061] In equations (6) to (26), R 26 To R 81 Each of these may optionally also include one or more divalent linking groups as part of its structure. Exemplary divalent linking groups may be selected from the following group: -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R ’ -, -C(O)N(R')-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 heteroaryl, or combinations thereof, wherein R ’ It can be hydrogen, deuterium, substituted or unsubstituted C 1-20Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Mixed aromatic compounds.

[0062] In equation (6), two or more adjacent R 26 To R 31 Optionally, a ring is formed between each other by one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0063] In equation (7), two or more adjacent R 32 To R 36 Optionally, a ring is formed between each other by one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0064] In equation (7), X - These are organic anions. Exemplary organic anions include those whose conjugate acid has a pKa typically between -15 and 10. For example, X - It can be a sulfonate, carboxylate, sulfonamide anion, sulfonamide anion, or methyl anion.

[0065] In equation (8), two or more adjacent R 37 To R 40 Optionally, a ring is formed between the rings via one or more divalent linking groups, each of which is substituted or unsubstituted, and the ring is substituted or unsubstituted. The ring may be aromatic or non-aromatic.

[0066] In formula (8), Y and Z each independently contain an electron-withdrawing group. Exemplary electron-withdrawing groups include, but are not limited to, cyano (including C(CN)2 and N-CN), pyridinium, oxo, nitro, thiol, disulfide, halogen, haloalkyl, ester, sulfone, sulfonamide, sulfonylimide, phthalimide, and naphthalimide.

[0067] In equation (9), two or more adjacent R 41 To R 46 Optionally, rings are formed between each other via one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted. For example, two or more adjacent R... 41 To R 43Optionally, rings are formed between each other via one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted; and / or two or more adjacent R 44 To R 46 Optionally, a ring is formed between each other by one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0068] In equation (10), two or more adjacent R 47 To R 51 Optionally, a ring is formed between each other by one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0069] In equation (11), R 52 and R 53 They can form rings without being linked together by connecting groups.

[0070] In equation (12), two or more adjacent R 54 To R 55 Optionally, rings are formed between each other via one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted. For example, two or more adjacent R... 54 Optionally, rings are formed between each other via one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted; and / or two or more adjacent R 55 Optionally, a ring is formed between each other by one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0071] In formula (12), X contains an electron-withdrawing group. Exemplary electron-withdrawing groups include, but are not limited to, cyano (including C(CN)2 and N-CN), pyridinium, oxo, nitro, thiol, disulfide, halogen, haloalkyl, ester, sulfone, sulfonamide, sulfonylimide, phthalimide, and naphthalimide.

[0072] In equation (12), n1 and n2 are each an independent integer from 0 to 4. Typically, n1 and n2 are each an independent integer of 0 or 1.

[0073] In equation (13), two or more adjacent R 56 To R 57Optionally, rings are formed between each other via one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted. For example, two or more adjacent R... 56 Optionally, rings are formed between each other via one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted; and / or two or more adjacent R 57 Optionally, a ring is formed between each other by one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0074] In equation (13), n4 and n5 are each an independent integer from 0 to 2. Typically, n4 and n5 are each 0 or 1 independently.

[0075] In equation (14), two or more adjacent R 58 To R 59 Optionally, rings are formed between each other via one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted. For example, two or more adjacent R... 58 Optionally, rings are formed between each other via one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted; and / or two or more adjacent R 59 Optionally, a ring is formed between each other by one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0076] In equation (14), n6 and n7 are each an independent integer from 0 to 4. Typically, n6 and n7 are each 0 or 1 independently.

[0077] In equation (15), two or more adjacent R 60 To R 61 Optionally, rings are formed between each other via one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted. For example, two or more adjacent R... 60 Optionally, rings are formed between each other via one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted; and / or two or more adjacent R 61Optionally, a ring is formed between each other by one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0078] In equation (15), n8 and n9 are each an independent integer from 0 to 4. Typically, n8 and n9 are each 0 or 1.

[0079] In equation (16), two or more adjacent R 64 To R 65 Optionally, rings are formed between each other via one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted. For example, two or more adjacent R... 64 Optionally, rings are formed between each other via one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted; and / or two or more adjacent R 65 Optionally, a ring is formed between each other by one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0080] In equation (16), each I is an integer from 0 to 4. Typically, each I is 0 or 1 independently.

[0081] In equation (17), two or more adjacent R 68 Optionally, a ring is formed between each other by one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0082] In equation (17), I is an integer from 0 to 4. Usually, I is 0 or 1.

[0083] In equation (18), two or more adjacent R 70 Optionally, a ring is formed between each other by one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0084] In equation (18), I is an integer from 0 to 4. Usually, I is 0 or 1.

[0085] In equation (19), two or more adjacent R 71 Optionally, a ring is formed between each other by one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0086] In equation (19), I is an integer from 0 to 4. Usually, I is 0 or 1.

[0087] In equation (20), two or more adjacent R 73 Optionally, a ring is formed between each other by one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0088] In equation (21), two or more adjacent R 73 Optionally, a ring is formed between each other by one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0089] In equation (21), M is a transition metal. Exemplary transition metals include, but are not limited to, Cu, Zn, Co, Fe, Mn, etc. Typically, M is Zn.

[0090] In equation (22), two or more adjacent R 74 Optionally, a ring is formed between each other by one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0091] In equation (22), k is an integer from 0 to 30. Usually, k is 0 or 1.

[0092] In equation (23), two or more adjacent R 75 Optionally, a ring is formed between each other by one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0093] In equation (23), each p is an integer from 0 to 4. Typically, each p is either 0 or 1.

[0094] In equation (24), two or more adjacent R 76 To R 77 Optionally, rings are formed between each other via one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted. For example, two or more adjacent R... 76 Optionally, rings are formed between each other via one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted; and / or two or more adjacent R 77Optionally, a ring is formed between each other by one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0095] In equation (24), p is an integer from 0 to 4. Usually, p is 0 or 1. In equation (24), q is an integer from 0 to 5. Usually, q is 0 or 1.

[0096] In equation (25), two or more adjacent R 78 To R 79 Optionally, rings are formed between each other via one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted. For example, two or more adjacent R... 78 Optionally, rings are formed between each other via one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted; and / or two or more adjacent R 79 Optionally, a ring is formed between each other by one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0097] In formula (25), X and Y each independently contain an electron-withdrawing group. Exemplary electron-withdrawing groups include, but are not limited to, cyano (including C(CN)2 and N-CN), pyridinium, oxo, nitro, thiol, disulfide, halogen, haloalkyl, ester, sulfone, sulfonamide, sulfonylimide, phthalimide, and naphthalimide.

[0098] In equation (25), r is an integer from 0 to 4. Usually, r is 0 or 1. In equation (25), q is an integer from 0 to 5. Usually, q is 0 or 1.

[0099] In equation (26), two or more adjacent R 80 To R 81 Optionally, rings are formed between each other via one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted. For example, two or more adjacent R... 80 Optionally, rings are formed between each other via one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted; and / or two or more adjacent R 81 Optionally, a ring is formed between each other by one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0100] In formula (26), X and Y each independently contain an electron-withdrawing group. Exemplary electron-withdrawing groups include, but are not limited to, cyano (including C(CN)2 and N-CN), pyridinium, oxo, nitro, thiol, disulfide, halogen, haloalkyl, ester, sulfone, sulfonamide, sulfonylimide, phthalimide, and naphthalimide.

[0101] In equation (26), r is an integer from 0 to 4. Usually, r is 0 or 1. In equation (25), q is an integer from 0 to 5. Usually, q is 0 or 1.

[0102] For example, in some embodiments, the nonpolymeric electron acceptor compound comprises a compound represented by one of formulas (1), (8), or (9):

[0103]

[0104] Equations (1), (8) and (9) are as defined in this paper.

[0105] In some embodiments, the nonpolymeric electron acceptor compound may comprise a compound represented by one of formulas (27A) to (30A):

[0106]

[0107] In equation (27A), R 82 To R 83 Each is independently hydrogen, deuterium, halogen, nitro, amino, cyano, pyridinium, substituted or unsubstituted C. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 1-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 Aryl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 2-30 heteroaryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 3-30 Alkyl heteroaryl.

[0108] In equation (27A), R 82 To R 83Each of these may optionally also include one or more divalent linking groups as part of its structure. Exemplary divalent linking groups may be selected from the following group: -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R ’ -, -C(O)N(R')-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 heteroaryl, or combinations thereof, wherein R ’ It can be hydrogen, deuterium, 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 Mixed aromatic compounds.

[0109] In equation (27A), R 82 and R 83 Optionally, a ring is formed between each other by one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0110] In equation (27A), x is 1 or 2.

[0111] In equation (28A), R 84 To R 87 Each is independently hydrogen, deuterium, halogen, nitro, amino, cyano, pyridinium, substituted or unsubstituted C. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 1-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 Aryl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 2-30 heteroaryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 3-30 Alkyl heteroaryl.

[0112] In equation (28A), R 84 To R 87Each of these may optionally also include one or more divalent linking groups as part of its structure. Exemplary divalent linking groups may be selected from the following group: -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R ’ -, -C(O)N(R')-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 heteroaryl, or combinations thereof, wherein R ’ It can be hydrogen, deuterium, 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 Mixed aromatic compounds.

[0113] In equation (28A), two or more adjacent R 84 To R 87 Optionally, a ring is formed between each other by one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0114] In equation (29A), R 88 To R 91 Each is independently hydrogen, deuterium, halogen, nitro, amino, cyano, pyridinium, substituted or unsubstituted C. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 1-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 Aryl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 2-30 heteroaryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 3-30 Alkyl heteroaryl.

[0115] In equation (29A), R 88 To R 91Each of these may optionally also include one or more divalent linking groups as part of its structure. Exemplary divalent linking groups may be selected from the following group: -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R ’ -, -C(O)N(R')-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 heteroaryl, or combinations thereof, wherein R ’ It can be hydrogen, deuterium, 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 Mixed aromatic compounds.

[0116] In equation (29A), two or more adjacent R 88 To R 91 Optionally, a ring is formed between each other by one or more divalent linking groups, wherein each of the one or more divalent linking groups is substituted or unsubstituted, and wherein the ring is substituted or unsubstituted.

[0117] In equation (30A), R 92 and R 93 Each is independently hydrogen, deuterium, halogen, nitro, amino, cyano, pyridinium, substituted or unsubstituted C. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 1-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 Aryl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 2-30 heteroaryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 3-30 Alkyl heteroaryl.

[0118] In equation (30A), R 92 and R 93Each of these may optionally also include one or more divalent linking groups as part of its structure. Exemplary divalent linking groups may be selected from the following group: -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R ’ -, -C(O)N(R')-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 heteroaryl, or combinations thereof, wherein R ’ It can be hydrogen, deuterium, 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 Mixed aromatic compounds.

[0119] Non-limiting examples of nonpolymeric electron acceptor compounds include the following:

[0120]

[0121]

[0122]

[0123]

[0124] Electron acceptor compounds can accept one, two, or more electrons, depending on their molecular structure and redox properties. When an electron acceptor compound can accept up to two electrons, it is preferable that the electron affinity of the intermediate formed after the first electron transfer is higher than that of the photoacid-producing compound. This ensures that the second electron transfer is thermodynamically favorable and kinetically efficient, thereby promoting the complete reduction of the acceptor substance and thus more effectively quenching secondary electrons. Representative examples of such compounds are o-quinone derivatives. For example, in the case of benzoquinone, the initial acceptance of one electron forms a radical anion, which can then be further reduced by accepting a second electron to generate the corresponding divalent anion. This stepwise electron transfer mechanism is particularly advantageous in photochemical systems where controlling electron diffusion is crucial.

[0125] Preferred electron acceptor compounds are those capable of suppressing electron diffusion without affecting photoresist sensitivity. While the quenching of secondary electrons by electron acceptor compounds reduces the effective availability of thermally generated secondary electrons for photoacid generator (PAG) activation and acid formation, the electron acceptor compounds of this invention can lead to a higher dissolution rate in the photoresist exposure area. This enhanced dissolution rate compensates for the reduced acid formation, thereby improving overall sensitivity. Therefore, photoresist sensitivity may not be affected, and may even be improved due to the synergistic effect of localized electron trapping and the enhanced solubility contrast.

[0126] In some embodiments, the composition may comprise two or more different nonpolymeric electron acceptor compounds as described herein. Each of the two or more nonpolymeric electron acceptor compounds may have an electron affinity greater than that of the photoacid-producing agent. In still other embodiments, each of the two or more nonpolymeric electron acceptor compounds may have an electron affinity greater than that of any added PDQ compound.

[0127] Nonpolymeric electron acceptor compounds can be prepared using any suitable method in the art, including those described in the embodiments herein.

[0128] The nonpolymeric electron acceptor compound may be included in the composition in an amount of 0.1 to 50% by weight, preferably 1 to 40% by weight, more preferably 2 to 20% by weight, based on the total solids of the composition.

[0129] The composition also includes an acid-sensitive polymer comprising a first repeating unit derived from a monomer containing an acid-degradable group.

[0130] Suitable acid-degradable or acid-indestabilized groups include, for example, tertiary alkyl esters, secondary aryl esters or tertiary aryl esters, secondary esters or tertiary esters having an alkyl and aryl combination, tertiary alkoxy groups, acetals, ketals, tertiary carbonates, and tertiary carbamates. Typically, the acid-indestabilized group may be an acetal, a ketal, a tertiary carbonate, a tertiary carbamate, or a tertiary ester. As used herein, "tertiary carbamate" includes tertiary carbamates having an alkyl group, tertiary carbamates having an aryl group, and tertiary carbamates having a combination of alkyl and aryl groups. As used herein, "tertiary carbonate" includes tertiary carbonates having an alkyl group, tertiary carbonates having an aryl group, and tertiary carbonates having a combination of alkyl and aryl groups. Preferably, the acid-indestabilized group comprises a tertiary ester.

[0131] An exemplary repeating unit having an acid-labile group comprises one or more repeating units represented by formulas (27) to (31):

[0132]

[0133] In equations (27) to (31), each R a Independently hydrogen, deuterium, fluorine, cyano, substituted or unsubstituted C 1-10 Alkyl, or substituted or unsubstituted C 1-10 Fluoroalkyl. Preferably, R a It is hydrogen, fluorine, or substituted or unsubstituted C 1-5 Alkyl, usually methyl.

[0134] In equation (27), L 1 It is a divalent linker. For example, L 1 It can be a divalent linking group containing at least one carbon atom, at least one heteroatom, or a combination thereof. For example, L 1 It may contain 1 to 10 carbon atoms and at least one heteroatom. In one or more embodiments, L 1 It can be -OCH2-, -OCH2CH2O-, or -N(R) c )-, where R c C is hydrogen, deuterium, substituted or unsubstituted. 1-10 Alkyl, substituted or unsubstituted C 1-10 Heteroalkyl, substituted or unsubstituted C 6-10 aryl, substituted or unsubstituted C 3-10 Mixed aromatic compounds.

[0135] In equations (27), (28) and (30), R 101 To R 103 Each can be independently hydrogen, deuterium, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 1-20 Heterocyclic alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 3-20 Cycloalkenyl, substituted or unsubstituted C 3-20 Heterocyclic alkenyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 2-20 heteroaryl; condition is R 101 To R 103 Only one of them can be hydrogen, and when R 101 To R 103 When one of them is hydrogen, R 101 To R 103 The remaining one or two are substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 4-20 heteroaryl. Preferred R 101 To R 103 Each is independently either substituted or unsubstituted C 1-6Alkyl, substituted or unsubstituted C 3-10 Cycloalkyl.

[0136] In equations (27), (28) and (30), R 101 To R 103 Any two of them can be arbitrarily combined to form a ring, and R 101 To R 103 Each of these optionally contains one or more groups selected from the group consisting of: -O-, -C(O)-, -N(R-). c -, -S-, -S(O)-, or -S(O)2-, where R c It can be hydrogen, deuterium, straight-chain or branched C 1-20 Alkyl, monocyclic or polycyclic C 3-20 Cycloalkyl, or monocyclic or polycyclic C 1-20 Heterocyclic alkyl groups. For example, R 101 To R 103 Any one or more of the terms can be independently represented by the formula -CH2C(=O)CH (3-n) Y n The group, wherein each Y is independently a substituted or unsubstituted C. 1-30 Heterocyclic alkyl groups, and n is 1 or 2. For example, each Y can independently be an inclusive -O(C a1 (C) a2 The substitution or unsubstituted C of the O- group 1-30 Heterocyclic alkyl, wherein C a1 and C a2 Each is independently hydrogen, deuterium, substituted or unsubstituted C 1-10 Alkyl, and wherein C a1 and C a2 They can be arbitrarily combined to form a ring.

[0137] In equations (29) and (31), R 104 and R 105 Each can be independently hydrogen, deuterium, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 1-20 Heterocyclic alkyl, substituted or unsubstituted C 6-20 aryl, or substituted or unsubstituted C 2-20 heteroaryl; and R 106 C can be substituted or unsubstituted. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 1-30 Heterocyclic alkyl groups. Optionally, R 104 Or R 105 One of them with R 106 They can form heterocyclic rings together. Preferably, R104 and R 105 Each can be independently hydrogen, deuterium, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl or substituted or unsubstituted C 1-20 Heterocyclic alkyl groups.

[0138] In equations (30) and (31), L 2 and L 3 Each is an independent single-bonded or divalent linker. Preferably, L 2 To L 3 Each is independently either substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Cycloalkylene compounds. For example, in some embodiments, L 3 It does not contain (meth)acrylate groups as part of its structure.

[0139] In equations (30) and (31), each of n1 and n2 can be independently 0 or 1. It should be understood that when n1 or n2 is 0, L correspondingly... 2 or L 3 The groups are directly attached to their respective oxygen atoms.

[0140] Non-limiting examples of repeating units having acid-labile groups include the following:

[0141]

[0142]

[0143]

[0144]

[0145] Among them, R d It is hydrogen, deuterium, halogen, substituted or unsubstituted C 1-6 Alkyl, or substituted or unsubstituted C 3-6 Cycloalkyl.

[0146] The repeating units having acid-labile groups are present in the polymer in an amount of 25 to 75 mol%, more typically 25 to 50 mol%, and even more typically 30 to 50 mol%, based on the total repeating units in the polymer.

[0147] The polymer may also contain one or more additional repeating units. These repeating units may be, for example, units used to modulate properties of the composition (e.g., etching rate and solubility). Exemplary repeating 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. The polymer of the composition may be a homopolymer or a copolymer containing two or more structurally different repeating units. For example, the polymer may contain one or more repeating units comprising functional groups selected from the group consisting of hydroxyaryl, base-solubilizing, lactone-containing, sulfonyl lactone-containing, polar, crosslinkable, crosslinking, etc., or combinations thereof.

[0148] The repeating unit of the polymer may contain a hydroxyaryl group. Exemplary hydroxyaryl groups include phenolic or naphthol groups. For example, the repeating unit of the polymer may contain a hydroxyaryl group represented by formula (32):

[0149]

[0150] In equation (32), R a It can be hydrogen, deuterium, fluorine, cyano, or substituted or unsubstituted C. 1-10 Alkyl group. Preferably, R a It is hydrogen, deuterium, fluorine, or substituted or unsubstituted C. 1-5 Alkyl groups are usually hydrogen or methyl.

[0151] In equation (32), L 5 It can be a single bond or one or more divalent linking groups. For example, L 5 It can be -O-, -C(O)-, -C(O)O-, -N(R) c )-、-C(O)N(R c -, substituted or unsubstituted C 1-10 Alkylene, substituted or unsubstituted C 3-10 Cycloalkylene, substituted or unsubstituted C 3-10 Heterocyclic alkyl, substituted or unsubstituted C 6-10 aryl, substituted or unsubstituted C 3-10 heteroaryl or combinations thereof, wherein R c It can be hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 1-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30Alkyne, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 Aryl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 2-30 heteroaryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 3- 30-alkyl heteroaryl. In some respects, L 5 It may be a single bond, or one or more groups selected from the group consisting of: -C(O)O-, substituted or unsubstituted C 1-10 Alkylene, substituted or unsubstituted C 3-10 Cycloalkylene, substituted or unsubstituted C 3-10 Heterocyclic alkyl, substituted or unsubstituted C 6-10 aryl, substituted or unsubstituted C 3-10 Hybrid aryl groups, or combinations thereof.

[0152] In equation (32), Ar 1 C can be replaced 5-60 An aromatic group, optionally comprising one or more aromatic ring heteroatoms selected from N, O, S, or combinations thereof, wherein the aromatic group may be monocyclic, non-fused polycyclic, or fused polycyclic. When C 5-60 When the aromatic group is polycyclic, the ring or cyclic group can be fused (such as naphthyl), non-fused, or a combination thereof. When the polycyclic C... 5-60 When aromatic groups are non-fused, rings or cyclic groups can be directly connected (e.g., biaryl, biphenyl, etc.) or bridged by heteroatoms (e.g., triphenylamino or diphenyl ether). In some aspects, polycyclic C 5-60 Aromatic groups may include combinations of fused rings and directly linked rings (e.g., binaphthyl).

[0153] In equation (32), y can be an integer from 1 to 12, preferably from 1 to 6, and usually from 1 to 3.

[0154] In equation (32), each R x It can be hydrogen or methyl independently, provided that at least one R x It is hydrogen.

[0155] Non-limiting examples of such repeating units in equation (32) may include:

[0156]

[0157]

[0158] Among them, R d It can be hydrogen, deuterium, fluorine, cyano, or substituted or unsubstituted C. 1-10 Alkyl group. Preferably, Rd It can be hydrogen, fluorine, or substituted or unsubstituted C. 1-5 Alkyl, usually methyl.

[0159] The repeating units in polymers containing hydroxyaryl groups are typically present in an amount of 10 to 90 mol%, more typically 15 to 75 mol%, and more typically 20 to 70 mol%, based on the total repeating units of the polymer.

[0160] The repeating unit of the polymer may contain a lactone group. For example, the repeating unit of the polymer may contain a lactone group represented by formula (33):

[0161]

[0162] In equation (33), R a It can be hydrogen, deuterium, fluorine, cyano, or substituted or unsubstituted C. 1-10 Alkyl group. Preferably, R a It is hydrogen, fluorine, or substituted or unsubstituted C 1-5 Alkyl groups are usually hydrogen or methyl.

[0163] In equation (33), L 4 It can be a single bond or one or more divalent linking groups. For example, L 4 It can be -O-, -C(O)-, -C(O)O-, -N(R) c )-、-C(O)N(R c -, substituted or unsubstituted C 1-10 Alkylene, substituted or unsubstituted C 3-10 Cycloalkylene, substituted or unsubstituted C 3-10 Heterocyclic alkyl, substituted or unsubstituted C 6-10 aryl, substituted or unsubstituted C 3-10 heteroaryl or combinations thereof, wherein R c It can be hydrogen, deuterium, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 1-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 Aryl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C 2-30 heteroaryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 3-30 Alkyl heteroaryl. In some respects, L 4 It may be a single bond, or one or more groups selected from the group consisting of: -C(O)O-, substituted or unsubstituted C 1-10 Alkylene, substituted or unsubstituted C 3-10 Cycloalkylene, substituted or unsubstituted C 3-10 Heterocyclic alkyl, substituted or unsubstituted C 6-10 aryl, substituted or unsubstituted C 3-10 Hybrid aryl groups, or combinations thereof.

[0164] In equation (33), R 107 C can be monocyclic, polycyclic, or fused polycyclic. 4-20 It contains a lactone group.

[0165] Non-limiting examples of lactone-containing repeating units of formula (33) may include:

[0166]

[0167]

[0168] Among them, R d It can be hydrogen, deuterium, fluorine, cyano, or substituted or unsubstituted C. 1-10 Alkyl group. Preferably, R d It can be hydrogen, fluorine, or substituted or unsubstituted C. 1-5 Alkyl, usually methyl.

[0169] Repeating units containing lactone groups are typically present in amounts of 5 to 90 mol%, more typically 10 to 75 mol%, and even more typically 15 to 70 mol%, based on the total repeating units of the polymer.

[0170] The repeating units of the polymer may contain salt groups. As used herein, a "salt group" refers to a positively and / or negatively charged portion, such as a positively or negatively charged portion side-bonded to the backbone of a block copolymer. The repeating units of a block polymer containing salt groups may contain photoacid-producing (PAG) groups or photodegradable quenching (PDQ) groups. For example, the repeating units of the polymer may contain salt groups represented by formula (34a) or (34b):

[0171]

[0172] In equations (34a) and (34b), each R m It can be hydrogen, deuterium, fluorine, cyano, or substituted or unsubstituted C. 1-10 Alkyl group. Preferably, R m It is hydrogen, fluorine, or substituted or unsubstituted C 1-5 Alkyl, usually methyl.

[0173] In equations (34a) and (34b), Q 1 and Q 2 Each can be an independent single bond or a divalent linker. Preferably, Q 1 and Q 2 Each may independently contain 1 to 10 carbon atoms and at least one heteroatom, more preferably -C(O)-O-.

[0174] In equations (34a) and (34b), A 1 and A 2 Each can be independently substituted or unsubstituted C. 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl or substituted or unsubstituted C 3-30 One or more of the heteroaryl groups. In some embodiments, A 1 and A 2 Each can be independently substituted divalent C. 1-30 Perfluoroalkylene groups.

[0175] In equation (34a), Z - For bonding to A 1 The anionic moiety of Z typically has a pKa of -15 to 10 for its conjugate acid. - It can be a sulfonate, carboxylate, sulfonamide anion, sulfonamide anion, or methyl anion.

[0176] In equation (34a), G + G is an organic cation as defined herein. In some embodiments, G + It is an iodonium cation substituted with two alkyl groups, two aryl groups, or a combination of alkyl and aryl groups; or a sulfonium cation substituted with three alkyl groups, three aryl groups, or a combination of alkyl and aryl groups.

[0177] In equation (34b), Z - For anionic compounds as defined herein, the pKa of their conjugate acids is typically -15 to 10. -It can be a sulfonate, carboxylate, sulfonamide anion, sulfonamide anion, or methyl anion. For example, Z - This could be as described in this article regarding anion A. - That's how it's defined.

[0178] In equation (34b), G + For bonding to A 2 Organic cations. For example, G + It may contain iodonium cations substituted with two alkyl groups, two aryl groups, or a combination of alkyl and aryl groups; or matte cations substituted with three alkyl groups, three aryl groups, or a combination of alkyl and aryl groups.

[0179] In some other embodiments, when the polymer comprises repeating units having salt groups, the polymer may contain zwitterionic substances. For example, the polymer may comprise repeating units having salt groups of formula (34c):

[0180]

[0181] In equation (34c), each R m Independently as defined by equations (34a) and (34b).

[0182] In equation (34c), Q 1 A 1 and Z - As defined in equation (20a), Q 2 A 2 and G + As defined in equation (34b).

[0183] An exemplary repeating unit of equation (34a) includes the following:

[0184]

[0185]

[0186] Where G is an organic cation, and each R d Independently defined as in equation (34a). An exemplary repeating unit of equation (34b) includes the following:

[0187]

[0188] Z - For anionic groups as defined herein, and each R d Independently as defined in equation (34b).

[0189] The repeating units of the salt-containing polymer may typically be present in amounts from 1 to 35 mol%, typically from 1 to 25 mol%, and more typically from 2 to 15 mol%, based on the total repeating units of the polymer.

[0190] In some embodiments, the polymer may include repeating units containing polar groups. Exemplary polar groups include cyano, sulopentalide, sulfonamide, hydroxyalkyl, hydroxycycloalkyl, or combinations thereof. It should be understood that some groups (e.g., lactone or hydroxyaryl) may be considered polar groups; however, these groups differ from those used herein.

[0191] The repeating unit of the polymer may contain a polar group represented by formula (35):

[0192]

[0193] In equation (35), R a It can be hydrogen, deuterium, fluorine, cyano, or substituted or unsubstituted C. 1-10 Alkyl group. Preferably, R a It is hydrogen, fluorine, or substituted or unsubstituted C 1-5 Alkyl groups are usually hydrogen or methyl.

[0194] In equation (35), L 6 It can be a single bond or one or more divalent linking groups. For example, L 6 It can be -O-, -C(O)-, -C(O)O-, -N(R) c )-、-C(O)N(R c -, substituted or unsubstituted C 1-10 Alkylene, substituted or unsubstituted C 3-10 Cycloalkylene, substituted or unsubstituted C 3-10 Heterocyclic alkyl, substituted or unsubstituted C 6-10 aryl, substituted or unsubstituted C 3-10 heteroaryl or combinations thereof, wherein R c It can be hydrogen, deuterium, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 1-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30Aryl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 2-30 heteroaryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 3-30 Alkyl heteroaryl. In some respects, L 6 It may be a single bond, or one or more groups selected from the group consisting of: -C(O)O-, substituted or unsubstituted C 1-10 Alkylene, substituted or unsubstituted C 3-10 Cycloalkylene, substituted or unsubstituted C 3-10 Heterocyclic alkyl, substituted or unsubstituted C 6-10 aryl, substituted or unsubstituted C 3-10 Hybrid aryl groups, or combinations thereof.

[0195] In equation (35), R 108 C can be substituted or unsubstituted. 1-100 Or C 1-20 Alkyl, usually C 1-12 Alkyl; substituted or unsubstituted C 3-30 Or C 3-20 cycloalkyl; or substituted or unsubstituted poly(C) 1-3 Alkylene oxides). 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 oxides are substituted with one or more sulfonamide groups (e.g., -NHSO2CF3), hydroxyl groups (-OH), or fluorool groups (e.g., -C(CF3)2OH).

[0196] Non-limiting examples of the repeating unit in equation (35) may include:

[0197]

[0198] Among them, R g It can be hydrogen, deuterium, fluorine, cyano, or substituted or unsubstituted C. 1-10 Alkyl group. Preferably, R g It is hydrogen, fluorine, or substituted or unsubstituted C 1-5 Alkyl group, usually methyl. Y 1 It can be F or C 1-4 Perfluoroalkyl.

[0199] In some embodiments, the polymer may include repeating units containing acid groups. Exemplary acid groups include carboxylic acid groups. The repeating units of the polymer may contain acid groups represented by formula (36):

[0200]

[0201] In equation (36), R a It can be hydrogen, deuterium, fluorine, cyano, or substituted or unsubstituted C. 1-10 Alkyl group. Preferably, R a It is hydrogen, fluorine, or substituted or unsubstituted C 1-5 Alkyl groups are usually hydrogen or methyl.

[0202] In equation (36), L 7 It can be a single bond or one or more of the following: substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 1-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted divalent C 7-30 Aryl, substituted or unsubstituted C 1-30 Heteroaryl, substituted or unsubstituted divalent C 3-30 Heteroalkyl, or -C(O)-O-.

[0203] In equation (36), R 109 It can be -C(O)-OH.

[0204] Non-limiting examples of the repeating unit in equation (36) may include:

[0205]

[0206] Among them, R d It can be hydrogen, deuterium, fluorine, cyano, or substituted or unsubstituted C. 1-10 Alkyl group. Preferably, R d It can be hydrogen, fluorine, or substituted or unsubstituted C. 1-5 Alkyl, usually methyl.

[0207] Repeating units containing acid groups are typically present in amounts of 1 to 20 mol%, more typically 5 to 20 mol%, and more typically 5 to 10 mol%, based on the total repeating units of the polymer. Repeating units containing hydroxyaryl groups are typically present in amounts of 1 to 20 mol%, more typically 5 to 20 mol%, and more typically 5 to 10 mol%, based on the total repeating units of the polymer.

[0208] Non-limiting exemplary polymers of the present invention include one or more of the following:

[0209]

[0210]

[0211] Where x, y, and z are each mole fractions of the relevant repeating units, the sum of the mole fractions of each polymer is 1, and each R d Independently hydrogen, deuterium, halogen, substituted or unsubstituted C 1-6 Alkyl, or substituted or unsubstituted C 3-6 Cycloalkyl.

[0212] The weight-average molecular weight (Mw) of the polymer is typically from 1,000 to 50,000 Daltons (Da), preferably from 2,000 to 30,000 Da, more preferably from 3,000 to 20,000 Da, and even more preferably from 4,000 to 15,000 Da. The polydispersity index (PDI) of the first polymer [i.e., M] w Number-average molecular weight (M n The ratio of [ ) is typically 1.1 to 3, and more commonly 1.1 to 2. Molecular weight values ​​are determined using polystyrene standards via gel permeation chromatography (GPC).

[0213] In the compositions of the present invention, the polymer is typically present in the composition in an amount of 10 to 99.9% by weight, typically 25 to 99% by weight, and more typically 50 to 95% by weight, based on the total solids of the composition. It should be understood that the total solids comprise one or more polymers, PAG, and other non-solvent components.

[0214] The polymer can be prepared using any suitable method in the art. For example, one or more monomers corresponding to the repeating units described herein can be combined or fed individually, using a suitable solvent and initiator, and polymerized in a reactor. For example, the polymer can be obtained by polymerizing the corresponding monomers under any suitable conditions (e.g., by heating at an effective temperature, irradiation with photochemical radiation of an effective wavelength, or a combination thereof).

[0215] The composition also contains a photoacid-producing agent (PAG). PAG can be in ionic or nonionic form. PAG can be in polymeric or nonpolymeric form. In the polymeric form, PAG may be present as part of a repeating unit in a polymer derived from a polymerizable PAG monomer.

[0216] In some embodiments, the composition may comprise two or more different photoacid-producing compounds. In some embodiments, when the photoresist compound comprises two or more different photoacid-producing compounds, the non-polymeric electron acceptor compound has a greater electron affinity than each of the two or more different photoacid-producing compounds.

[0217] Suitable PAG compounds can be of formula G + A - G+ A is an electroactive cation. - The anion is capable of producing a photoacid. This electroactive cation is preferably selected from onium cations, more preferably iodonium cations or sulfonium cations. Particularly suitable anions include those whose conjugate acid has a pKa of -15 to 10. This anion is typically an organic anion having a sulfonate group or a non-sulfonate group, such as sulfonamide, sulfonimide, methyl, or borate.

[0218] In some respects, the anion of PAG does not contain or is free of -F, -CF3, or -CF2- groups. It should be understood that "free of -F, -CF3, or -CF2- groups" means that the anion of PAG does not include groups such as -CH2CF3 and -CH2CF2CH3. In still other respects, the anion of PAG is fluorine-free (i.e., it contains no fluorine atoms and is not substituted by fluorine-containing groups). In some respects, the photoacid-producing agent is fluorine-free (i.e., neither the photoactive cation nor the anion contains fluorine).

[0219] The PAG compound contains an organic cation. For example, the organic cation may be a sulfonium cation or an iodonium cation. In some embodiments, the organic cation may be a sulfonium cation of formula (37a) or an iodonium cation of formula (37b):

[0220]

[0221] In equations (37a) and (37b), R 110 To R 114 Each is independently either 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 6-30 Iodinated aryl, substituted or unsubstituted C 3-30 heteroaryl, substituted or unsubstituted C 7-20 Aryl, or substituted or unsubstituted C 4-20 Heteroaryl groups, or combinations thereof. 110 To R 114 Each of them can be independent or can be linked to R via a single bond or a divalent linking group. 110 To R 112 Another group in R is attached to form a ring. 113 and R 114 They can be independent or linked together by single or divalent connecting groups to form a ring. R 110 To R 114 Each of these may optionally contain a divalent linker as part of its structure. R 110 To R114 Each of the groups may independently and optionally contain an acid-indestructible group selected, for example, from: tertiary alkyl ester, secondary aryl ester or tertiary aryl ester, secondary ester or tertiary ester having a combination of alkyl and aryl, tertiary alkoxy, acetal or ketal.

[0222] The exemplary sulfonium cation of formula (37a) comprises one or more of the following:

[0223]

[0224]

[0225] An exemplary iodonium cation of formula (37b) may comprise one or more of the following:

[0226]

[0227] Exemplary organic anions having a sulfonate group include one or more of the following:

[0228]

[0229] Exemplary nonsulfonated anions include one or more of the following:

[0230]

[0231]

[0232] Commonly used onium salts may include, for example, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tri(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; di-tert-butylphenyliodomonium perfluorobutanesulfonate and di-tert-butylphenyliodomonium camphorsulfonate. Other useful PAG compounds are known in the field of chemically amplified photoresists, including, for example: nonionic sulfonyl compounds, such as 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, and 2,4-dinitrobenzyl p-toluenesulfonate; sulfonates, such as 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene; and diazomethane derivatives, such as bis(benzenesulfonyl)diazomethane and bis(p-toluenesulfonyl)diazomethane. ; dioxime derivatives, such as bis-O-(p-toluenesulfonyl)-α-dimethyldioxime and bis-O-(n-butanesulfonyl)-α-dimethyldioxime; sulfonate derivatives of N-hydroxyimide compounds, such as N-hydroxysuccinimide methanesulfonate and N-hydroxysuccinimide trifluoromethanesulfonate; and halogenated 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 photoacid-generating agents are further described in U.S. Patent Nos. 8,431,325 and 4,189,323.

[0233] If the composition comprises a nonpolymeric electron acceptor compound and a PAG compound, both of which are in ionic form, the nonpolymeric electron acceptor compound may contain an anion with the same anionic structure as the PAG compound. Alternatively, the anion of the nonpolymeric electron acceptor compound may have a different anionic structure than that of the PAG compound. For example, in some embodiments, the photoacid-producing compound contains a first anion and the nonpolymeric electron acceptor compound contains a second anion, wherein the first anion and the second anion have the same structure.

[0234] Typically, when the composition contains a nonpolymeric PAG compound, the PAG compound is present in the composition in an amount of 0.1 to 55% by weight, more typically 1 to 25% by weight, based on the total solids of the composition. When present in polymeric form, the PAG compound is typically contained in the polymer in an amount of 1 to 25 mol%, more typically 1 to 8 mol%, or 2 to 6 mol%, based on the total repeating units in the polymer.

[0235] The composition also includes a solvent for dissolving the composition components and promoting their coating on a substrate. Preferably, the solvent is an organic solvent commonly used in the manufacture of electronic devices. Suitable solvents include, for example: aliphatic hydrocarbons, such as hexane and heptane; aromatic hydrocarbons, such as toluene and xylene; halogenated hydrocarbons, such as dichloromethane, 1,2-dichloroethane, and 1-chlorohexane; alcohols, such as methanol, ethanol, 1-propanol, isopropanol, tert-butanol, 2-methyl-2-butanol, 4-methyl-2-pentanol, and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone) (DAA); propylene glycol monomethyl ether (PGME); ethers, such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and anisole; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2... - Heptanone and cyclohexanone (CHO); esters, such as ethyl acetate, n-butyl acetate, propylene glycol methyl ether acetate (PGMEA), ethyl lactate (EL), methyl hydroxyisobutyrate (HBM), and ethyl acetoacetate; lactones, such as γ-butyrolactone (GBL) and ε-caprolactone; lactams, such as N-methylpyrrolidone; nitriles, such as acetonitrile and propionitrile; cyclic or acyclic carbonates, such as propylene carbonate, dimethyl carbonate, ethylene carbonate, diphenyl carbonate, and propylene carbonate; polar aprotic solvents, such as dimethyl sulfoxide and dimethylformamide; water; and combinations thereof. Preferred solvents include one or more of PGME, PGMEA, EL, GBL, HBM, CHO, DAA, or combinations thereof.

[0236] The total solvent content in the composition (i.e., the cumulative solvent content of all solvents) is typically 40 to 99% by weight, for example, 60 to 99% by weight, or 85 to 99% by weight, based on the total solids of the composition. The required solvent content depends, for example, the required coating (photoresist) layer thickness and coating conditions.

[0237] In some aspects, the composition may also comprise materials containing one or more base-indestructible groups (“base-indestructible materials”) and / or base-soluble groups. As mentioned herein, base-soluble groups are typically polar functional groups that can ionize in TMAH-type bases and thus dissolve during the development stage, while base-indestructible groups are functional groups that can undergo cleavage reactions in the presence of an aqueous alkaline developer after exposure and post-exposure baking steps, generating similar polar groups (such as base-soluble groups), such as hydroxyl groups (including phenolic hydroxyl groups), HFA (hexafluoroalcohol), carboxylic acids, sulfonic acids, etc. Base-indestructible groups do not undergo significant reactions (e.g., no bond-breaking reactions) prior to the development step of the composition containing base-indestructible groups. Therefore, for example, base-indestructible groups are substantially inert during pre-exposure soft baking, exposure, and post-exposure baking steps. “Substantially inert” means that ≤5% (typically ≤1%) of the base-indestructible groups (or a portion thereof) will decompose, break down, or react during pre-exposure soft baking, exposure, and post-exposure baking steps. The alkali-indestructible group is reactive under typical photoresist development conditions, such as aqueous solutions of alkaline photoresist developers [e.g., 0.26 N normol (N) aqueous solution of tetramethylammonium hydroxide (TMAH)]. For example, a 0.26 N TMAH aqueous solution can be used for single-puddle development or dynamic development, such as dispensing the 0.26 N TMAH developer onto the surface of the imaged photoresist layer and holding it for an appropriate time (e.g., 10 to 120 seconds). An exemplary alkali-indestructible group is an ester group, typically a fluorinated ester group. Preferably, the alkali-indestructible material is substantially immiscible with the first and / or second polymer and other fixed components in the composition, and has a lower surface energy. When coated on a substrate, the alkali-indestructible material can thus separate from the other solid components in the composition and reach the top surface of the formed photoresist layer.

[0238] In some aspects, the alkali-insecure material can be a polymeric material (also referred to herein as an alkali-insecure polymer) that may comprise one or more repeating units containing one or more alkali-insecure groups. For example, an alkali-insecure polymer may comprise repeating units containing two or more identical or different alkali-insecure groups. Alkali-insecure or alkali-soluble polymers may comprise one or more other repeating units, such as (meth)acrylate monomers, vinyl aromatic monomers, vinyl ether monomers, vinyl ketone monomers, and / or vinyl ester monomers. Preferred alkali-insecure polymers comprise at least one repeating unit containing two or more alkali-insecure groups, for example, repeating units containing two or three alkali-insecure groups. Another preferred alkali-insecure polymer comprises at least one repeating unit containing an acid-degradable group.

[0239] Alkali-instable polymers can be prepared using any suitable method in the art. For example, alkali-instable polymers can be obtained by polymerizing the corresponding monomers under any suitable conditions (e.g., by heating at an effective temperature, irradiation with photochemical radiation of an effective wavelength, or a combination thereof). Alternatively, one or more alkali-instable groups can be grafted onto the polymer backbone using suitable methods.

[0240] In some aspects, the base-insecure material is a monomolecule containing one or more base-insecure ester groups, preferably one or more fluorinated ester groups. The Mw of a monomolecule base-insecure material is typically in the range of 50 to 1,500 Da.

[0241] When present, alkali-instable and / or alkali-soluble materials are typically present in the composition in amounts from 0.01 to 10% by weight, and usually from 1 to 5% by weight, based on the total solids of the composition.

[0242] In addition to the polymers described above, the composition may also contain one or more polymers different from those described above. For example, the composition may contain additional polymers as described above, but with different compositions. Additionally, or alternatively, one or more additional polymers may contain those known in the field of photoresists, such as those selected from the group consisting of: polyacrylates, polyvinyl ethers, polyesters, polynorbornene, polyacetals, polyethylene glycol, polyamides, polyacrylamide, polyphenols, phenolic varnishes (novolac), styrene polymers, polyvinyl alcohol, or combinations thereof.

[0243] The composition may also contain one or more additional optional additives. For example, optional additives may include photochemical dyes and contrast dyes, anti-stripping agents, plasticizers, speed enhancers, sensitizers, photodegradable quenchers (PDQ) (also known as photodegradable bases), alkaline quenchers, hot acid generators, surfactants, etc., or combinations thereof. If present, optional additives are typically present in the composition in an amount from 0.01 to 10% by weight, based on the total solids of the composition.

[0244] PDQs generate weak acids under radiation. The acids generated by photodegradable quenchers are insufficient to react rapidly with the acid-indestructible groups present in the photoresist matrix. Exemplary photodegradable quenchers include, for example, photodegradable cations (preferably those suitable for preparing strong acid-generating compounds) paired with an anion of a weak acid (pKa > 1), such as C. 1-20 Carboxylic acid anion or C 1-20Sulfonic acid anions. Exemplary carboxylic acids include formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexanecarboxylic acid, benzoic acid, salicylic acid, etc. Exemplary sulfonic acids include p-toluenesulfonic acid, camphorsulfonic acid, etc. In a preferred embodiment, the photodegradable quencher is a photodegradable organic zwitterionic compound, such as diphenyliodonium-2-carboxylate. When the composition contains PDQ, PDQ has a lower electron affinity than non-polymeric electron acceptor compounds.

[0245] PDQ can be in a non-polymeric form or a polymer-bound form. The polymeric unit containing the photodegradable 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 repeating units of the polymer.

[0246] Exemplary alkaline quenchers include, for example, linear aliphatic amines such as tributylamine, trioctylamine, triisopropanolamine, tetra(2-hydroxypropyl)ethylenediamine, N-tert-butyldiethanolamine, tris(2-acetoxy-ethyl)amine, 2,2',2”,2”'-(ethane-1,2-diylbis(azatriyl))tetraethanol, 2-(dibutylamino)ethanol, and 2,2',2”-azatriethanol; cyclic aliphatic amines, such as 1- (tert-Butoxycarbonyl)-4-hydroxypiperidine, tert-butyl-1-pyrrolidine carboxylate, tert-butyl-2-ethyl-1H-imidazol-1-carboxylate, di-tert-butylpiperazine-1,4-dicarboxylate, and N-(2-acetoxy-ethyl)morpholine; aromatic amines, such as pyridine, di-tert-butylpyridine, and pyridinium; linear and cyclic amides and their derivatives, such as N,N-bis(2-hydroxyethyl)neopentamide, N,N-diethylacetamide, N... 1 N 1 N 3 N 3 -Tetrabutylmalonamide, 1-methylazacycloheptane-2-one, 1-allylazacycloheptane-2-one and tert-butyl-1,3-dihydroxy-2-(hydroxymethyl)propane-2-ylcarbamate; ammonium salts, such as quaternary ammonium salts of sulfonates, aminosulfonates, carboxylates and phosphonates; imines, such as primary aldehyde imines and primary ketone imines and secondary aldehyde imines and secondary ketone imines; diazines, such as optionally substituted pyrazines, piperazines and phenazines; diazoles, such as optionally substituted pyrazoles, thiadiazoles and imidazoles; and optionally substituted pyrrolidones, such as 2-pyrrolidone and cyclohexylpyrrolidine.

[0247] The alkali quencher can be in a non-polymeric or polymer-bonded form. When in a polymeric form, the quencher can be present in the repeating units of the polymer. The repeating units containing the quencher are typically present in amounts of 0.1 to 30 mol%, preferably 1 to 10 mol%, more preferably 1 to 2 mol%, based on the total repeating units of the polymer.

[0248] Exemplary surfactants include fluorinated and nonfluorinated surfactants and can be ionic or nonionic, with nonionic surfactants being preferred. Exemplary fluorinated nonionic surfactants include perfluorinated C4 surfactants, such as FC-3340 and FC-4432 surfactants, which are available from 3M; and fluorinated glycols, such as POLYFOX PF-636, PF-6320, PF-656, and PF-6520 fluorinated surfactants from Omnova. In one aspect, the composition further comprises a surfactant polymer containing fluorinated repeating units.

[0249] A patterning method using the compositions of the present invention will now be described. Suitable substrates for coating the compositions include electronic device substrates. A variety of electronic device substrates can be used in the present invention, such as: semiconductor wafers; polycrystalline silicon substrates; packaging substrates such as multi-chip modules; flat panel display substrates; light-emitting diode (LED) substrates [including organic light-emitting diodes (OLEDs)], etc., with semiconductor wafers being typical. Such substrates are typically composed of one or more of silicon, polycrystalline silicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. Suitable substrates can be in wafer form, such as those used for manufacturing integrated circuits, optical sensors, flat panel displays, integrated optical paths, and LEDs. Such substrates can be of any suitable size. Typically, wafer substrates have a diameter of 200 to 300 millimeters (mm), but smaller or larger diameter wafers can also be used according to the present invention. The substrate may contain one or more layers or structures, which may optionally contain active or operable portions of the formed device.

[0250] Typically, prior to coating the composition of the present invention, one or more photolithographic layers are provided on the upper surface of the substrate, such as hard mask layers [e.g., spin-coated carbon (SOC), amorphous carbon, or metal hard mask layers], CVD layers [e.g., silicon nitride (SiN), silicon oxide (SiO), or silicon oxynitride (SiON) layers], organic or inorganic underlayers, or combinations thereof. These layers, together with the coated photoresist layer, form a photolithographic material stack.

[0251] Optionally, an adhesion promoter may be applied to the substrate surface prior to coating the composition. If an adhesion promoter is required, any adhesion promoter suitable for polymer films may be used, such as silanes, typically organosilanes such as trimethoxyvinylsilane, triethoxyvinylsilane, hexamethyldisilazane, or aminosilane coupling agents such as γ-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those formulated with AP... TM 3000, AP TM 8000 and AP TMThose sold under the 9000S name are available from DuPont Electronics & Industrial (Marlborough, Massachusetts).

[0252] The composition can be coated onto a substrate by any suitable method, including spin coating, spray coating, dip coating, blade coating, etc. For example, a photoresist layer can be applied by spin coating a photoresist in a solvent using a coating track, wherein the photoresist layer is dispensed onto a rotating wafer. During the dispensing process, the wafer is typically rotated at speeds up to 4,000 rpm, for example, 200 to 3,000 rpm, or 1,000 to 2,500 rpm, for 15 to 120 seconds to obtain a layer of composition on the substrate. Those skilled in the art will understand that the thickness of the coating can be adjusted by changing the spin coating speed and / or the total solids of the composition. The dried layer thickness of the EUV (photoresist) composition layer formed by the compositions of the present invention is typically 5 nm to 100 nm, preferably greater than 10 nm to 80 nm, more preferably 20 nm to 70 nm. The dried layer thickness of the electron beam photoresist composition formed by the compositions of the present invention is typically 50 nm to 3 mm, preferably greater than 70 nm to 1 nm, more preferably 100 nm to 500 nm.

[0253] The composition is then typically soft-baked to minimize the solvent content in the layer, thereby forming a tack-free coating and improving adhesion between the layer and the substrate. Soft baking is typically performed on a hot plate or in an oven, usually a hot plate. The temperature and time of soft baking depend on, for example, the composition and thickness. Soft baking temperatures are typically 80 to 170°C, more typically 90 to 150°C. Soft baking times are typically 10 seconds to 20 minutes, more typically 1 to 10 minutes, and even more typically 1 to 2 minutes. Those skilled in the art can readily determine the heating time based on the composition's components.

[0254] Next, the photoresist layer or electron beam photoresist layer is exposed to activating radiation in a patterned manner to create a solubility difference between exposed and unexposed areas. The exposure of the photoresist composition to activating radiation, as mentioned herein, refers to radiation that can form a latent image within the photoresist composition. Exposure is typically performed using a patterned photomask with optically transparent and optically opaque regions corresponding to the exposed and unexposed areas of the photoresist layer, respectively. Alternatively, exposure can be performed without a photomask using a direct writing method typically used in electron beam lithography. Exposure is performed using activating radiation [e.g., 13.5 nm (EUV) or shorter wavelengths] or an electron beam (e-beam). Exposure energy is typically 1 to 200 millijoules per square centimeter (mJ / cm²). 2 The preferred concentration is 5 to 100 mJ / cm³. 2 More preferably 20 to 50 mJ / cm 2 This depends on the exposure tool and the composition of the photoresist composition.

[0255] After the photoresist layer is exposed, it undergoes post-exposure baking (PEB). PEB can be performed, for example, on a hot plate or in an oven, typically a hot plate. The conditions for PEB depend on, for example, the photoresist composition and layer thickness. PEB is typically performed at a temperature of 70 to 150°C, preferably 75 to 150°C, for 30 to 120 seconds. A latent image is formed in the photoresist, defined by polarity-converted regions (exposed regions) and unconverted regions (unexposed regions).

[0256] The exposed photoresist layer is then developed using a suitable developer to selectively remove areas soluble in the developer, while the remaining insoluble areas form the final photoresist pattern relief image. In the case of a positive development (PTD) process, the exposed areas of the photoresist layer are removed during development, while the unexposed areas are retained. Conversely, in the case of a negative development (TTD) process, the exposed areas of the photoresist layer are retained during development, while the unexposed areas are removed. The developer can be applied by any suitable method, such as the methods described above related to composition application, typically spin coating. The development time is the time required to effectively remove the soluble areas of the photoresist, typically 5 to 60 seconds. Development is usually performed at room temperature.

[0257] Developers suitable for PTD processes include alkaline aqueous solutions, such as quaternary ammonium hydroxide solutions (e.g., TMAH, preferably 0.26N TMAH), tetraethylammonium hydroxide, tetrabutylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. Developers suitable for NTD processes are organic solvent-based, meaning the cumulative content of organic solvents in the developer is 50% by weight or higher, typically 95% by weight or higher, 98% by weight or higher, or 100% by weight, based on the total weight of the developer. Organic solvents suitable for NTD developers include, for example, those selected from ketones, esters, ethers, hydrocarbons, and mixtures thereof. Developers are typically 2-heptanone or n-butyl acetate.

[0258] The compositions of the present invention can be used to form coated substrates. Such coated substrates include: (a) a substrate having one or more layers to be patterned on its surface; and (b) a composition layer on said one or more layers to be patterned.

[0259] Photoresist patterns can be used, for example, as an etching mask, allowing the pattern to be transferred to one or more layers sequentially below using known etching techniques (typically dry etching, such as reactive ion etching). Photoresist patterns can also be used, for example, to transfer a pattern to an underlying hard mask layer, which in turn acts as an etching mask to transfer the pattern to one or more layers below the hard mask layer. If the photoresist pattern is not consumed during the pattern transfer process, it can be removed from the substrate using known techniques such as oxygen plasma ashing. When used in one or more such patterning processes, the composition can be used to manufacture semiconductor devices, such as memory devices, processor chips (CPUs), graphics chips, optoelectronic chips, LEDs, OLEDs, and other electronic devices.

[0260] The following non-limiting embodiments further illustrate the present invention.

[0261] Example

[0262] Electron affinity and LUMO energy calculation

[0263] The calculated electron affinity (EA) of the PAG cationic triphenyl sulfonium and nonpolymeric electron acceptor compounds of the present invention is summarized in Table 1. For the calculations, density functional theory (DFT) at the B3LYP level was used with a 6-31+G(d,p) basis set. Each molecule in solution was modeled using a polarizable continuum (PC) model with propylene carbonate as the solvent. Vibrational frequency analysis was used to determine the overall minimum energy geometry. The energy calculated from the optimized structure was used to calculate the adiabatic electron affinity. The electron affinity was calculated as the energy difference between the neutral form and the form produced after adding an electron (i.e., the corresponding anionic radical form). For positively charged substances (e.g., sulfonium cations with a charge of +1), the electron affinity was calculated as the energy difference between the +1 charged sulfonium and the radical form produced after adding an electron.

[0264] Quantum chemical calculations were used to calculate the lowest unoccupied molecular orbital (LUMO) energy. DFT calculations were performed using the Gaussian 16 software package with B3LYP functions and a 6-31+G(d,p) basis set. Each molecule in solution was modeled using a polarizable continuum (PC) model with propylene carbonate as the solvent. Vibrational frequency analysis was used to determine the overall lowest energy geometry. After optimization, a DFT output file containing molecular orbital energies was obtained. The LUMO energy was extracted from the output.

[0265] Table 1

[0266]

[0267]

[0268] As can be seen from Table 1, each of the non-polymeric electron acceptor compounds EA1 to EA11 of the present invention exhibits a higher energy (EA) than the cationic TPS (EA12). Similarly, as can be seen from Table 1, each of the non-polymeric electron acceptor compounds EA1 to EA11 of the present invention exhibits a lower LUMO energy than the cationic TPS (EA12).

[0269] The structures of electron acceptor compounds EA1 to EA11 and the cationic TPS (EA12) are as follows:

[0270] Reduction potential measurement

[0271] Et2-Vio-Br2 (EA9) was purchased from Aldrich and used directly. Cyclic voltammetry measurements were performed as described below.

[0272] The reduction potential represents the electron affinity of a material and is usually closely related to electron affinity. It can be measured using cyclic voltammetry (Ereduction). o’ The response of cyclic voltammetry is irreversible, therefore E cannot be directly measured. o’ Instead of using cathode peak potential, the reduction potential was estimated. Specifically, each material was dissolved in acetonitrile (HPLC grade, Sigma-Aldrich) to prepare a 1 mM solution of the test molecule for measurement. A 0.1 M tetrabutylammonium perchlorate solution (>99%, Sigma-Aldrich) was used as the supporting electrolyte. For electrodes, a 4 mm disc Pt electrode, a wound Pt wire, and an Ag / AgCl electrode were used as the working electrode, counter electrode, and reference electrode, respectively. Prior to electrochemical measurements, the solution was purged with N2 gas for 5–10 minutes to displace dissolved O2. Measurements were performed at approximately 23.5 °C (these experiments were not temperature-controlled / performed at room temperature). The scan rate was 50 mV / s.

[0273] Table 2 provides a comparison between the dibromo viologen compound Et2-Vio-Br2 (EA9) and the TPS cation and diphenyliodonium cation:

[0274]

[0275]

[0276] Table 2

[0277] As can be seen from Table 2, the electron acceptor compound EA9 (i.e. its cationic portion) of the present invention has a higher reduction potential than sulfonium cation and iodonium cation.

[0278] Synthesis of Et2Vio Di-PFBuS(A1)

[0279]

[0280] The synthesis reactions were carried out under a nitrogen atmosphere. All chemicals were purchased from commercial suppliers and were ready for use without further purification. Proton nuclear magnetic resonance (¹H-NMR) spectra of all compounds were obtained on a 500 MHz NMR spectrometer. Chemical shifts are reported as δ (parts per million, ppm) relative to the internal standard tetramethylsilane. Multiplicity is expressed as singlet (s), doublet (d), triplet (t), tetrat (q), multipeak (m), doublet (dd), doubletuplet (dt), tripletuplet (tt), or broad singlet (br).

[0281] 1,1'-Diethyl-[4,4'-bipyridine]-1,1'-dibromide (3.74 g), sodium nonafluoro-1-butanesulfonate (6.44 g), dichloromethane (DCM) (50 mL), and water (50 mL) were added to a round-bottom flask and stirred at room temperature for 1 day. A white solid precipitated. The mixture was filtered, and the solid was washed three times with water and three times with DCM. It was dried in a vacuum oven for 2 days to obtain a white solid product (6.12 g, 75% yield). 1 ¹H-NMR (500MHz, acetone-d6) d: 9.49 (d, 4H), 8.89 (d, 4H), 5.04 (q, 4H), 1.82 (t, 6H).

[0282] Photoresist composition

[0283] The chemical structures of the polymer (MP1), quencher (Q1), photoacid-producing agents PAG1, PAG2 and PAG3, and electron acceptor compounds A1, A2, A3 and A4 used in the examples and comparative examples are shown below.

[0284]

[0285] The photoresist composition was prepared by dissolving the solid components in a solvent. The materials and amounts used are shown in Table 3, where amounts are listed in grams. The total solids content of the photoresist composition is 2.27% by weight. The solvent blend contains propylene glycol methyl ether acetate (S1), propylene glycol methyl ether (S2), methyl-2-hydroxyisobutyrate (S3), ethyl lactate (S4), and / or diacetone alcohol (S5). Each solution was filtered four times through a 0.01 μm high-density polyethylene disc filter before use and then placed in a microclean bottle.

[0286] Table 3

[0287]

[0288]

[0289] EUV lithography evaluation

[0290] EUV lithography was performed on a 300 mm diameter silicon wafer, in which photoresist was coated onto a 60 nm thick underlying stack (a 20 nm silicon substrate layer on a 60 nm organic substrate) and baked at 110 °C for 60 seconds. Subsequently, the coated wafer was exposed to contact hole masks in a matrix with different dose and focal length settings on an ASML NXE3400B EUV scanner with a numerical aperture of 0.33. After exposure, the wafer was baked with exposure-before-exposure (PEB) at 100 °C for 60 seconds, developed in CD-26 for 30 seconds, rinsed with deionized water, and then spin-dried. The critical size (CD) of the imaging aperture was measured using a Hitachi CG5000CD scanning electron microscope (SEM). Size-dose ratio (E) was also measured. 尺寸 The exposure dose required to print a hole at a target CD of 24 nm and a spacing of 64 nm is defined as the exposure dose required to print a hole at a target CD of 28 nm and a spacing of 44 nm. The local critical size uniformity (LCDU) of the hole at or near the target CD is defined as 3 multiplied by the standard deviation (σ) of the hole CD measured from 20 fields of view (FOV). The pseudo-Z factor is reported below and determined according to Formula 1:

[0291] Pseudo-Z factor = (E 尺寸 )x(LCDU) 2 Formula 1

[0292] Among them, E 尺寸 millijoules per square centimeter (mJ / cm²) 2 Reports are in units of nanometers (nm) for LCDU and in units of nanometers (nm) for LCDU. The pseudo-Z-factor (Z'-factor) is a photoresist performance metric improved upon the Z-factor, a known parameter indicating RLS (resolution, line edge roughness, sensitivity) photoresist performance (e.g., see Wallow, T. et al., Proc. SPIE 6921, 69211F, 2008). The pseudo-Z-factor is calculated at constant resolution (CD size).

[0293] The EUV lithography results are shown in Table 4 (24nm / 64nm pitch contact holes) and Table 5 (28nm / 44nm pitch contact holes).

[0294] Table 4

[0295]

[0296] Table 5

[0297]

[0298] As shown in Tables 4 and 5, photolithography performance can be improved by using nonpolymerized secondary electron acceptor compounds with higher electron affinity than photoacid-producing compounds.

[0299] While this disclosure has been described in conjunction with exemplary embodiments that are now considered practical, it should be understood that the invention is not limited to the disclosed embodiments, but rather is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A composition comprising: An acid-sensitive polymer comprising a first repeating unit derived from a monomer containing an acid-degradable group; Photoacid-producing compounds; A nonpolymerizable electron acceptor compound having a greater electron affinity than a photoacid-producing compound, wherein the nonpolymerizable electron acceptor compound does not produce photoacids, and wherein the nonpolymerizable electron acceptor compound does not contain a plurality of diazonoquinone (DNQ) groups; and Solvent, wherein the solvent is present in the composition in an amount greater than 50% by weight, based on the total weight of the composition. The composition is a positive EUV photoresist or an electron beam photoresist.

2. The composition of claim 1, comprising two or more photoacid-producing compounds, wherein the nonpolymeric electron acceptor compound has a greater electron affinity than each of the two or more photoacid-producing compounds.

3. The composition of claim 1 or 2, further comprising an alkali-instable material, an alkali-soluble material, or a combination thereof.

4. The composition of any one of claims 1 to 3, wherein the photoacid-producing compound comprises a first anion and the nonpolymeric electron acceptor compound comprises a second anion, wherein the first anion has the same structure as the second anion.

5. The composition of any one of claims 1 to 4, wherein the acid-sensitive polymer further comprises a second repeating unit, and wherein the second repeating unit comprises a hydroxyaryl group.

6. The composition according to any one of claims 1 to 5, wherein the nonpolymeric electron acceptor compound comprises a compound represented by one of formulas (1) to (5): in, In equations (1) to (5), R 1 To R 25 R 20a and R 21a Each is independently hydrogen, deuterium, halogen, nitro, amino, cyano, pyridinium, substituted or unsubstituted C. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 1-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 Aryl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 2-30 heteroaryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 3-30 Alkyl heteroaryl; R 1 To R 25 R 20a and R 21a Each of them optionally also includes one or more divalent linking groups as part of its structure. R 1 To R 10 Two or more adjacent R groups optionally form a ring with each other via one or more divalent linking groups. 11 To R 19 Two or more adjacent R groups optionally form a ring with each other through one or more divalent linking groups. 20 Optionally, they form rings with each other via one or more divalent linking groups, with two or more adjacent R groups... 21 Optionally, they form rings with each other via one or more divalent linking groups, R 22 To R 25 Two or more of them may optionally form a ring with each other through one or more divalent linking groups; L 1 It is a single bond or a divalent linker; L 2 It is a single bond or a multivalent linker; p is an integer from 2 to 6; n1 is an integer from 0 to 4; n2 is an integer from 0 to 5; X is a single bond or one or more divalent linkers; and A - and B - Each is an organic anion independently, of which A - and B - They can be arbitrarily linked together to form divalent organic anions.

7. The composition of any one of claims 1 to 6, wherein the nonpolymeric electron acceptor compound comprises a compound represented by one of formulas (6) to (26): in, In equations (6) to (26), R 26 to R81 Each is independently hydrogen, deuterium, halogen, nitro, amino, cyano, pyridinium, substituted or unsubstituted C. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 1-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 Aryl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 2-30 heteroaryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 3-30 Alkyl heteroaryl; R 26 To R 81 Each of them optionally also includes one or more divalent linking groups as part of its structure; R 26 To R 31 Two or more adjacent groups optionally form a ring with each other through one or more divalent linking groups; R 32 To R 36 Two or more adjacent groups optionally form a ring with each other through one or more divalent linking groups; R 37 To R 40 Two or more adjacent groups optionally form a ring with each other through one or more divalent linking groups; R 41 To R 46 Two or more adjacent groups optionally form a ring with each other through one or more divalent linking groups; R 47 To R 51 Two or more adjacent groups optionally form a ring with each other through one or more divalent linking groups; R 54 To R 55 Two or more adjacent groups optionally form a ring with each other through one or more divalent linking groups; R 56 To R 57 Two or more adjacent groups optionally form a ring with each other through one or more divalent linking groups; R 58 To R 59 Two or more adjacent groups optionally form a ring with each other through one or more divalent linking groups; R 60 To R 61 Two or more adjacent groups optionally form a ring with each other through one or more divalent linking groups; R 64 To R 65 Two or more adjacent R groups optionally form a ring with each other through one or more divalent linking groups; two or more adjacent R groups 68 Optionally, they form rings with each other via one or more divalent linking groups; two or more adjacent R 70 Optionally, they form rings with each other via one or more divalent linking groups; two or more adjacent R 71 Optionally, they form rings with each other via one or more divalent linking groups; two or more adjacent R 73 Optionally, they form rings with each other via one or more divalent linking groups; two or more adjacent R 74 Optionally, they form rings with each other via one or more divalent linking groups; two or more adjacent R 75 Optionally, they form rings with each other via one or more divalent linking groups; R 76 To R 77 Two or more adjacent groups optionally form a ring with each other through one or more divalent linking groups; R 78 To R 79 Two or more adjacent groups optionally form a ring with each other through one or more divalent linking groups; R 80 To R 81 Two or more adjacent groups may optionally form a ring with each other through one or more divalent linking groups; X - It is an organic anion. n1, n2, and n6 through n9 are each independent integers from 0 to 4. n4 and n5 are each independent integers from 0 to 2. Each I is an integer from 0 to 4; Each k is an integer between 0 and 30; Each p is an integer from 0 to 4; Each q is an integer from 0 to 5; Each r is an integer from 0 to 4; M is a transition metal; and X, Y, and Z each independently contain electron-withdrawing groups.

8. The composition according to any one of claims 1 to 7, wherein the nonpolymeric electron acceptor compound comprises a compound represented by one of formulas (27A) to (30A): in, In equations (27A) to (30A), R 82 To R 93 Each is independently hydrogen, deuterium, halogen, nitro, amino, cyano, pyridinium, substituted or unsubstituted C. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 1-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 Aryl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 2-30 heteroaryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 3-30 Alkyl heteroaryl; R 82 To R 93 Each of them optionally also includes one or more divalent linking groups as part of its structure; R 82 and R 83 Optionally, they form rings with each other via one or more divalent linking groups; R 84 To R 87 Two or more adjacent groups may optionally form a ring with each other through one or more divalent linking groups; R 88 To R 91 Two or more adjacent groups optionally form a ring with each other via one or more divalent linking groups; and x is 1 or 2.

9. The composition of any one of claims 1 to 8, comprising two or more nonpolymeric electron acceptor compounds, wherein the two or more nonpolymeric electron acceptor compounds have a greater electron affinity than the photoacid-producing compound.

10. The composition of any one of claims 1 to 9, wherein the photoacid-producing compound comprises an onium salt.

11. The composition of any one of claims 1 to 9, wherein the photoacid-producing compound comprises a nonionic compound or a zwitterionic compound.

12. The composition of any one of claims 1 to 11, wherein the photoacid-producing compound is a photoacid-producing polymer.

13. A method for forming a pattern, comprising: (a) Applying a layer of the composition according to any one of claims 1 to 12 onto a substrate; (b) Soft-baking the layer of the composition; (c) Expose the soft-baked layer of the composition to EUV or electron beam activation radiation; (d) Baking the layer of the composition after exposure; as well as (e) Develop the layer of the exposed and baked composition to provide a photoresist relief image.

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