Electroactive compound, composition containing electroactive compound, and pattern forming method

Abstract

The present invention provides electroactive compounds, compositions containing electroactive compounds, and methods for pattern formation. [Solution] A composition comprising: an acid-sensitive polymer containing a first repeating unit derived from a monomer containing an acid-degradable group; a photoacid generator compound; a nonpolymer electron acceptor compound having an electron affinity greater than the electron affinity of the photoacid generator compound, which does not generate photoacid and does not contain a plurality of diazonaphthoquinone (DNQ) groups; and a solvent present in the composition in an amount exceeding 50 weight percent based on the total weight of the composition, wherein the composition is a positive-type EUV photoresist or electron beam resist.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority and all interests of U.S. Provisional Patent Application No. 63 / 699,950, filed September 27, 2024, the entirety of which is incorporated herein by reference. field The present invention relates to an electroactive compound for a composition comprising a photoresist composition, and a patterning method using the composition. The present invention is applicable to lithography applications in the semiconductor manufacturing industry. [Background technology]

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

[0003] Chemically amplified photoresists have been conventionally used for high-resolution processing. Such resists typically utilize polymers with acid-unstable groups, photoacid generators, and acid quenching materials. Pattern-like exposure to activating radiation via a photomask causes the acid generator to form acid, which, during post-exposure baking, causes cleavage of acid-unstable groups within the exposed regions of the polymer. Acid quenching materials are often added to the photoresist composition to control the diffusion of acid into unexposed regions and improve contrast. As a result of the lithography process, a difference in solubility occurs between the exposed and unexposed regions of the resist in the developer. In the positive-tone development (PTD) process, the exposed regions of the photoresist layer become soluble in the developer and are 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.

[0004] Extreme ultraviolet lithography (EUVL) is a photolithography technique capable of imaging the most critical small feature patterns for advanced integrated circuits. The semiconductor industry has adopted EUVL as its preferred patterning technique to print critical features on sub-7nm node devices within contacts, vias, metal lines, and cut layers, for example, when cutting can be applied to FinFETs, nanosheet FETs, or metal lines. Single-exposure EUV enables chip manufacturers to pattern the most challenging features at the 5nm node. Significant advancements in EUV technology over the past few years have enabled acceptable throughput, for example, using ASML's EUV NXE:3400C scanner incorporating a 0.33 numerical aperture (NA) lens. Extending 0.33NA EUV single-exposure patterning to nodes above 3nm requires continued progress in photoresist technology. Essential to the continued advancement of patterning technology is the development of lithography patterning solutions to support high-NA EUV. As the industry anticipates the implementation of High NA (0.55NA) EUV, the demand for new materials will increase further. These essential materials include photoresist materials, underlayer materials, and rinse materials, which will help the industry surpass current industry requirements for resolution, linewidth roughness, and sensitivity in modern photoresists while meeting targets for stochastic and non-stochastic defect handling and etching pattern transfer. Balancing these properties is a challenge for the entire industry. To overcome this trade-off and extend Moore's Law to next-generation devices, it is essential to develop new chemistry, new formulation strategies, and deepen their fundamental understanding. [Overview of the project]

[0005] One embodiment provides a composition which is a positive EUV photoresist or electron beam resist, comprising: an acid-sensitive polymer comprising a first repeating unit derived from a monomer containing an acid-degradable group; a photoacid generator compound; a nonpolymer electron acceptor compound having an electron affinity greater than that of the photoacid generator compound, which does not generate photoacid and does not contain a plurality of diazonaphthoquinone (DNQ) groups; and a solvent present in the composition in an amount exceeding 50 weight percent based on the total weight of the composition.

[0006] Another embodiment provides a pattern forming method comprising: coating a layer of composition onto a substrate; soft baking the composition layer; exposing the soft-baked composition layer to EUV or electron beam activated radiation; post-exposure baking the composition layer; and developing the post-exposure baked composition layer to provide a resist relief image. [Modes for carrying out the invention]

[0007] Here, exemplary embodiments are described in detail, and examples thereof are shown herein. These exemplary embodiments may take different forms and are not limited to those described herein. Therefore, exemplary embodiments are described below simply by reference to the drawings to illustrate aspects of this specification. The terms “and / or” as used herein include any combination of one or more of the related enumerated items. Expressions such as “at least one” preceding a list of elements modify the entire list of elements, and not the individual elements of the list.

[0008] As used herein, the terms “a,” “an,” and “the” are not limited in quantity and should be interpreted as encompassing both singular and plural unless otherwise indicated herein or unless clearly contradicted by the context. “Or” means “and / or” unless otherwise specified. The modifier “about” used in relation to quantity includes the stated value and has a meaning indicated by the context (e.g., including the degree of error associated with a measurement of a particular quantity). All scopes disclosed herein include endpoints, which can be combined independently of each other. The suffix “(s)” is intended to include at least one of the terms it modifies, by including both the singular and plural forms of that term. “Optional” or “optionally” means that the event or situation described thereafter may or may not occur, and that the description includes both cases where the event occurs and cases where it does not. Terms such as “first,” “second,” etc., used herein are not used to indicate order, quantity, or importance, but to distinguish one element from another. When an element is described as being "on" another element, it may be in direct contact with the other element, or there may be an intervening element between them. In contrast, when an element is described as being "directly on" another element, there is no intervening element. It should be understood that the components, elements, limitations, and / or features of the embodiments described may be combined in any appropriate way in various embodiments.

[0009] Unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as commonly understood by those skilled in the art in which the invention pertains. Terms as defined in commonly used dictionaries should be construed to have the meaning consistent with their meaning in the context of the relevant art and this disclosure, and it will be further understood that, unless expressly defined herein, they should not be interpreted in an idealized or overly formal sense.

[0010] As used herein, "active rays" or "radiation" means, for example, the emission spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet (EUV) light, X-rays, or particle beams, such as electron beams and ion beams. In this invention, "light" means active rays or radiation. A krypton fluoride laser (KrF laser) is a specific type of excimer laser, sometimes called an exciplex laser. "Excimer" is an abbreviation for "excitation dimer," while "exciplex" is an abbreviation for "excitation complex." Excimer lasers use a mixture of noble gases (argon, krypton, xenon) and halogen gases (fluorine or chlorine) and emit coherent stimulating radiation (laser light) in the ultraviolet region under appropriate conditions of electrical stimulation and high pressure. Furthermore, unless otherwise specified, "exposure" in this specification includes not only exposure using mercury lamps, excimer lasers, or other far-ultraviolet, X-ray, or extreme ultraviolet (EUV) light, but also lighting using particle beams such as electron beams and ion beams.

[0011] As used herein, “organic group” refers to a group having one or more carbon atoms, e.g., 1 to 60 carbon atoms. The term “hydrocarbon” refers to an organic compound, or an organic group having at least one carbon atom and at least one hydrogen atom. The term “alkyl” refers to a monovalent linear or branched saturated hydrocarbon group having a specified number of carbon atoms. “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 a group having the formula “-C(=O)-OH”. “Cycloalkyl” refers to a monovalent group having one or more saturated rings where all ring members are carbon. “Cycloalkylene” refers to a divalent cycloalkyl group. “Alkenyl” refers to a linear or branched monovalent hydrocarbon group having at least one carbon-carbon double bond. “Alkenoxy” refers to “alkenyl-O-”. “Alkenylene” refers to a divalent alkenyl group. "Cycloalkenyl" refers to a non-aromatic cyclic divalent hydrocarbon group having at least three carbon atoms and having at least one carbon-carbon double bond. "Alkynyl" refers to a monovalent hydrocarbon group having at least one carbon-carbon triple bond. The term "aromatic group" refers to a monocyclic or polycyclic ring system that satisfies Huckel's rule, contains carbon atoms in the ring, and may contain one or more heteroatoms selected from N, O, and S instead of carbon atoms. "Aryl" refers to a monovalent aromatic monocyclic or polycyclic ring system in which all ring members are carbon, and may include a group having an aromatic ring fused to at least one cycloalkyl or heterocycloalkyl ring. "Arylene" refers to a divalent aryl group. "Alkylaryl" refers to an aryl group substituted with an alkyl group. "Arylalkyl" refers to an alkyl group substituted with an aryl group. "Aryloxy" refers to "aryl-O-". "Arylthio" refers to "aryl-S-".

[0012] The prefix "hetero" means that a compound or group contains at least one member that is a heteroatom (e.g., 1, 2, 3, or 4, or more heteroatoms) instead of carbon atoms, and that each heteroatom is independently N, O, S, Si, or P. A "heteroatom-containing group" refers to a substituent that contains at least one heteroatom. A "heteroalkyl group" refers to an alkyl group that has 1 to 4, or more, heteroatoms instead of carbon atoms. A "heterocycloalkyl group" refers to a cycloalkyl group that has 1 to 4, or more, heteroatoms as ring members instead of carbon atoms. A "heterocycloalkylene group" refers to a divalent heterocycloalkyl group. A "heteroaryl group" refers to an aryl group that has 1 to 4, or more, heteroatoms as ring members instead of carbon atoms. A "heteroarylene group" refers to a divalent heteroaryl group.

[0013] Each of the aforementioned substituents may be substituted unless otherwise specified. For example, if a group is mentioned without specifying whether it is substituted or unsubstituted, that group includes both unsubstituted and substituted groups. The term "may be substituted" means either substituted or unsubstituted.

[0014] "Substituted" means that at least one hydrogen atom in the chemical structure is replaced by another terminal substituent, typically monovalent, as long as it does not exceed the normal valence of the specified atom. If the substituent is oxo (i.e., =O), the two geminal hydrogen atoms on the carbon atom are replaced by the terminal oxo group. Combinations of substituents or variables are permitted. Exemplary substituents that may be present on a "substituted" position include nitro (-NO2), cyano (-CN), hydroxyl (-OH), oxo (=O), amino (-NH2), mono- or di-(C) 1~6 ) Alkylamino, alkanoyl (e.g., acyl, etc.) 2~6 Alkanoyl group), formyl (-C(=O)H), carboxylic acid or its alkali metal or ammonium salt; C 2~6Alkyl esters (-C(=O)O-alkyl or -OC(=O)-alkyl) and C 7~13 esters such as aryl esters (-C(=O)O-aryl or -OC(=O)-aryl) (including acrylates, methacrylates, and lactones), amides (-C(=O)NR2 where R is hydrogen or C 1~6 alkyl), carboxamides (-CH2C(=O)NR2 where R is hydrogen or C 1~6 alkyl), halogen, thiol (-SH), C 1~6 alkylthio (-S-alkyl), thiocyano (-SCN), C 1~6 alkyl, C 2~6 alkenyl, C 2~6 alkynyl, C 1~6 haloalkyl, C 1~9 alkoxy, C 1~6 haloalkoxy, C 3~12 cycloalkyl, C 5~18 cycloalkenyl, C 2~18 heterocycloalkenyl, C having at least one aromatic ring (e.g., phenyl, biphenyl, or naphthyl, etc. (each ring is a substituted or unsubstituted aromatic)) 6~12 aryl, C having 1 to 3 separate or fused rings and 6 to 18 ring carbon atoms 7~19 arylalkyl, arylalkoxy having 1 to 3 separate or fused rings and 6 to 18 ring carbon atoms, C 7~12 alkylaryl, C 3~12 heterocycloalkyl, C 3~12 heteroaryl, C 1~6 alkylsulfonyl (-S(=O)2-alkyl), C 6~12 arylsulfonyl (-S(=O)2-aryl), or tosyl (CH3C6H4SO2-), etc., but not limited thereto.

[0015] The term "halogen" refers to a monovalent substituent that is fluorine (fluoro), chlorine (chloro), bromine (bromo), or iodine (iodo). The prefix "halo" refers to a group that contains one or more fluoro, chloro, bromo, or iodo substituents instead of a hydrogen atom. A combination of halo groups (e.g., bromo and fluoro) or a fluoro group alone may be present. For example, the term "haloalkyl" refers to an alkyl group substituted with one or more halogens. As used herein, "substituted C 1~8 "Haloalkyl" refers to a C atom substituted with at least one halogen. 1~8 This refers to an alkyl group, which is optionally further substituted with one or more other non-halogen substituents.

[0016] As used herein, “acid-unstable group” refers to a group whose bond is optionally, and typically, cleaved by the action of an acid, resulting in the formation of a polar group such as a carboxylic acid or alcohol group on the polymer, and the portion linked to the cleaved bond being optionally, and typically, cleaved from the polymer. As used herein, the term “acid-degradable group” is synonymous with “acid-unstable group.” In other systems, nonpolymer compounds may contain acid-unstable groups that can be cleaved by the action of an acid, resulting in the formation of a polar group such as a carboxylic acid or alcohol group on the cleaved portion of the nonpolymer compound. Such acids are typically photo-generated acids in which bond cleavage occurs during post-exposure baking (PEB). However, embodiments are not limited thereto, and such acids may be thermally generated, for example. Suitable acid-unstable groups include, for example, tertiary alkyl ester groups, secondary or tertiary aryl ester groups, secondary or tertiary ester groups having a combination of alkyl and aryl groups, tertiary alkoxy groups, tertiary carbonate groups, acetal groups, or ketal groups. Furthermore, groups that are unstable to acids are generally referred to in this technical field as "acid-cleaving groups," "acid-cleaving protecting groups," "acid-unstable protecting groups," "acid-leaving groups," "acid-degradable groups," and "acid-sensitive groups."

[0017] As used herein, unless otherwise defined, “divalent linking group” refers to -O-, -S-, -Te-, -Se-, -C(O)-, -C(O)O-, -N(R a )-, -S(O)-, -S(O)2-, -C(S)-, -C(Te)-, -C(Se)-, substitution or non-substitution C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylenes, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 R refers to a divalent group containing one or more heteroarylenes or combinations thereof. 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 It is a heteroaryl compound. Typically, the divalent linking groups are -O-, -S-, -C(O)-, -C(O)O-, and -N(R a )-, -S(O)-, -S(O)2-, substitution or non-substitution C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylenes, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 It contains one or more heteroarylenes or combinations thereof, R a C is 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 It is a heteroaryl compound. More typically, the divalent linking groups are -O-, -C(O)-, -C(O)O-, -N(R a )-,-C(O)N(R a )-, substitution or non-substitution C 1~10 Alkylene, substituted or unsubstituted C 3~10 Cycloalkylene, substituted or unsubstituted C3~10 Heterocycloalkylenes, substituted or unsubstituted C 6~10 Arylene, substituted or unsubstituted C 3~10 The R includes at least one heteroarylene or a combination thereof. a C is hydrogen, deuterium, substituted or unsubstituted C 1~10 Alkyl, substituted, or unsubstituted C 1~10 Heteroalkyl, substituted, or unsubstituted C 6~10 Aryl, or substituted or unsubstituted C 3~10 It is a heteroaryl compound.

[0018] As mentioned above, chemically amplified photoresists have long been the workhorse for high-resolution semiconductor patterning. This method uses photoacid generated by radiation exposure to deprotect leaving groups on polymer chains and regenerates the photoacid itself for further deprotection of other leaving groups over many cycles. This results in solubility switching between exposed and unexposed areas of the substrate coating layer. Traditionally, chemically amplified photoresists have functioned based on the principle of acid diffusion to dramatically increase resist sensitivity. Deep UV photoresist products and low NA EUV photoresist products still utilize chemically amplified photoresist-based chemistry. Controlling the photoacid diffusion length can be important for performance, as broad acid diffusion can blur the resulting images and patterns and reduce their roughness and resolution.

[0019] EUV patterning presents additional challenges based on its inherent photochemical mechanism. During EUV exposure, when 92 eV photons (13.5 nm) are initially absorbed by the photoresist composition, most of these result in ionization of the polymer matrix, followed by the generation of primary electrons. These primary electrons, being high-energy, can further excite the matrix, generating additional secondary electrons, including thermally generated low-energy secondary electrons. These thermally generated low-energy secondary electrons essentially react irreversibly with the photoacid generator (PAG) component, leading to PAG decomposition and the release of photoacid. Therefore, to improve EUV resist sensitivity, the PAG component may be selected for its higher electron affinity (or higher reduction potential) to prioritize the addition of secondary electrons. In addition, the high energy of EUV radiation means a limited number of EUV photons at typical resist exposure doses. Thus, a high EUV absorbance profile of the photoresist composition is a useful factor in resist design and component selection.

[0020] In EUV chemically amplified photoresists, additional challenges arise due to the involvement of secondary electrons in the acid generation pathway. Since the electron thermalization distance (meaning the total distance electrons travel in a random walk model after generation and before quenching or reacting with PAG) in EUV resists is measured to be an average of 3–7 nm in organic polymer matrices, electron blurring can be significant. This can also be called secondary electron diffusion, which refers to the scattering and movement of secondary electrons generated when EUV photons interact with the resist material. Due to their ability to spread beyond the intended exposure area, this significantly impacts the accuracy of the final pattern, causing blurring at the edges of features. Increasing the resist film density in metal oxide resists, for example, may be beneficial in suppressing secondary electron blurring. However, low-density films fabricated from organic chemically amplified photoresist materials are thought to have higher electron blurring that may not meet the required level of roughness for EUV patterning of high-resolution features.

[0021] The present invention addresses the electron blurring problem by providing an electron blurring control additive. The additive is a nonpolymer electron acceptor compound used in EUV photoresists or E-beam compositions (including organic, inorganic, or metal resists). By using the electron acceptor compound, electron blurring estimation is controlled, thereby inherently improving the resolution and roughness of printed features. In chemically amplified EUV photoresists or E-beam resists, the disclosed nonpolymer electron acceptor compound additive has a higher electron affinity (or higher reduction potential) than the electron affinity of the present photoacid generator compound, so that secondary electrons are more preferentially quenched before reacting with the PAG compound, thereby effectively improving deprotection contrast and thus lithography performance.

[0022] While not limited to theory, the mechanism of secondary electron acceptors or quenchers mimics the photoacid diffusion control of basic quencher additives in conventional chemically amplified photoresist systems for deep UV lithography. Conceptually, by introducing a secondary electron quencher component into the formulation to eliminate rapidly diffusing electrons, electron blurring is inherently controlled, thereby improving contrast and ultimately enhancing resolution and coarseness.

[0023] As used herein, "reduction potential" represents the affinity of an electron-accepting material. This is the formal potential (E o’The reduction potential can be measured by cyclic voltammetry, which involves measuring the cathode peak potential. Using cyclic voltammetry of the acceptor compound, the reduction potential is estimated by the cathode peak potential. In a typical cyclic voltammetry measurement, each material is dissolved in a distilled dry solvent such as dry acetonitrile to prepare a 1 millimolar (mM) solution of the redox molecule for measurement. As a supporting electrolyte, an electrolyte such as a 0.1 M solution of tetrabutylammonium perchlorate is used. Regarding electrodes, a 4 mm Pt disk, a coiled Pt wire, and an Ag / AgCl electrode may be used as the working electrode, counter electrode, and reference electrode, respectively. The solution is purged with N2 gas for 5-10 minutes before the electrochemical measurement to replace dissolved O2. The measurement is typically performed at room temperature at the desired scanning speed.

[0024] As used herein, "electron affinity" refers to the affinity of an electron-accepting material. Electron affinity can be calculated by forming a sample layer on a quartz substrate. Subsequently, the absorption spectrum of the prepared sample may be measured using a spectrophotometer, and the optical band gap can be calculated from the absorption edge results of the obtained absorption spectrum. Electron affinity can be estimated by subtracting the calculated optical band gap from the ionization potential obtained below.

[0025] The ionization potential can be measured as follows. A sample was formed on a glass substrate with an ITO film. Subsequently, the number of photoelectrons was measured using photoelectron yield spectroscopy in air with varying ultraviolet irradiation energy, and the energy position at which the first photoelectrons were detected was assumed to be the ionization potential.

[0026] 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 provide accurate predictions of molecular properties. Those skilled in the art can use quantum chemical calculations to gain a detailed understanding of the molecular electronic structure and how that structure affects its overall properties. Lowest Unoccupied Molecular Orbital (LUMO) energies were calculated using quantum chemical calculations. Density Functional Theory (DFT) calculations were performed at the B3LYP level using the 6-31+G(d,p) basis set in the Gaussian 16 software package. The molecular geometry was initially optimized and verified using DFT. Typically, vibrational frequency analysis was used to verify the minimum energy geometry. Upon optimization, a DFT output file containing molecular orbital energies was obtained.

[0027] Furthermore, the reduction potential of molecules can be estimated using quantum chemical calculations. The calculation method specified in J.Phys.Chem.C 2014,118,12,6046-6051 is suitable for calculating the reduction potential of organic compounds. Using this method, density functional theory (DFT) calculations were performed to confirm the global minimum energy structure. Modeling was performed for each molecule in solution by using a polarization continuum (PC) model with a solvent such as propylene carbonate. The energy before and after electron addition (reduction) was calculated using DFT calculations. Then, the free energy ΔG of the reduction reaction was calculated using these calculated energies. The formal potential E of the molecule was calculated from the free energy difference ΔG of the reaction using ΔG=nFE (where n is the number of electrons transferred and F is the Faraday constant). This calculation result was converted to E versus vacuum and then to Ag / AgCl.

[0028] Furthermore, the electron affinity of PAG cations and electron acceptor-doped compounds can also be estimated using quantum chemical calculations. Electron affinity is defined as the energy released when an electron is added to the molecule. Typically, vibrational frequency analysis was used to determine the global minimum energy geometry. Adiabatic electron affinity was calculated using the calculated energy of the optimized structure. For unstable radicals, etc., where the geometry could not be optimized, perpendicular electron affinity was calculated. For neutral molecules, electron affinity was calculated as the energy difference between the neutral form and the corresponding anion-radical form, which is the form produced when one electron is added. For positively charged species, such as sulfonium cations with a charge of +1, perpendicular electron affinity was calculated as the energy difference between the cation with a charge of +1 and the radical form produced when one electron is added.

[0029] Here, a material that donates electrons to another molecule or chemical species during a chemical reaction is called an electron-donating material, and a material that accepts electrons from another molecule or chemical species during a chemical reaction is called an electron-accepting material. When two different types of organic materials are used, the type that becomes the donor material and the type that becomes the acceptor material are generally determined according to the relative positions of the energy levels of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of each of the two organic materials at the contact interface. The energy difference between the vacuum level (0 eV) and the LUMO energy level correlates with electron affinity. Generally, the lower the LUMO energy level, the better the electron-accepting ability. In addition, the energy difference between the vacuum level and the HOMO energy level correlates with the ionization potential, and the higher the HOMO energy, the better the electron-donating ability.

[0030] The inventors have discovered that EUV or E-beam photoresist compositions exhibit superior lithography performance when an efficient nonpolymer secondary electron acceptor compound with higher electron affinity than the photoacid generator compound is added to the composition. The inventors have also discovered that "fast-diffusing" secondary electrons diffusing into the non-exposed region can be eliminated (or quenched) before reacting with PAG cations to generate photoacids for undesirable resist leaving group deprotection. Materials with lower LUMO energy levels, i.e., materials with higher electron affinity and reduction potential, become electron acceptor materials.

[0031] Provided herein are compositions comprising an acid-sensitive polymer comprising a first repeating unit derived from a monomer containing an acid-degradable group. The composition comprises a photoacid generator compound. The composition comprises a nonpolymer electron acceptor compound having an electron affinity greater than that of the photoacid generator compound, wherein the nonpolymer electron acceptor compound does not generate photoacid, and the nonpolymer electron acceptor compound does not contain multiple diazonaphthoquinone (DNQ) groups. The composition also comprises a solvent, which is present in the composition in an amount exceeding 50 wt% based on the total weight of the composition. The composition is a positive EUV photoresist or electron beam resist.

[0032] Nonpolymer electron acceptor compounds have a greater electron affinity than the photoacid generator (or, in the case of ionic photoacid generator compounds, a greater electron affinity than the photoacid generator cation). In addition, nonpolymer electron acceptor compounds do not generate photoacid upon exposure to EUV radiation or electron beams, and nonpolymer electron acceptor compounds do not contain multiple DNQ groups. The electron affinity of a PAG compound can be determined based on the structure of the PAG compound. For example, a nonpolymer electron acceptor compound may have a greater electron affinity than the cationic moiety of the photoacid generator compound, a greater electron affinity than the zwitterionic moiety of the photoacid generator compound, or a greater electron affinity than the overall structure of a nonionic photoacid generator compound. The photoacid generator compounds used herein may have multiple active centers, such as multiple electron-reactive cations. The photoacid generator compounds may be small molecule compounds or polymer compounds.

[0033] In some embodiments, the nonpolymer electron acceptor compound has a greater electron affinity than triphenylsulfonium, for example, substituted triphenylsulfonium. In some embodiments, the nonpolymer electron acceptor compound has a greater electron affinity than diphenyliodonium, for example, substituted diphenyliodonium.

[0034] Nonpolymer electron acceptor compounds include a conjugated organic group, which may be substituted by conjugation with one or more electron-withdrawing groups. A conjugated organic compound or structure is a type of organic molecular structure in which single and double bonds alternate between carbon atoms and / or other atoms. In some embodiments, the nonpolymer electron acceptor compound includes a conjugated organic group but does not include an electron-withdrawing group. Exemplary conjugated organic groups include vinyl, 1,3-butadienyl, ethynyl, carbonyl, 1,3-butadienyl, and combinations thereof. Other exemplary conjugated organic groups include aromatic groups and heteroaromatic groups, e.g., those having a five-membered or six-membered ring, or combinations thereof. Some examples of suitable groups include five-membered or six-membered rings, or combinations of multiple rings, with or without heteroatoms. Another class of conjugated organic groups useful in the present invention are aromatic quinonoids, in particular substituted or unsubstituted benzoquinones or naphthoquinones. Quinones may be alkyl-substituted, alkoxy-substituted, hydroxy-substituted, halo-substituted, nitro-substituted, or cyano-substituted benzoquinones, or alkyl-substituted, alkoxy-substituted, hydroxy-substituted, halo-substituted, nitro-substituted, or cyano-substituted naphthoquinones, or combinations thereof. Other examples of quinonoid groups include dichlorobenzoquinone, dicyanobenzoquinone, cyanyl, chloranyl, bromonyl, and tetracyanoquinodimethane. Other examples of conjugated organic groups include, but are not limited to, tetracyanoethylene, fluorenone, or fluorenones substituted with electron-withdrawing groups, such as 2-nitrofluorenone, 2,7-dinitrofluorenone, 2,4,7-trinitrofluorenone, fullerenes and their derivatives, porphyrins and their derivatives, phthalocyanines and their derivatives, and groups derived from pyridinium salts, etc. Examples of electron-withdrawing groups include, but are not limited to, cyano (C(CN)2 and N-CN), pyridinium, oxo, nitro, halogen, haloalkyl, ester, sulfone, sulfonamide, sulfonimide, phthalimide, and naphthalimide groups. A combination of one or more different electron-withdrawing groups may be used.In some embodiments, the conjugated organic group may contain an electron-withdrawing group within its structure. In some embodiments, the conjugated organic group may contain a cationic atom, such as a nitrogen cation, which is considered to be the electron-withdrawing group within it.

[0035] Further examples of nonpolymer electron acceptor compounds include ammonium salts (substituted or unsubstituted) that have a greater electron affinity than the photoacid generator.

[0036] In some embodiments, the nonpolymer electron acceptor compound is formula (1) to (5): [ka] Examples of compounds that can be represented by one or more of the following:

[0037] In equations (1) to (5), R 1 ~R 25 , R 20a , and R 21a These are, independently, hydrogen, deuterium, halogen, nitro, amino, cyano, pyridinium, substituted or unsubstituted C, respectively. 1~30 Alkyl, substituted, or unsubstituted C 1~30 Heteroalkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 1~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 2~30 Heteroaryl, substituted, or unsubstituted C 3~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 It is an alkyl heteroaryl. In some embodiments, R 1 ~R 25 , R 20a , and R 21a These are, independently, hydrogen, deuterium, and C.1~4 It may be alkyl, cyano, pyridinium, nitro, or C 1~4 fluoroalkyl. Typically, R 1 ~R 25 、R 20a 、and R 21a are each independently hydrogen, substituted or unsubstituted C 1~4 alkyl, or substituted or unsubstituted C 1~4 fluoroalkyl.

[0038] In Formulas (1) to (5), R 1 ~R 25 、R 20a 、and R 21a may each further contain one or more divalent linking groups as part of its structure. Exemplary divalent linking groups are -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 heterocycloalkylene, substituted or unsubstituted C 6~30 arylene, substituted or unsubstituted C 3~30 heteroarylene, or a combination thereof, and R ’ is 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.

[0039] In Formula (1), two or more adjacent ones of R 1 ~R 10 may form a ring with each other via a divalent linking group, each of the one or more divalent linking groups is substituted or unsubstituted, and the ring is substituted or unsubstituted.

[0040] In Formula (1), L 1C is either a single bond or a divalent linking group. Examples of divalent linking groups include -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R')-, -C(O)N(R')-, and substituted or unsubstituted C. 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylenes, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 Heteroarrenes, or combinations thereof, may be selected. ’ C is 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 It can be a heteroaryl. For example, L 1 C is a single bond, substituted or unsubstituted C 6~30 Arylene, or substituted or unsubstituted C 3~30 It could be a heteroarrene.

[0041] In equation (2), R 11 ~R 19 Two or more adjacent elements may form a ring with each other via divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted.

[0042] In equation (2), L 2 C is either a single bond or a polyvalent linking group. Examples of polyvalent linking groups include -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 Heterocycloalkylenes, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 Heteroarrenes, or combinations thereof, may be selected.’ C is 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 It can be a heteroaryl compound. If the group is polyvalent, the valency is 2 or greater. For example, L 2 C is a single bond, substituted or unsubstituted polyvalent C 6~30 Arylene, or substituted or unsubstituted polyvalent C 3~30 It could be a heteroarrene.

[0043] In equation (2), p is an integer between 2 and 6. Typically, p is an integer between 2 and 4.

[0044] In equations (1) and (2), A - and B - These are each an independent organic anion, and A - and B - These may bond together to form a divalent organic anion. Exemplary organic anions include those whose conjugate acid typically has a pKa of -15 to 10. For example, A - and B - These can each be independently a sulfonate ion, a carboxylate ion, a sulfonamide anion, a sulfonimide anion, or a methide anion.

[0045] In equation (3), two or more adjacent R 20 However, they may form a ring with each other via divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted.

[0046] In equation (3), n1 is an integer between 0 and 4. Preferably, n1 is 0 or 1.

[0047] In equation (3), X is either 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 are, independently, -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -S(O)2-, and -N(R ’ )-, -C(O)N(R')-, substitution or non-substitution C 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylenes, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 Heteroarrenes, or combinations thereof, may be selected. ’ C is 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 It can be a heteroaryl group. Typically, X can be a single bond, or substituted or unsubstituted C. 1~20 It can be an alkylene, preferably a single bond, or substituted or unsubstituted carbon. 1~10 It could be alkylene.

[0048] In equation (4), A - A is an organic anion. Examples of organic anions include those whose conjugate acid typically has a pKa of -15 to 10. For example, A - This can be a sulfonate ion, a carboxylate ion, a sulfonamide anion, a sulfonimide anion, or a methide anion.

[0049] In equation (4), n² is an integer between 0 and 5. Typically, n² is either 0 or 1.

[0050] In equation (4), two or more adjacent R 21However, they may form a ring with each other via divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted.

[0051] In equation (5), R 22 ~R 25 Two or more of these may form a ring with each other via divalent linking groups, where the divalent linking groups are substituted or unsubstituted, and the ring is substituted or unsubstituted.

[0052] In equation (5), A - A is an organic anion. Examples of organic anions include those whose conjugate acid typically has a pKa of -15 to 10. For example, A - This can be a sulfonate ion, a carboxylate ion, a sulfonamide anion, a sulfonimide anion, or a methide anion.

[0053] In some embodiments, the nonpolymer electron acceptor compound is formula (6) to (26): [ka] [ka] One or more of these compounds may be mentioned.

[0054] In equations (6) to (26), R 26 ~R 81 These are, independently, hydrogen, deuterium, halogen, nitro, amino, cyano, pyridinium, substituted or unsubstituted C, respectively. 1~30 Alkyl, substituted, or unsubstituted C 1~30 Heteroalkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 1~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C7~30 Arylalkyl, substituted or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 2~30 Heteroaryl, substituted, or unsubstituted C 3~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 It is an alkyl heteroaryl. Typically, R 26 ~R 81 These are, independently, hydrogen, deuterium, halogen, substituted or unsubstituted C, respectively. 1~20 Alkyl, substituted, or unsubstituted C 1~20 Heteroalkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, substituted, or unsubstituted C 1~20 Heterocycloalkyl, substituted or unsubstituted C 2~20 Alkenyl, substituted or unsubstituted C 2~20 Alkynyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 2~30 Heteroaryl, substituted, or unsubstituted C 3~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 It is an alkyl heteroaryl.

[0055] In equations (6) to (26), R 26 ~R 81 Each of these may further contain one or more divalent linking groups as part of its structure. Exemplary divalent linking groups include -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 Heterocycloalkylenes, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 Heteroarrenes, or combinations thereof, may be selected. ’ C is 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 It could be a heteroaryl.

[0056] In equation (6), R 26 ~R 31 Two or more adjacent members may form a ring with each other via one or more divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted.

[0057] In equation (7), R 32 ~R 36 Two or more adjacent members may form a ring with each other via one or more divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted.

[0058] In equation (7), X - X is an organic anion. Examples of organic anions include those whose conjugate acid typically has a pKa of -15 to 10. For example, X - This can be a sulfonate ion, a carboxylate ion, a sulfonamide anion, a sulfonimide anion, or a methide anion.

[0059] In equation (8), R 37 ~R 40 Two or more adjacent elements may form a ring with each other via one or more divalent linking groups, each of which is either substituted or unsubstituted, and the ring may be either substituted or unsubstituted. The ring may be aromatic or unaromatic.

[0060] 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 group, sulfone group, sulfonamide group, sulfonimide group, phthalimide group, and naphthalimide group.

[0061] In formula (9), R 41 ~R 46 Two or more adjacent ones of them may form a ring with each other via one or more divalent linking groups, each of the one or more divalent linking groups may be substituted or unsubstituted, and the ring may be substituted or unsubstituted. For example, two or more adjacent ones of R 41 ~R 43 may form a ring with each other via one or more divalent linking groups, each of the one or more divalent linking groups may be substituted or unsubstituted, the ring may be substituted or unsubstituted, and / or two or more adjacent ones of R 44 ~R 46 may form a ring with each other via one or more divalent linking groups, each of the one or more divalent linking groups may be substituted or unsubstituted, and the ring may be substituted or unsubstituted.

[0062] In formula (10), two or more adjacent ones of R 47 ~R 51 may form a ring with each other via one or more divalent linking groups, each of the one or more divalent linking groups may be substituted or unsubstituted, and the ring may be substituted or unsubstituted.

[0063] In formula (11), R 52 and R 53 may not be linked to each other via a linking group to form a ring.

[0064] In formula (12), R 54 ~R 55Two or more adjacent elements may form a ring with each other via one or more divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted. For example, R 54 Two or more adjacent elements may form a ring with each other via one or more divalent linking groups, each of which is substituted or unsubstituted, and the ring is substituted or unsubstituted, and / or R 55 Two or more adjacent elements may form a ring with each other via one or more divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted.

[0065] In formula (12), X includes an electron-withdrawing group. Examples of electron-withdrawing groups include, but are not limited to, cyano (C(CN)2 and N-CN), pyridinium, oxo, nitro, thiol, disulfide, halogen, haloalkyl, ester, sulfone, sulfonamide, sulfonimide, phthalimide, and naphthalimide groups.

[0066] In equation (12), n1 and n2 are independently integers between 0 and 4. Typically, n1 and n2 are independently 0 or 1.

[0067] In equation (13), R 56 ~R 57 Two or more adjacent elements may form a ring with each other via one or more divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted. For example, R 56 Two or more adjacent elements may form a ring with each other via one or more divalent linking groups, each of which is substituted or unsubstituted, and the ring is substituted or unsubstituted, and / or R 57Two or more adjacent elements may form a ring with each other via one or more divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted.

[0068] In equation (13), n4 and n5 are independently integers between 0 and 2. Typically, n4 and n5 are independently 0 or 1.

[0069] In equation (14), R 58 ~R 59 Two or more adjacent elements may form a ring with each other via one or more divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted. For example, R 58 Two or more adjacent elements may form a ring with each other via one or more divalent linking groups, each of which is substituted or unsubstituted, and the ring is substituted or unsubstituted, and / or R 59 Two or more adjacent elements may form a ring with each other via one or more divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted.

[0070] In equation (14), n6 and n7 are independently integers between 0 and 4. Typically, n6 and n7 are independently 0 or 1.

[0071] In equation (15), R 60 ~R 61 Two or more adjacent elements may form a ring with each other via one or more divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted. For example, R 60Two or more adjacent elements may form a ring with each other via one or more divalent linking groups, each of which is substituted or unsubstituted, and the ring is substituted or unsubstituted, and / or R 61 Two or more adjacent elements may form a ring with each other via one or more divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted.

[0072] In equation (15), n8 and n9 are independently integers between 0 and 4. Typically, n8 and n9 are independently 0 or 1.

[0073] In equation (16), R 64 ~R 65 Two or more adjacent elements may form a ring with each other via one or more divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted. For example, R 64 Two or more adjacent elements may form a ring with each other via one or more divalent linking groups, each of which is substituted or unsubstituted, and the ring is substituted or unsubstituted, and / or R 65 Two or more adjacent elements may form a ring with each other via one or more divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted.

[0074] In equation (16), each l is an independent integer between 0 and 4. Typically, each l is either 0 or 1.

[0075] In equation (17), R 68 Two or more adjacent members may form a ring with each other via one or more divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted.

[0076] In equation (17), l is an integer between 0 and 4. Typically, l is 0 or 1.

[0077] In equation (18), R 70 Two or more adjacent members may form a ring with each other via one or more divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted.

[0078] In equation (18), l is an integer between 0 and 4. Typically, l is 0 or 1.

[0079] In equation (19), R 71 Two or more adjacent members may form a ring with each other via one or more divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted.

[0080] In equation (19), l is an integer between 0 and 4. Typically, l is 0 or 1.

[0081] In equation (20), R 73 Two or more adjacent members may form a ring with each other via one or more divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted.

[0082] In equation (21), R 73 Two or more adjacent members may form a ring with each other via one or more divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted.

[0083] In equation (21), M is a transition metal. Examples of transition metals include, but are not limited to, Cu, Zn, Co, Fe, or Mn. Typically, M is Zn.

[0084] In formula (22), R 74 Two or more adjacent ones of may form a ring with each other via one or more divalent linking groups, each of the one or more divalent linking groups being substituted or unsubstituted, and the ring being substituted or unsubstituted.

[0085] In formula (22), k is an integer from 0 to 30. Typically, k is 0 or 1.

[0086] In formula (23), R 75 Two or more adjacent ones of may form a ring with each other via one or more divalent linking groups, each of the one or more divalent linking groups being substituted or unsubstituted, and the ring being substituted or unsubstituted.

[0087] In formula (23), each p is independently an integer from 0 to 4. Typically, each p is independently 0 or 1.

[0088] In formula (24), R 76 ~R 77 Two or more adjacent ones of may form a ring with each other via one or more divalent linking groups, each of the one or more divalent linking groups being substituted or unsubstituted, and the ring being substituted or unsubstituted. For example, R 76 Two or more adjacent ones of may form a ring with each other via one or more divalent linking groups, each of the one or more divalent linking groups being substituted or unsubstituted, and the ring being substituted or unsubstituted, and / or R 77 Two or more adjacent ones of may form a ring with each other via one or more divalent linking groups, each of the one or more divalent linking groups being substituted or unsubstituted, and the ring being substituted or unsubstituted.

[0089] In equation (24), p is an integer between 0 and 4. Typically, p is 0 or 1. In equation (24), q is an integer between 0 and 5. Typically, q is 0 or 1.

[0090] In equation (25), R 78 ~R 79 Two or more adjacent elements may form a ring with each other via one or more divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted. For example, R 78 Two or more adjacent elements may form a ring with each other via one or more divalent linking groups, each of which is substituted or unsubstituted, and the ring is substituted or unsubstituted, and / or R 79 Two or more adjacent elements may form a ring with each other via one or more divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted.

[0091] In formula (25), X and Y each independently contain an electron-withdrawing group. Examples of electron-withdrawing groups include, but are not limited to, cyano (C(CN)2 and N-CN), pyridinium, oxo, nitro, thiol, disulfide, halogen, haloalkyl, ester, sulfone, sulfonamide, sulfonimide, phthalimide, and naphthalimide groups.

[0092] In equation (25), r is an integer between 0 and 4. Typically, r is 0 or 1. In equation (25), q is an integer between 0 and 5. Typically, q is 0 or 1.

[0093] In equation (26), R 80 ~R 81Two or more adjacent elements may form a ring with each other via one or more divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted. For example, R 80 Two or more adjacent elements may form a ring with each other via one or more divalent linking groups, each of which is substituted or unsubstituted, and the ring is substituted or unsubstituted, and / or R 81 Two or more adjacent elements may form a ring with each other via one or more divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted.

[0094] In formula (26), X and Y each independently contain an electron-withdrawing group. Examples of electron-withdrawing groups include, but are not limited to, cyano (C(CN)2 and N-CN), pyridinium, oxo, nitro, thiol, disulfide, halogen, haloalkyl, ester, sulfone, sulfonamide, sulfonimide, phthalimide, and naphthalimide groups.

[0095] In equation (26), r is an integer between 0 and 4. Typically, r is 0 or 1. In equation (25), q is an integer between 0 and 5. Typically, q is 0 or 1.

[0096] For example, in some embodiments, the nonpolymer electron acceptor compound is of formula (1), (8), or (9): [ka] The compounds include those represented by one of the formulas, where (1), (8), and (9) are as defined herein, respectively.

[0097] In some embodiments, the nonpolymer electron acceptor compound is of formula (27A) to (30A): [ka] A compound represented by one of these could be given.

[0098] In equation (27A), R 82 and R 83 These are, independently, hydrogen, deuterium, halogen, nitro, amino, cyano, pyridinium, substituted or unsubstituted C, respectively. 1~30 Alkyl, substituted, or unsubstituted C 1~30 Heteroalkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 1~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 2~30 Heteroaryl, substituted, or unsubstituted C 3~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 It is an alkyl heteroaryl.

[0099] In equation (27A), R 82 and R 83 Each of these may further contain one or more divalent linking groups as part of its structure. Exemplary divalent linking groups include -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 Heterocycloalkylenes, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 Heteroarrenes, or combinations thereof, may be selected. ’ C is hydrogen, deuterium, substituted or unsubstituted C 1~20 Alkyl, substituted, or unsubstituted C 1~20Heteroalkyl, substituted, or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 It could be a heteroaryl.

[0100] In equation (27A), R 82 and R 83 However, they may form a ring with each other via one or more divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted.

[0101] In equation (27A), x is either 1 or 2.

[0102] In equation (28A), R 84 ~R 87 These are, independently, hydrogen, deuterium, halogen, nitro, amino, cyano, pyridinium, substituted or unsubstituted C, respectively. 1~30 Alkyl, substituted, or unsubstituted C 1~30 Heteroalkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 1~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 2~30 Heteroaryl, substituted, or unsubstituted C 3~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 It is an alkyl heteroaryl.

[0103] In equation (28A), R 84 ~R 87 Each of these may further contain one or more divalent linking groups as part of its structure. Exemplary divalent linking groups include -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R')-, -C(O)N(R')-, substituted or unsubstituted C1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylenes, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 Heteroarrenes, or combinations thereof, may be selected. ’ C is 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 It could be a heteroaryl.

[0104] In equation (28A), R 84 ~R 87 Two or more adjacent members may form a ring with each other via one or more divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted.

[0105] In equation (29A), R 88 ~R 91 These are, independently, hydrogen, deuterium, halogen, nitro, amino, cyano, pyridinium, substituted or unsubstituted C, respectively. 1~30 Alkyl, substituted, or unsubstituted C 1~30 Heteroalkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 1~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 2~30 Heteroaryl, substituted, or unsubstituted C 3~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 It is an alkyl heteroaryl.

[0106] In equation (29A), R 88 ~R 91 Each of these may further contain one or more divalent linking groups as part of its structure. Exemplary divalent linking groups include -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 Heterocycloalkylenes, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 Heteroarrenes, or combinations thereof, may be selected. ’ C is 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 It could be a heteroaryl.

[0107] In equation (29A), R 88 ~R 91 Two or more adjacent members may form a ring with each other via one or more divalent linking groups, where each of the one or more divalent linking groups is either substituted or unsubstituted, and the ring is either substituted or unsubstituted.

[0108] In equation (30A), R 92 and R 93 These are, independently, hydrogen, deuterium, halogen, nitro, amino, cyano, pyridinium, substituted or unsubstituted C, respectively. 1~30 Alkyl, substituted, or unsubstituted C 1~30 Heteroalkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 1~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, substituted or unsubstituted C 6~30Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 2~30 Heteroaryl, substituted, or unsubstituted C 3~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 It is an alkyl heteroaryl.

[0109] In equation (30A), R 92 and R 93 Each of these may further contain one or more divalent linking groups as part of its structure. Exemplary divalent linking groups include -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 Heterocycloalkylenes, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 Heteroarrenes, or combinations thereof, may be selected. ’ C is 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 It could be a heteroaryl.

[0110] Non-limiting examples of nonpolymer electron acceptor compounds include: [ka] [ka] [ka] These are some examples.

[0111] Electron acceptor compounds can accept one 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 species formed after the first electron transfer is higher than that of the photoacid generator compound. This ensures that the second electron transfer is thermodynamically favorable and kinetically efficient, thereby promoting the complete reduction of the acceptor species and thus more efficient secondary electron quenching. Representative examples of such compounds include ortho-quinone derivatives. For example, in the case of benzoquinone, a radical anion is formed when one electron is initially accepted, which is then further reduced by accepting a second electron to obtain the corresponding dianion. This stepwise electron transfer mechanism is particularly advantageous in photosystems where controlled electron diffusion is important.

[0112] Preferred electron acceptor compounds suppress electron diffusion without impairing resist sensitivity. While secondary electron quenching by electron acceptor compounds can reduce the potential for efficient utilization of thermal secondary electrons for photoacid generator (PAG) activation and acid formation, the electron acceptor compounds of the present invention can result in a higher dissolution rate in the resist exposure region. This increased dissolution rate can boost overall sensitivity by compensating for a reduction in acid production yield. As a result, resist sensitivity is not impaired and may even be improved due to the synergistic effect of local electron capture and enhanced solubility contrast.

[0113] In some embodiments, the composition may comprise two or more different nonpolymer electron acceptor compounds described herein. Each of the two or more nonpolymer electron acceptor compounds may have an electron affinity greater than that of the photoacid generator compound. In yet other embodiments, each of the two or more nonpolymer electron acceptor compounds may have an electron affinity greater than that of any PDQ compound added.

[0114] Nonpolymer electron acceptor compounds can be prepared using any suitable method in the art, including the methods described herein in the examples.

[0115] Nonpolymer electron acceptor compounds may be included in the composition in an amount of 0.1 to 50 wt%, preferably 1 to 40 wt%, and more preferably 2 to 20 wt%, based on the total solid content of the composition.

[0116] The composition also includes an acid-sensitive polymer comprising a first repeating unit derived from a monomer containing an acid-degradable group.

[0117] Suitable acid-degradable or acid-unstable groups include, for example, tertiary alkyl ester groups, secondary or tertiary aryl ester groups, secondary or tertiary ester groups having a combination of alkyl and aryl groups, tertiary alkoxy groups, acetal groups, ketal groups, tertiary carbonate groups, and tertiary carbamate groups. Typically, acid-unstable groups may be acetal groups, ketal groups, tertiary carbonate groups, tertiary carbamate groups, or tertiary ester groups. As used herein, "tertiary carbamate groups" include tertiary carbamate groups having alkyl groups, tertiary carbamate groups having aryl groups, and tertiary carbamate groups having a combination of alkyl and aryl groups. As used herein, "tertiary carbonate groups" include tertiary carbonate groups having alkyl groups, tertiary carbonate groups having aryl groups, and tertiary carbonate groups having a combination of alkyl and aryl groups. Preferably, tertiary ester groups are used as acid-unstable groups.

[0118] Examples of repeating units having acid-unstable groups include formulas (27)-(31): [ka] Examples include those represented by one or more of the following:

[0119] In equations (27) to (31), each R a These are independently hydrogen, deuterium, fluorine, cyano, substituted or unsubstituted C 1~10 Alkyl, or substituted or unsubstituted C 1~10 It is a fluoroalkyl group. Preferably, R a is hydrogen, fluorine, or substituted or unsubstituted C 1~5 Alkyl, typically methyl.

[0120] In equation (27), L 1 L is a divalent linking group. For example, L 1 This 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 These are -OCH2-, -OCH2CH2O-, or -N(R c )- which is possible, and in the formula, R c C is hydrogen, deuterium, substituted or unsubstituted C 1~10 Alkyl, substituted, or unsubstituted C 1~10 Heteroalkyl, substituted, or unsubstituted C 6~10 Aryl, or substituted or unsubstituted C 3~10 It is a heteroaryl compound.

[0121] In equations (27), (28), and (30), R 101 ~R 103 These are, independently, hydrogen, deuterium, and substituted or unsubstituted C. 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, substituted, or unsubstituted C 1~20 Heterocycloalkyl, substituted or unsubstituted C 2~20 Alkenyl, substituted or unsubstituted C 3~20 Cycloalkenyl, substituted or unsubstituted C 3~20 Heterocycloalkenyl, substituted or unsubstituted C 6~20 Aryl, or substituted or unsubstituted C 2~20 It may be a heteroaryl. However, R 101 ~R103 Only one of them may be hydrogen, but R 101 ~R 103 If one of them is hydrogen, then R 101 ~R 103 The other one or both, substituted or non-substituted C 6~20 Aryl, substituted, or unsubstituted C 4~20 It is a heteroaryl compound. Preferably, R 101 ~R 103 These are, independently, substitutional or non-substitutional C. 1~6 Alkyl, substituted, or unsubstituted C 3~10 It is a cycloalkyl group.

[0122] In equations (27), (28), and (30), R 101 ~R 103 Any two of them may come together to form a ring, R 101 ~R 103 Each of these is part of their structure -O-, -C(O)-, -N(R c )-, -S-, -S(O)-, or -S(O)2-(wherein R c This includes hydrogen, deuterium, and straight-chain or branched carbon. 1~20 Alkyl, monocyclic, or polycyclic C 3~20 Cycloalkyl, or monocyclic or polycyclic C 1~20 It may contain one or more groups selected from (which may be heterocycloalkyl). For example, R 101 ~R 103 One or more of the following conditions must be met independently: -CH2C(=O)CH (3-n) Y n It may also be a base of C, where each Y is independently a substitution or non-substitution C 1~30 It is a heterocycloalkyl group where n is 1 or 2. For example, each Y independently corresponds to formula -O(C a1 )(C a2 )O-(wherein, C a1 and C a2 These are, independently, hydrogen, deuterium, or substituted or unsubstituted C. 1~10 It is alkyl, C a1 and C a2Substituted or unsubstituted C (which may together form a ring) containing the group 1~30 It may be a heterocycloalkyl.

[0123] In equations (29) and (31), R 104 and R 105 These are, independently, hydrogen, deuterium, and substituted or unsubstituted C. 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, substituted, or unsubstituted C 1~20 Heterocycloalkyl, substituted or unsubstituted C 6~20 Aryl, or substituted or unsubstituted C 2~20 It can be a heteroaryl, R 106 is a substitution or non-substitution C 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 1~30 It may be a heterocycloalkyl group. Optionally, R 104 or R 105 One of them is R 106 They may form a complex ring together. Preferably, R 104 and R 105 These are, independently, hydrogen, deuterium, and substituted or unsubstituted C. 1~20 Alkyl, substituted, or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 1~20 It may be a heterocycloalkyl.

[0124] In equations (30) and (31), L 2 and L 3 Each of these is independently a single bond or a divalent linking group. Preferably, L 2 and L 3 These are, independently, substitutional or non-substitutional C. 6~30 Arirene or substituted or unsubstituted C 3~30 It is a cycloalkylene. For example, in some embodiments, L 3 It does not contain a (meth)acrylate group as part of its structure.

[0125] In equations (30) and (31), each of n1 and n2 can independently be 0 or 1. If n1 or n2 is 0, the corresponding L 2 or L 3 Please understand that the base is directly bonded to each oxygen atom.

[0126] As a non-limiting example of a repeating unit having an acid-unstable group, see below: [ka] [ka] [ka] These are listed, and in the formula, R d This includes hydrogen, deuterium, halogens, and substituted or unsubstituted C. 1~6 Alkyl, or substituted or unsubstituted C 3~6 It is a cycloalkyl group.

[0127] Repeating units with acid-unstable groups are present in the polymer in amounts of 25–75 mol%, more typically 25–50 mol%, and even more typically 30–50 mol%, based on the total number of repeating units in the polymer.

[0128] The polymer may further contain one or more additional repeating units. These repeating units may be, for example, one or more units intended to adjust properties of the composition such as etching rate and solubility. Examples of repeating units include those derived from one or more (meth)acrylates, vinyl aromatics, vinyl ethers, vinyl ketones, and / or vinyl ester monomers. The polymer of the composition may be a homopolymer or a copolymer containing two or more structurally distinct repeating units. For example, the polymer may contain one or more repeating units containing functional groups selected from hydroxyaryl groups, base-solubilizing groups, lactone-containing groups, sultone-containing groups, polar groups, crosslinking groups, or combinations thereof.

[0129] The repeating units of the polymer may contain hydroxyaryl groups. Examples of hydroxyaryl groups include phenol groups or naphthol groups. For example, the repeating units of the polymer are given by formula (32): [ka] It may contain a hydroxyaryl group represented by .

[0130] In equation (32), R a This is hydrogen, deuterium, fluorine, cyano, or substituted or unsubstituted C 1~10 It may be alkyl. Preferably, R a is hydrogen, deuterium, fluorine, or substituted or unsubstituted C 1~5 Alkyl, typically hydrogen or methyl.

[0131] In equation (32), L 5 It can be a single bond or one or more divalent linking groups. For example, L 5 -O-, -C(O)-, -C(O)O-, -N(R c )-,-C(O)N(R c )-, substitution or non-substitution C 1~10 Alkylene, substituted or unsubstituted C 3~10 Cycloalkylene, substituted or unsubstituted C 3~10 Heterocycloalkylenes, substituted or unsubstituted C 6~10 Arylene, substituted or unsubstituted C 3~10 This can be heteroarylene or a combination thereof, where R c C is hydrogen, substituted or unsubstituted. 1~30 Alkyl, substituted, or unsubstituted C 1~30 Heteroalkyl, substituted, or unsubstituted C 3~30 Cycloalkyl, substituted, or unsubstituted C 1~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, substituted or unsubstituted C 6~30Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 2~30 Heteroaryl, substituted, or unsubstituted C 3~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 It may be an alkyl heteroaryl. In some embodiments, L 5 This can be a single bond, -C(O)O-, substituted or unsubstituted C. 1~10 Alkylene, substituted or unsubstituted C 3~10 Cycloalkylene, substituted or unsubstituted C 3~10 Heterocycloalkylenes, substituted or unsubstituted C 6~10 Arylene, substituted or unsubstituted C 3~10 It may be one or more groups selected from heteroarylenes or combinations thereof.

[0132] In equation (32), Ar 1 Substitutive C may contain one or more aromatic ring heteroatoms selected from N, O, S, or combinations thereof. 5~60 It may be an aromatic group, and the aromatic group may be monocyclic, non-condensed polycyclic, or condensed polycyclic. 5~60 When the aromatic group is polycyclic, the ring or ring group may be fused (e.g., naphthyl), unfused, or a combination thereof. 5~60 If the aromatic groups are not fused, the ring or ring group may be directly linked (e.g., biaryl or biphenyl) or bridged by a heteroatom (e.g., triphenylamino or diphenylene ether). In some embodiments, polycyclic C 5~60 Aromatic groups can include combinations of fused rings and directly linked rings (such as binaphthyl).

[0133] In equation (32), y can be an integer between 1 and 12, preferably between 1 and 6, and typically between 1 and 3.

[0134] In equation (32), each R xR can independently be hydrogen or methyl, provided that at least one R x It is hydrogen.

[0135] As an example of such an unrestricted repeating unit in equation (32): [ka] Possible examples include, in the formula, R d This is hydrogen, deuterium, fluorine, cyano, or substituted or unsubstituted C 1~10 It may be alkyl. Preferably, R d is hydrogen, fluorine, or substituted or unsubstituted C 1~5 Alkyl, typically methyl.

[0136] Repeating units containing hydroxyaryl groups in polymers can typically be present in amounts of 10–90 mol%, more typically 15–75 mol%, and even more typically 20–70 mol%, based on the total repeating units of the polymer.

[0137] The repeating units of the polymer may contain lactone groups. For example, the repeating units of the polymer may be of formula (33): [ka] It may contain a lactone group represented by .

[0138] In equation (33), R a This is hydrogen, deuterium, fluorine, cyano, or substituted or unsubstituted C 1~10 It may be alkyl. Preferably, R a is hydrogen, fluorine, or substituted or unsubstituted C 1~5 Alkyl, typically hydrogen or methyl.

[0139] In equation (33), L 4 It can be a single bond or one or more divalent linking groups. For example, L 4 -O-, -C(O)-, -C(O)O-, -N(R c )-,-C(O)N(R c )-, substitution or non-substitution C 1~10 Alkylene, substituted or unsubstituted C 3~10 Cycloalkylene, substituted or unsubstituted C 3~10 Heterocycloalkylenes, substituted or unsubstituted C 6~10 Arylene, substituted or unsubstituted C 3~10 This can be heteroarylene or a combination thereof, where R c C is 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 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 2~30 Heteroaryl, substituted, or unsubstituted C 3~30 Heteroarylalkyl, or substituted or unsubstituted C 3~30 It may be an alkyl heteroaryl. In some embodiments, L 4 This can be a single bond, -C(O)O-, substituted or unsubstituted C. 1~10 Alkylene, substituted or unsubstituted C 3~10 Cycloalkylene, substituted or unsubstituted C 3~10 Heterocycloalkylenes, substituted or unsubstituted C 6~10 Arylene, substituted or unsubstituted C 3~10 It may be one or more groups selected from heteroarylenes or combinations thereof.

[0140] In equation (33), R 107 C is a monocyclic, polycyclic, or fused polycyclic C 4~20 It may be a lactone-containing group.

[0141] As a non-limiting example of the lactone-containing repeating unit in formula (33): [ka] Possible examples include, in the formula, R d This is hydrogen, deuterium, fluorine, cyano, or substituted or unsubstituted C 1~10 It may be alkyl. Preferably, R d is hydrogen, fluorine, or substituted or unsubstituted C 1~5 Alkyl, typically methyl.

[0142] Repeating units containing lactone groups may typically be present in amounts of 5–90 mol%, more typically 10–75 mol%, and even more typically 15–70 mol%, based on the total repeating units of the polymer.

[0143] The repeating units of the polymer may contain salt groups. As used herein, “salt groups” refers to positively and / or negatively charged portions having positive and / or negative charges, for example, bonded pendant to the backbone of a block copolymer. The repeating units of a block copolymer containing salt groups may contain photoacid generator (PAG) groups or photodegradable quencher (PDQ) groups. For example, the repeating units of the polymer may be of formula (34a) or (34b): [ka] It may contain a salt base represented by .

[0144] In equations (34a) and (34b), each Rm This is hydrogen, deuterium, fluorine, cyano, or substituted or unsubstituted C 1~10 It may be alkyl. Preferably, R m is hydrogen, fluorine, or substituted or unsubstituted C 1~5 Alkyl, typically methyl.

[0145] In equations (34a) and (34b), Q 1 and Q 2 Each of these can independently be a single bond or a divalent linking group. Preferably, Q 1 and Q 2 Each of these may independently contain 1 to 10 carbon atoms and at least one heteroatom, more preferably -C(O)-O-.

[0146] In equations (34a) and (34b), A 1 and A 2 These are, independently, substitutional or non-substitutional C. 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 2~30 Heterocycloalkylenes, substituted or unsubstituted C 6~30 Arylene, or substituted or unsubstituted C 3~30 It may be one or more heteroarylenes. In some embodiments, A 1 and A 2 These are, independently, divalent C which may be substituted. 1~30 It may be a perfluoroalkylene group.

[0147] In equation (34a), Z - is, A 1 The anionic moiety bonded to it has a conjugate acid with a pKa of typically -15 to 10. - This can be a sulfonate ion, a carboxylate ion, a sulfonamide anion, a sulfonimide anion, or a methide anion.

[0148] In equation (34a), G +is an organic cation as defined herein. In some embodiments, G + This refers to 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.

[0149] In equation (34b), Z - Z is an anionic compound as defined herein, whose conjugate acid typically has a pKa of -15 to 10. - This can be a sulfonate ion, a carboxylate ion, a sulfonamide anion, a sulfonimide anion, or a methido anion species. For example, Z - Anion A - This may be as defined herein.

[0150] In equation (34b), G + is, A 2 It is an organic cation bonded to it. For example, G + This may include 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.

[0151] In yet another embodiment, if the polymer contains repeating units having salt groups, the polymer may contain zwitterionic species. For example, the polymer may be of formula (34c): [ka] It may contain repeating units having a salt base, and in formula (34c), each R m These are defined independently for equations (34a) and (34b).

[0152] In equation (34c), Q 1 , A 1, and Z - Q is defined as shown in equation (20a), 2 , A 2 , and G + This is defined in equation (34b).

[0153] The exemplary repeating units of equation (34a) are as follows: [ka] The formula includes, where G is an organic cation, and each R d These are defined independently for equation (34a).

[0154] The exemplary repeating units in equation (34b) are as follows: [ka] Including, in the formula, Z - R is an anionic group as defined herein, and each R d This is defined independently for equation (34b).

[0155] Repeating units of a polymer containing salts can typically be present in amounts of 1–35 mol%, typically 1–25 mol%, and more typically 2–15 mol%, based on the total repeating units of the polymer.

[0156] In some embodiments, the polymer may contain repeating units that include polar groups. Exemplary polar groups include cyano groups, sultone groups, sulfonamide groups, hydroxyalkyl groups, hydroxycycloalkyl groups, or combinations thereof. While some groups, such as lactone or hydroxyaryl groups, may be considered polar groups, it should be understood that these groups are distinct from the polar groups used herein.

[0157] The repeating unit of the polymer is given by equation (35): [ka] It may contain polar groups represented by .

[0158] In equation (35), R a This is hydrogen, deuterium, fluorine, cyano, or substituted or unsubstituted C 1~10 It may be alkyl. Preferably, R a is hydrogen, fluorine, or substituted or unsubstituted C 1~5 Alkyl, typically hydrogen or methyl.

[0159] In equation (35), L 6 It can be a single bond or one or more divalent linking groups. For example, L 6 -O-, -C(O)-, -C(O)O-, -N(R c )-,-C(O)N(R c )-, substitution or non-substitution C 1~10 Alkylene, substituted or unsubstituted C 3~10 Cycloalkylene, substituted or unsubstituted C 3~10 Heterocycloalkylenes, substituted or unsubstituted C 6~10 Arylene, substituted or unsubstituted C 3~10 This can be heteroarylene or a combination thereof, where R c C is 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 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, substituted or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 2~30 Heteroaryl, substituted, or unsubstituted C 3~30Heteroarylalkyl, or substituted or unsubstituted C 3~30 It may be an alkyl heteroaryl. In some embodiments, L 6 This can be a single bond, -C(O)O-, substituted or unsubstituted C. 1~10 Alkylene, substituted or unsubstituted C 3~10 Cycloalkylene, substituted or unsubstituted C 3~10 Heterocycloalkylenes, substituted or unsubstituted C 6~10 Arylene, substituted or unsubstituted C 3~10 It may be one or more groups selected from heteroarylenes or combinations thereof.

[0160] In equation (35), R 108 is a substitution or non-substitution C 1~100 Or C 1~20 Alkyl, typically C 1~12 Alkyl, substituted, or unsubstituted C 3~30 Or C 3~20 Cycloalkyl, or substituted or unsubstituted poly(C) 1~3 It can be an alkylene oxide. Substitution 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 fluoroalcohol groups (e.g., -C(CF3)2OH).

[0161] As an example of a non-restrictive repeating unit in equation (35): [ka] Possible examples include, in the formula, R g This is hydrogen, deuterium, fluorine, cyano, or substituted or unsubstituted C 1~10 It may be alkyl. Preferably, R g is hydrogen, fluorine, or substituted or unsubstituted C 1~5 Alkyl, typically methyl. 1is F or C 1~4 It may be a perfluoroalkyl group.

[0162] In some embodiments, the polymer may contain repeating units that include acid groups. An example of an acid group is a carboxylic acid group. The repeating unit of the polymer is given by formula (36): [ka] It may contain an acid group represented by .

[0163] In equation (36), R a This is hydrogen, deuterium, fluorine, cyano, or substituted or unsubstituted C 1~10 It may be alkyl. Preferably, R a is hydrogen, fluorine, or substituted or unsubstituted C 1~5 Alkyl, typically hydrogen or methyl.

[0164] In equation (36), L 7 This can be a single bond, or a substituted or unsubstituted C. 1~30 Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 1~30 Heterocycloalkylenes, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted divalent carbon (C) 7~30 Arylalkyl, substituted or unsubstituted C 1~30 Heteroarylene, or substituted or unsubstituted divalent C 3~30 It may be a heteroarylalkyl or one or more of -C(O)-O-.

[0165] In equation (36), R 109 It may also be -C(O)-OH.

[0166] As an example of a non-restrictive repeating unit in equation (36): [ka] Possible examples include, in the formula, R dThis is hydrogen, deuterium, fluorine, cyano, or substituted or unsubstituted C 1~10 It may be alkyl. Preferably, R d is hydrogen, fluorine, or substituted or unsubstituted C 1~5 Alkyl, typically methyl.

[0167] Repeating units containing acidic groups may typically be present in amounts of 1–20 mol%, more typically 5–20 mol%, and even more typically 5–10 mol%, based on the total repeating units of the polymer. Repeating units containing hydroxyaryl groups may typically be present in the polymer in amounts of 1–20 mol%, more typically 5–20 mol%, and even more typically 5–10 mol%, based on the total repeating units of the polymer.

[0168] Non-limiting exemplary polymers of the present invention are as follows: [ka] [ka] [ka] The formula includes one or more of the following, where x, y, and z are each mole fractions of the associated repeating unit, the sum of the mole fractions for each polymer reaches 1, and each R d These are, independently, hydrogen, deuterium, halogen, substituted or unsubstituted C 1~6 Alkyl, or substituted or unsubstituted C 3~6 It is a cycloalkyl group.

[0169] Polymers typically have a weight-average molecular weight (M w The power is 1,000 to 50,000 Daltons (Da), preferably 2,000 to 30,000 Da, more preferably 3,000 to 20,000 Da, and even more preferably 4,000 to 15,000 Da. w The number average molecular weight (M nThe polydispersity index (PDI) of the first polymer, which is the ratio to ), is typically 1.1–3, more typically 1.1–2. The molecular weight is determined by gel permeation chromatography (GPC) using a polystyrene standard.

[0170] In the compositions of the present invention, the polymer is typically present in the composition in an amount of 10 to 99.9 wt%, typically 25 to 99 wt%, and more typically 50 to 95 wt%, based on the total solids content of the composition. The total solids content will be understood to include the polymer, PAG, and other non-solvent components.

[0171] Polymers can be prepared using any suitable method in the art. For example, one or more monomers corresponding to the repeating units described herein may be combined using a suitable solvent and initiator, or supplied separately, and polymerized in a reactor. For example, polymers can be obtained by polymerization of each monomer under any suitable conditions, such as heating at an effective temperature, irradiation with active radiation at an effective wavelength, or a combination thereof.

[0172] The composition also contains a photoacid generator (PAG). The PAG may be in ionic or nonionic form. The PAG may be in polymer or nonpolymer form. In polymer form, the PAG may exist as a part of repeating units of a polymer derived from polymerizable PAG monomers.

[0173] In some embodiments, the composition may contain two or more different photoacid-generating compounds. In some embodiments, when the photoresist compound contains two or more different photoacid-generating compounds, the nonpolymer electron acceptor compound has an electron affinity greater than the electron affinity of each of the two or more photoacid-generating compounds.

[0174] A suitable PAG compound is, formula G + A - It can be, and in the formula, G + A is an electroactive cation, -This is an anion capable of generating a photoacid. The electroactive cation is preferably selected from onium cations, preferably iodonium or sulfonium cations. Particularly suitable anions include those with a conjugate acid pKa of -15 to 10. The anions are typically organic anions having a sulfonate group or a non-sulfonate type group, such as sulfonamide, sulfonimidate, methide, or borate ion.

[0175] In some embodiments, the PAG anion does not contain -F, -CF3, or -CF2- groups. It should be understood that "does not contain -F, -CF3, or -CF2- groups" means that the PAG anion excludes groups such as -CH2CF3 and -CH2CF2CH3. In yet other embodiments, the PAG anion is fluorine-free (i.e., it does not contain a fluorine atom and is not substituted by a fluorine-containing group). In some embodiments, the photoacid generator is fluorine-free (i.e., both the photoactive cation and anion are fluorine-free).

[0176] PAG compounds contain an organic cation. For example, the organic cation may be a sulfonium cation or an iodonium cation. In some embodiments, the organic cation is a sulfonium cation of formula (37a) or an iodonium cation of formula (37b): [ka] It is possible.

[0177] In equations (37a) and (37b), R 110 ~R 114 These are, independently, substitutional or non-substitutional 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 Iodoaryl, substituted or unsubstituted C 3~30Heteroaryl, substituted, or unsubstituted C 7~20 Arylalkyl, or substituted or unsubstituted C 4~20 It is a heteroarylalkyl group, or a combination thereof. 110 ~R 114 Each of these may be separate, 110 ~R 112 It may be linked to another group via a single bond or a divalent linking group to form a ring. 113 and R 114 These may be separate or linked to each other via single bonds or divalent linking groups to form a ring. 110 ~R 114 Each of these may include a divalent linking group as part of its structure. 110 ~R 114 Each of these may independently contain an acid-unstable group selected from, for example, a tertiary alkyl ester group, a secondary or tertiary aryl ester group, a secondary or tertiary ester group having a combination of an alkyl group and an aryl group, a tertiary alkoxy group, an acetal group, or a ketal group.

[0178] The exemplary sulfonium cations of formula (37a) are as follows: [ka] Includes one or more of the following.

[0179] The exemplary iodonium cations of formula (37b) are as follows: [ka] It may include one or more of the following.

[0180] Examples of organic anions having a sulfonate group are as follows: [ka] Includes one or more of the following.

[0181] Examples of non-sulfonated anions are as follows: [ka] Includes one or more of the following.

[0182] Commonly used onium salts include, for example, triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, di-t-butylphenyliodonium perfluorobutanesulfonate, and di-t-butylphenyliodonium camphorsulfonate. Other useful PAG compounds are known in the field of chemically amplified photoresists, for example, nonionic sulfonyl compounds, e.g., 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate, and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonic acid esters, e.g., 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives, e.g., bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl) Examples include diazomethanes; glyoxime derivatives, e.g., bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime and bis-O-(n-butanesulfonyl)-α-dimethylglyoxime; sulfonic acid ester derivatives of N-hydroxyimide compounds, e.g., N-hydroxysuccinimodomethanesulfonic acid and N-hydroxysuccinimodotrifluoromethanesulfonic acid; and halogen-containing triazine compounds, e.g., 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 generators are further described in U.S. Patents 8,431,325 and 4,189,323.

[0183] If the composition contains an ionic nonpolymer electron acceptor compound and a PAG compound, the nonpolymer electron acceptor compound may contain an anion that is structurally the same as the anion of the PAG compound. Otherwise, the anion of the nonpolymer electron acceptor compound may be structurally different from the anion of the PAG compound. For example, in some embodiments, the photoacid generator compound contains a first anion and the nonpolymer electron acceptor compound contains a second anion, and the first and second anions are structurally the same.

[0184] Typically, when a composition contains a non-polymeric PAG compound, the PAG compound is present in the composition in an amount of 0.1–55 wt%, more typically 1–25 wt%, based on the total solids content of the composition. When present in polymeric form, the PAG compound is typically present in the polymer in an amount of 1–25 mol%, more typically 1–8 mol%, or 2–6 mol%, based on the total repeating units in the polymer.

[0185] The composition further comprises a solvent to dissolve the components of the composition and facilitate coating onto a substrate. Preferably, the solvent is an organic solvent conventionally used in the manufacture of electronic devices. Suitable solvents include, for example, aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, and 1-chlorohexane; alcohols such as methanol, ethanol, 1-propanol, isopropanol, tert-butanol, 2-methyl-2-butanol, 4-methyl-2-pentanol, and diacetone alcohol (4-hydroxy-4-methyl-2-pentanone) (DAA); propylene glycol monomethyl ether (PGME); ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and anisole; acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone. Examples of solvents include ketones such as (CHO); esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), methyl hydroxyisobutyrate (HBM), and ethyl acetoacetate; lactones such as gamma-butyrolactone (GBL) and epsilon-caprolactone; lactams such as N-methylpyrrolidone; nitriles such as acetonitrile and propionitrile; cyclic or acyclic carbonate esters such as propylene carbonate, dimethyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, and propylene carbonate; polar aprotic solvents such as dimethyl sulfoxide and dimethylformamide; water; and combinations thereof. Of these, preferred solvents include one or more of PGME, PGMEA, EL, GBL, HBM, CHO, DAA, or combinations thereof.

[0186] The total solvent content in the composition (i.e., the cumulative solvent content for all solvents) is typically 40–99 wt%, for example 60–99 wt%, or 85–99 wt%, based on the total solids content of the composition. The desired solvent content is determined, for example, by the desired thickness of the coated (photoresist) layer and the coating conditions.

[0187] In some embodiments, the composition may further comprise a material containing one or more base-unstable groups ("base-unstable material") and / or base-soluble groups. Base-soluble groups as used herein are generally polar functional groups that can become soluble during the development step by ionizing in a TMAH-type base, while base-unstable groups are functional groups that, after the exposure and post-exposure bake steps, undergo cleavage reactions in the presence of an aqueous alkaline developer to provide the same type of polar groups (e.g., base-soluble groups), such as hydroxyl (phenol), HFA (hexafluoroalcohol), carboxylic acids, and sulfonic acids. Base-unstable groups do not react significantly (e.g., do not undergo bond-breaking reactions) before the development step of a composition containing base-unstable groups. Therefore, for example, base-unstable groups are substantially inert during the pre-exposure soft bake step, the exposure step, and the post-exposure bake step. "Substantially inert" means that ≤5%, typically ≤1%, of the base-unstable groups (or portions) decompose, cleave, or react during the pre-exposure soft bake, exposure, and post-exposure bake processes. Base-unstable groups are reactive under typical photoresist development conditions, such as using an aqueous alkaline photoresist developer, for example, a 0.26 N aqueous solution of tetramethylammonium hydroxide (TMAH). For example, a 0.26 N aqueous solution of TMAH may be used for single-paddle or dynamic development, where, for example, the 0.26 N TMAH developer is dispensed onto the imaged photoresist layer for an appropriate time, such as 10–120 seconds. Exemplary base-unstable groups include ester groups, typically fluorinated ester groups. Preferably, the base-unstable material is substantially miscible with the first and / or second polymer and other solid components of the composition, and has a lower surface energy than the first and / or second polymer and other solid components. When coated onto a substrate, base-unstable materials can be separated from the other solid components of the composition and placed on the upper surface of the formed photoresist layer.

[0188] In some embodiments, the base-unstable material may also be a polymer material, also referred to herein as a base-unstable polymer, which may comprise one or more repeating units comprising one or more base-unstable groups. For example, a base-unstable polymer may comprise repeating units comprising two or more identical or different base-unstable groups. A base-unstable or base-soluble polymer may comprise one or more other repeating units, such as (meth)acrylates, vinyl aromatics, vinyl ethers, vinyl ketones, and / or vinyl ester monomers. A preferred base-unstable polymer comprises at least one repeating unit comprising two or more base-unstable groups, for example, a repeating unit comprising two or three base-unstable groups. Another preferred base-unstable polymer comprises at least one repeating unit comprising one acid-degradable group.

[0189] Base-unstable polymers can be prepared using any suitable method in the art. For example, base-unstable polymers can be obtained by polymerization of each monomer under any suitable conditions, such as heating at an effective temperature, irradiation with active radiation at an effective wavelength, or a combination thereof. In addition to or otherwise, one or more base-unstable groups may be grafted onto the polymer backbone using a suitable method.

[0190] In some embodiments, the base-unstable material is a single molecule containing one or more base-unstable ester groups, preferably one or more fluorinated ester groups. A base-unstable material that is a single molecule is typically M w The range is between 50 Da and 1,500 Da.

[0191] If present, base-unstable and / or base-soluble materials are typically present in the composition in amounts of 0.01–10 wt%, typically 1–5 wt%, based on the total solids content of the composition.

[0192] In addition, the composition may further contain one or more polymers other than those described above. For example, the composition may contain the additional polymers described above, but the composition may differ. In addition to or other than these, one or more additional polymers may be selected from those well known in the photoresist technology, such as polyacrylates, polyvinyl ethers, polyesters, polynorbornene, polyacetals, polyethylene glycols, polyamides, polyacrylamides, polyphenols, novolacs, styrene polymers, polyvinyl alcohols, or combinations thereof.

[0193] The composition may further contain one or more additional optional additives. For example, optional additives may include active dyes and contrast dyes, antistriating agents, plasticizers, speed enhancers, sensitizers, photodegradable quenchers (PDQ) (also known as photodegradable bases), basic quenchers, thermoacid generators, and surfactants, or combinations thereof. If present, optional additives are typically present in the composition in amounts of 0.01 to 10 wt%, based on the total solids content of the composition.

[0194] PDQ generates a weak acid when irradiated. The acid generated from the photodegradable quencher is not strong enough to react rapidly with acid-unstable groups present in the resist matrix. Exemplary photodegradable quenchers include, for example, photodegradable cations, preferably weak acid anions (pKa>1), such as C, which are also useful for preparing strong acid-generating compounds. 1~20 Carboxylic acid or C 1~20Examples include photodegradable cations paired with sulfonic acid anions. Exemplary carboxylic acids include formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexanecarboxylic acid, benzoic acid, and salicylic acid. Exemplary sulfonic acids include p-toluenesulfonic acid and camphorsulfonic acid. In preferred embodiments, the photodegradable quencher is a photodegradable organic zwitterionic compound such as diphenyliodonium-2-carboxylate. When PDQ is included in the composition, the electron affinity of PDQ is lower than that of the nonpolymer electron acceptor compound.

[0195] PDQ may be in a non-polymeric form or a polymer-bound form. Polymerization units containing the photodegradable quencher are typically present in amounts of 0.1 to 30 mol%, preferably 1 to 10 mol%, and more preferably 1 to 2 mol%, based on the total repeating units of the polymer.

[0196] Examples of basic quenchers include linear aliphatic amines such as tributylamine, trioctylamine, triisopropanolamine, tetrakis(2-hydroxypropyl)ethylenediamine:n-tert-butyldiethanolamine, tris(2-acetoxyethyl)amine, 2,2',2'',2'''-(ethane-1,2-diyrbis(azantriyl))tetraethanol, 2-(dibutylamino)ethanol, and 2,2',2''-nitrilotriethanol; 1-(tert- Cyclic aliphatic amines such as butoxycarbonyl)-4-hydroxypiperidine, tert-butyl1-pyrrolidinecarboxylate, tert-butyl2-ethyl-1H-imidazole-1-carboxylate, di-tert-butylpiperazine-1,4-dicarboxylate, and N-(2-acetoxyethyl)morpholine; aromatic amines such as pyridine, di-tert-butylpyridine, and pyridinium; N,N-bis(2-hydroxyethyl)pivalamide, N,N-diethylacetamide, N 1 ,N 1 ,N 3 ,N 3Examples include linear and cyclic amides and their derivatives such as tetrabutylmalonamide, 1-methylazepan-2-one, 1-allylazepan-2-one, and tert-butyl1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylcarbamate; ammonium salts such as quaternary ammonium salts of sulfonates, sulfamates, carboxylates, and phosphonates; imines such as primary and secondary aldimines and ketimines; diazines such as pyrazine, piperazine, and phenazine, which may be substituted; diazoles such as pyrazole, thiadiazole, and imidazole, which may be substituted; and pyrrolidones, such as 2-pyrrolidone and cyclohexylpyrrolidine, which may be substituted.

[0197] The basic quencher may be in a non-polymeric form or a polymer-bound form. If in a polymeric form, the quencher may be present in the repeating units of the polymer. Repeating units containing the quencher are typically present in an amount of 0.1 to 30 mol%, preferably 1 to 10 mol%, and more preferably 1 to 2 mol%, based on the total repeating units of the polymer.

[0198] Examples of surfactants include fluorinated and non-fluorinated surfactants, which may be ionic or nonionic, with nonionic surfactants being preferred. Examples of fluorinated nonionic surfactants include perfluoroC4 surfactants such as FC-4430 and FC-4432 surfactants available from 3M Corporation, as well as fluorodiols, such as Omnova's POLYFOX PF-636, PF-6320, PF-656, and PF-6520 fluorosurfactants. In one embodiment, the composition further comprises a surfactant polymer containing fluorine-containing repeating units.

[0199] Next, a patterning method using the composition of the present invention will be described. Suitable substrates to which the composition can be coated include electronic device substrates. In the present invention, a wide variety of electronic device substrates can be used, such as semiconductor wafers; polycrystalline silicon substrates; packaging substrates such as multi-chip modules; flat panel display substrates; and substrates for light-emitting diodes (LEDs) including organic light-emitting diodes (OLEDs), with semiconductor wafers being typical. Such substrates are typically composed of one or more of silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. Suitable substrates may also be in the form of wafers, such as wafers used in the manufacture of integrated circuits, optical sensors, flat panel displays, integrated optical circuits, and LEDs. Such substrates can be of any suitable size. Typical wafer substrates have a diameter of 200-300 millimeters (mm), but wafers with smaller and larger diameters can be appropriately used according to the present invention. The substrate may include one or more layers or structures that can optionally contain the active or operable parts of the device to be formed.

[0200] Typically, before coating the composition of the present invention, one or more lithography layers are provided on the upper surface of the substrate, such as a hard mask layer (e.g., a spin-on carbon (SOC), amorphous carbon, or metal hard mask layer), a CVD layer (e.g., a silicon nitride (SiN), silicon oxide (SiO), or silicon oxynitride (SiON) layer), an organic or inorganic underlayer, or a combination thereof. Such layers, together with the overcoated photoresist layer, form a lithography material stack.

[0201] Optionally, a layer of adhesion promoter may be applied to the substrate surface before coating the composition. If an adhesion promoter is desired, any adhesion promoter suitable for polymer films may be used, such as silanes, typically organosilanes, e.g., trimethoxyvinylsilane, triethoxyvinylsilane, hexamethyldisilazane, or aminosilane couplers, e.g., gamma-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those available from DuPont Electronics & Industrial (Marlborough, Massachusetts), marketed under the names AP® 3000, AP® 8000, and AP® 9000S.

[0202] The composition can be coated onto a substrate by any suitable method, including spin coating, spray coating, dip coating, or doctor blade coating. For example, coating a layer of photoresist can be achieved by spin coating a photoresist in a solvent using a coating track, where the photoresist is dispensed onto a spin wafer. During dispensing, the wafer is typically rotated for 15 to 120 seconds at a speed of up to 4,000 revolutions per minute (rpm), e.g., 200 to 3,000 rpm, e.g., 1,000 to 2,500 rpm, to obtain a layer of the composition on the substrate. It will be understood by those skilled in the art that the thickness of the coated layer can be adjusted by changing the spin speed and / or total solids content of the composition. The EUV (photoresist) composition layer formed from the composition of the present invention typically has a dry layer thickness of 5 nm to 100 nm, preferably more than 10 nm to 80 nm, more preferably 20 nm to 70 nm. The E-beam resist composition layer derived from the composition of the present invention typically has a dry layer thickness of 50 nm to 3 μm, preferably more than 70 nm to 1 μm, and more preferably 100 nm to 500 nm.

[0203] The composition is typically then soft-baked to minimize the solvent content in the layer, thereby forming a non-stick coating and improving the adhesion of the layer to the substrate. Soft baking is performed, for example, on a hot plate or in an oven, with a hot plate being typical. The temperature and time of soft baking are determined, for example, by the composition and thickness. Soft baking temperatures are typically 80–170°C, more typically 90–150°C. Soft baking times are typically 10 seconds–20 minutes, more typically 1–10 minutes, and even more typically 1–2 minutes. The heating time can be easily determined by those skilled in the art based on the components of the composition.

[0204] Next, the photoresist layer or E-beam resist layer is exposed to activating radiation in a patterned manner to create a difference in solubility between exposed and unexposed areas. References herein to exposing a photoresist composition to activating radiation indicate that the radiation can form latent images within the photoresist composition. Exposure is typically performed via a patterned photomask having optically transparent and optically opaque areas corresponding to the areas of the resist layer to be exposed and the areas not to be exposed, respectively. Alternatively, such exposure may be performed without a photomask in direct writing methods typically used in e-beam lithography. Exposure is performed with activating radiation, such as wavelengths of 13.5 nm (EUV) or less, or by an electron beam (e-beam). The exposure energy is typically 1 to 200 millijoules / cm² (mJ / cm²), depending on the exposure tool and the components of the photoresist composition. 2 ), preferably 5 to 100 mJ / cm² 2 More preferably 20-50 mJ / cm² 2 That is the case.

[0205] Following the exposure of the photoresist layer, a post-exposure bake (PEB) of the exposed photoresist layer is performed. PEB can be performed, for example, on a hot plate or in an oven, with a hot plate being typical. The conditions for PEB depend, for example, on the photoresist composition and layer thickness. PEB is typically performed for 30 to 120 seconds at a temperature of 70 to 150°C, preferably 75 to 120°C. A latent image is formed in the photoresist, defined by regions where the polarity is switched (exposed regions) and regions where it is not switched (unexposed regions).

[0206] Next, the exposed photoresist layer is developed with a suitable developer, selectively removing the soluble regions of the layer while the remaining insoluble regions form the resulting photoresist pattern relief image. In a positive development (PTD) process, the exposed regions of the photoresist layer are removed during development, leaving the unexposed regions. Conversely, in a negative development (NTD) process, the exposed regions of the photoresist layer remain, and the unexposed regions are removed during development. The application of the developer can be achieved by any suitable method as described above for the application of the composition, with spin coating being a typical example. The development time is an effective period for removing the soluble regions of the photoresist, typically 5 to 60 seconds. Development is typically carried out at room temperature.

[0207] Suitable developers for the PTD process include aqueous base developers, such as quaternary ammonium hydroxide solutions, such as TMAH, preferably 0.26N TMAH, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. Suitable developers for the NTD process are organic solvent-based, meaning that the cumulative content of the organic solvent in the developer is 50 wt% or more, typically 95 wt% or more, 98 wt% or more, or 100 wt%, based on the total weight of the developer. Suitable organic solvents for NTD developers include, for example, those selected from ketones, esters, ethers, hydrocarbons, and mixtures thereof. The developer is typically 2-heptanone or n-butyl acetate.

[0208] A coated substrate may be formed from the composition of the present invention. Such a coated substrate comprises (a) a substrate having one or more layers to be patterned on its surface, and (b) a layer of the composition covering the one or more layers to be patterned.

[0209] A photoresist pattern can be used, for example, as an etching mask, thereby allowing the pattern to be transferred to one or more consecutively underlying layers by known etching techniques, typically by dry etching such as reactive ion etching. A photoresist pattern can also be used, for example, for pattern transfer to an underlying hard mask layer, which is then used as an etching mask for pattern transfer to one or more layers below the hard mask layer. If the photoresist pattern is not consumed during pattern transfer, it can be removed from the substrate by known techniques, such as oxygen plasma ashing. When used in one or more such patterning processes, 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.

[0210] The present invention can be further illustrated by the following non-limiting examples. [Examples]

[0211] Calculation of electron affinity and LUMO energy Table 1 summarizes the electron affinity (EA) energies calculated from the present invention for PAG cation triphenylsulfonium and nonpolymer electron acceptor compounds. Density functional theory (DFT) at the B3LYP level using the 6-31+G(d,p) basis set was employed for the calculations. Modeling was performed for each molecule in solution using a polarization continuum (PC) model with propylene carbonate as the solvent. Global minimum energy geometry was confirmed using vibrational frequency analysis. Adiabatic electron affinity was calculated using the calculated energies of the optimized structure. Electron affinity was calculated as the energy difference between the neutral form and the corresponding anion-radical form, which is the form produced upon the addition of one electron. For positively charged species such as sulfonium cations with a +1 charge, electron affinity was calculated as the energy difference between sulfonium with a +1 charge and the radical form produced upon the addition of one electron.

[0212] The lowest-empty molecular orbital (LUMO) energy was calculated using quantum chemical calculations. DFT calculations were performed using the Gaussian 16 software package with the B3LYP function and the 6-31+G(d,p) basis set. Modeling was performed on a molecule-by-molecule basis in solution using a polarization continuum (PC) model with propylene carbonate as the solvent. The global minimum energy geometry was verified using vibrational frequency analysis. After optimization, a DFT output file containing molecular orbital energies was obtained. The lowest-empty molecular orbital (LUMO) energy was extracted from the output. [Table 1]

[0213] As shown in Table 1, each of the nonpolymer electron acceptor compounds EA1 to EA11 of the present invention showed a higher EA compared to cation TPS(EA12). Similarly, as shown in Table 1, each of the electron acceptor compounds EA1 to EA11 of the present invention showed a lower LUMO energy level compared to cation TPS(EA12).

[0214] The structures of electron acceptor compounds EA1-EA11 and cation TPS (EA12) were as follows. [ka]

[0215] Reduction potential measurement I purchased Et2-Vio-Br2(EA9) from Aldrich and used it as received. Cyclic voltammetry measurements were performed as described below.

[0216] The "reduction potential" represents the affinity of a material to accept electrons and generally correlates well with electron affinity. This is the formal potential (E o’ This can be measured by cyclic voltammetry, which measures E. Here, the cyclic voltammetry response is E o’ The reduction potential was irreversible and could not be measured directly; instead, it was estimated by the cathode peak potential. Specifically, each material was dissolved in acetonitrile (HPLC grade, Sigma-Aldrich) to prepare a 1 mM test molecular solution for measurement. A 0.1 M solution of tetrabutylammonium perchlorate (>99%, Sigma-Aldrich) was used as the supporting electrolyte. For electrodes, a 4 mm Pt disk electrode, a coiled Pt wire, and an Ag / AgCl electrode were used as the working electrode, counter electrode, and reference electrode, respectively. The solutions were purged with N2 gas for 5–10 minutes before electrochemical measurements to replace dissolved O2. Measurements were performed at approximately 23.5°C (temperature was not controlled for these experiments / performed at room temperature). The scanning speed was 50 mV / s.

[0217] Table 2 shows a comparison of the dibromo viologen compound Et2-Vio-Br2(EA9) with the TPS cation and the diphenyliodonium cation. [Table 2]

[0218] As shown in Table 2, the electron acceptor compound EA9 of the present invention (i.e., its cationic moiety) has a reduction potential higher than that of sulfonium cations and iodonium cations.

[0219] Synthesis of Et2Vio Di-PFBuS(A1) [ka] The synthesis reactions were carried out under a nitrogen atmosphere. All chemicals were used as received from commercial suppliers without further purification. Proton nuclear magnetic resonance (1H-NMR) spectra for all compounds were obtained using a 500 megahertz (MHz) NMR spectrometer. Chemical shifts are reported in δ (parts per million, ppm) relative to an internal tetramethylsilane standard. Multiples are indicated by singlet (s), doublet (d), triplet (t), quartet (q), multiplet (m), doublet of doublets (dd), doublet of triplets (dt), triplet of triplets (tt), or broad singlet (br).

[0220] 1,1'-Diethyl-[4,4'-bipyridine]-1,1'-diium bromide (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. The solid was dried in a vacuum oven for 2 days to obtain the product as a white solid (6.12 g, yield 75%). 1¹H-NMR (500MHz, acetone-d6): d: 9.49 (d, 4H), 8.89 (d, 4H), 5.04 (q, 4H), 1.82 (t, 6H).

[0221] Photoresist composition The chemical structures of the polymer (MP1), quencher (Q1), photoacid generators PAG1, PAG2, and PAG3, and electron acceptor compounds A1, A2, A3, and A4 used in the examples and comparative examples are shown below. [ka]

[0222] Photoresist compositions were prepared by dissolving solid components in a solvent using the materials and quantities shown in Table 3 (quantities are listed in grams). The total solids content of the photoresist compositions was 2.27 wt%. The solvent blends contained 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 and packaged in microclean bottles before use. [Table 3]

[0223] EUV lithography evaluation EUV lithography was performed on a 300 mm diameter silicon wafer coated with a 60 nm thick photoresist on a lower stack (a 20 nm silicon-based lower layer covering a 60 nm organic lower layer), using a post-coating bake at 110°C for 60 seconds. The coated wafer was then exposed using an ASML NXE3400B EUV scanner with a numerical aperture of 0.33, through contact hole masks of various dose and focus settings. After exposure, the wafer was post-exposure baked (PEB) at 100°C for 60 seconds, developed with CD-26 for 30 seconds, rinsed with deionized water, and spin-dried. The critical diameter (CD) of the imaged holes was measured using a Hitachi CG5000 CD scanning electron microscope (SEM). The ratio of dose to size (E) was also measured. size The exposure amount was defined as the amount of exposure required to print holes with a target CD of 24 nm and a pitch of 64 nm, or with a target CD of 28 nm and a pitch of 44 nm. The local limiting dimensional uniformity (LCDU) of the target CD or the holes in its vicinity was defined as the standard deviation (σ) of the hole CD measured from 20 fields of view (FOV) multiplied by 3. The pseudo-Z coefficient is reported below, and is given by Equation 1:

number

[0224] The EUV lithography results are shown in Table 4 (24nm / 64nm pitch contact holes) and Table 5 (28nm / 44nm pitch contact holes). [Table 4] [Table 5]

[0225] As shown in Tables 4 and 5, lithographic performance was improved by using nonpolymer secondary electron acceptor compounds with higher electron affinity than photoacid generator compounds.

[0226] While this disclosure is described in relation to what are currently considered to be exemplary practical embodiments, it should be understood that the present invention is not limited to the disclosed embodiments, but rather intended to cover various modifications and equivalent configurations that fall within the spirit and scope of the appended claims.

Claims

1. A composition, An acid-sensitive polymer comprising a first repeating unit derived from a monomer containing an acid-degradable group, Photoacid generating compound, A nonpolymer electron acceptor compound having a greater electron affinity than the photoacid generator compound, which does not generate photoacid and does not contain multiple diazonaphthoquinone (DNQ) groups, Based on the total weight of the composition, the solvent present in the composition in an amount exceeding 50 weight percent Includes, A composition that is a positive-type EUV photoresist or electron beam resist.

2. The composition according to claim 1, comprising two or more photoacid-generating compounds, wherein the nonpolymer electron acceptor compound has an electron affinity greater than the electron affinity of each of the two or more photoacid-generating compounds.

3. The composition according to claim 1 or 2, further comprising a base-unstable material, a base-soluble material, or a combination thereof.

4. The composition according to any one of claims 1 to 3, wherein the photoacid generator compound comprises a first anion, and the nonpolymer electron acceptor compound comprises a second anion, wherein the first anion and the second anion are structurally the same.

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

6. The aforementioned nonpolymer electron acceptor compounds are given by formulas (1) to (5) 【Chemistry 1】 It includes a compound represented by one of the following, in formulas (1) to (5), R １ ~R ２５ 、R ２０ａ 、and R ２１ａ are each 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 heterocycloalkyl, substituted or unsubstituted C ２～３０ alkenyl, substituted or unsubstituted C ２～３０ alkynyl, substituted or unsubstituted C ６～３０ aryl, substituted or unsubstituted C ７～３０ arylalkyl, substituted or unsubstituted C ７～３０ alkylaryl, substituted or unsubstituted C ２～３０ heteroaryl, substituted or unsubstituted C ３～３０ heteroarylalkyl, or substituted or unsubstituted C ３～３０ alkylheteroaryl, and R １ ~R ２５ , R ２０ａ , and R ２１ａ Each of these may further include one or more divalent linking groups as part of its structure. R １ ~R １０ Two or more adjacent members of these may form a ring with each other via one or more divalent linking groups, R １１ ~R １９ Two or more adjacent R groups may form a ring with each other via one or more divalent linking groups, and two or more adjacent R groups ２０ These may form rings with each other via one or more divalent linking groups, and two or more adjacent R ２１ They may form rings with each other via one or more divalent linking groups, R ２２ ~R ２５ Two or more of these may form a ring with each other via one or more divalent linking groups. L １ It is either a single bond or a divalent linking group. L ２ It is either a single bond or a polyvalent linking group. p is an integer between 2 and 6. n １ is an integer between 0 and 4, n ２ is an integer between 0 and 5, X is either a single bond or one or more divalent linking groups. A － and B － Each of these is an organic anion, and A － and B － The composition according to any one of claims 1 to 5, wherein the elements may be linked together to form a divalent organic anion.

7. The aforementioned nonpolymer electron acceptor compounds are given by formulas (6) to (26). 【Chemistry 2】 【Transformation 3】 It includes a compound represented by one of the following, in formulas (6) to (26), R ２６ ~R ８１ These are, independently, hydrogen, deuterium, halogen, nitro, amino, cyano, pyridinium, substituted or unsubstituted C, respectively. １～３０ Alkyl, substituted, or unsubstituted C １～３０ Heteroalkyl, substituted, or unsubstituted C ３～３０ Cycloalkyl, substituted, or unsubstituted C １～３０ Heterocycloalkyl, substituted or unsubstituted C ２～３０ Alkenyl, substituted or unsubstituted C ２～３０ Alkynyl, substituted or unsubstituted C ６～３０ Aryl, substituted, or unsubstituted C ７～３０ Arylalkyl, substituted or unsubstituted C ７～３０ Alkylaryl, substituted, or unsubstituted C ２～３０ Heteroaryl, substituted, or unsubstituted C ３～３０ Heteroarylalkyl, or substituted or unsubstituted C ３～３０ It is an alkyl heteroaryl, R ２６ ~R ８１ Each of these may further include one or more divalent linking groups as part of its structure. R ２６ ~R ３１ Two or more adjacent R may form a ring with each other via one or more divalent linking groups. ３２ ~R ３６ Two or more adjacent R may form a ring with each other via one or more divalent linking groups. ３７ ~R ４０ Two or more adjacent R may form a ring with each other via one or more divalent linking groups. ４１ ~R ４６ Two or more adjacent R may form a ring with each other via one or more divalent linking groups. ４７ ~R ５１ Two or more adjacent R may form a ring with each other via one or more divalent linking groups. ５４ ~R ５５ Two or more adjacent R may form a ring with each other via one or more divalent linking groups. ５６ ~R ５７ Two or more adjacent R may form a ring with each other via one or more divalent linking groups. ５８ ~R ５９ Two or more adjacent R may form a ring with each other via one or more divalent linking groups. ６０ ~R ６１ Two or more adjacent R may form a ring with respect to one or more divalent linking groups, ６４ ~R ６５ Two or more adjacent R may form a ring with each other via one or more divalent linking groups. ６８ Two or more adjacent R may form a ring with each other via one or more divalent linking groups. ７０ Two or more adjacent R may form a ring with each other via one or more divalent linking groups. ７１ Two or more adjacent R may form a ring with each other via one or more divalent linking groups. ７３ Two or more adjacent R may form a ring with each other via one or more divalent linking groups. ７４ Two or more adjacent R may form a ring with each other via one or more divalent linking groups. ７５ Two or more adjacent R may form a ring with each other via one or more divalent linking groups. ７６ ~R ７７ Two or more adjacent R may form a ring with each other via one or more divalent linking groups. ７８ ~R ７９ Two or more adjacent R may form a ring with each other via one or more divalent linking groups. ８０ ~R ８１ Two or more adjacent elements may form a ring with respect to one or more divalent linking groups. X － It is an organic anion, n1, n2, and n6-n9 are each independent integers between 0 and 4. n4 and n5 are each independent integers between 0 and 2. Each l is an integer from 0 to 4. Each k is an integer from 0 to 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, The composition according to any one of claims 1 to 6, wherein X, Y, and Z each independently contain an electron-withdrawing group.

8. The aforementioned nonpolymer electron acceptor compounds are given by formulas (27A) to (30A): 【Chemistry 4】 It includes a compound represented by one of the following, in formulas (27A) to (30A), R ８２ ~R ９３ each independently represents 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 heterocycloalkyl, substituted or unsubstituted C ２～３０ alkenyl, substituted or unsubstituted C ２～３０ alkynyl, substituted or unsubstituted C ６～３０ aryl, substituted or unsubstituted C ７～３０ arylalkyl, substituted or unsubstituted C ７～３０ alkylaryl, substituted or unsubstituted C ２～３０ heteroaryl, substituted or unsubstituted C ３～３０ heteroarylalkyl, or substituted or unsubstituted C ３～３０ alkylheteroaryl, and R ８２ ~R ９３ Each of these may further include one or more divalent linking groups as part of its structure. R ８２ and R ８３ These may form rings with one or more divalent linking groups. R ８４ ~R ８７ Two or more adjacent elements may form a ring with each other via one or more divalent linking groups. R ８８ ~R ９１ Two or more adjacent elements may form a ring with each other via one or more divalent linking groups. The composition according to any one of claims 1 to 7, wherein x is 1 or 2.

9. The composition according to any one of claims 1 to 8, comprising two or more of the nonpolymer electron acceptor compounds, wherein the electron affinity of the two or more nonpolymer electron acceptor compounds is greater than the electron affinity of the photoacid generator compound.

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

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

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

13. (a) A layer of the composition according to any one of claims 1 to 12 is applied to a substrate, (b) The composition layer is soft baked, (c) Expose the soft-baked composition layer to EUV or electron beam-activated radiation, (d) The composition layer is baked after exposure, (e) Develop the post-exposure baked composition layer to provide a resist relief image. A patterning formation method that includes the following.

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