Thiol-containing photoresist composition for extreme ultraviolet lithography

Abstract

The present application relates to a thiol-containing photoresist composition for use in extreme ultraviolet lithography. The photoresist composition may be used to fabricate a semiconductor device. A method of fabricating a semiconductor device includes forming a photoresist layer from the photoresist composition over a substrate. The photoresist layer is selectively exposed to actinic radiation to form a potential pattern, and the potential pattern is developed by applying a developer to the selectively exposed photoresist layer to form a patterned photoresist. The photoresist composition comprises a photoactive compound, a thiol-containing polymer comprising an aryl group and an acid labile group. The thiol groups may cross-link the polymer via disulfide oxide bond formation and / or a thiol-ene / alkyne "click" reaction.

Description

[0001] Priority Claims and Cross-References

[0002] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 588,880, filed on October 9, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present application relates to thiol-containing photoresist compositions for use in extreme ultraviolet lithography. Background Art

[0004] The semiconductor integrated circuit (IC) industry has experienced exponential growth. Technological advances in IC materials and design have produced multiple generations of ICs, each with smaller and more complex circuits than the previous generation. In the course of IC evolution, functional density (i.e., the number of interconnected devices per chip area) has generally increased, while geometric size (i.e., the smallest component (or line) that can be created using a manufacturing process) has decreased. This process of continuous scaling down generally provides benefits by increasing production efficiency and reducing associated costs. This continuous scaling down has also increased the complexity of processing and manufacturing ICs. Summary of the invention

[0005] Some embodiments of the present invention relate to a photoresist composition, comprising:

[0006] photoactive compounds; and

[0007] A thiol-containing polymer having the following structure (I):

[0008]

[0009] in:

[0010] L1, L2 and L3 are independently, at each occurrence, a direct bond or an oxy (—O—), carbonyl (—C(═O)—), carbonyloxy (—C(═O)—O—), oxycarbonyl (—OC(═O)—), carbonate (—OC(═O)—O—), C1-C20 alkylene, C1-C20 heteroalkylene, C4-C20 cycloalkylene, C4-C20 heterocycloalkylene, C5-C20 arylene or C5-C20 heteroarylene linker;

[0011] R1 is independently a C5-C20 aryl group at each occurrence, wherein the aryl group is unsubstituted or substituted by halogen, carbonyl group, hydroxyl group or R s1 replace;

[0012] R2 is independently an acid-labile group at each occurrence, wherein the acid-labile group is unsubstituted or replaced by R s1 replace;

[0013] R3 is independently C1-C20 alkyl, C1-C20 heteroalkyl, C4-C20 cycloalkyl, C2-C30 heterocycloalkyl, C5-C20 aryl, C5-C20 heteroaryl or R s1 Group;

[0014] R s1 is SH, a C1-C20 sulfanyl group, a C3-C20 sulfadyl group, a C1-C20 thiolalkyl group, a C2-C20 sulfadyloxy group, a C3-C20 sulfadyloxyalkyl group, a C1-C20 thioacetyl group, a C2-C20 thioacetylalkyl group, a thiocarboxyl group, a C2-C20 sulfanylcarboxyl group, a C4-C20 sulfadylcarboxyl group, a C3-C20 sulfadylcarbocycle group or a C3-C20 heterosulfur ring group;

[0015] R a , R b and R c is independently at each occurrence H or a C1-C3 alkyl group; and

[0016] 0<x≤1, 0<y≤1, and 0≤z≤1, provided that one or more of R1, R2 and R3 contains R s1 , such that the compound of structure (I) comprises at least one R s1 .

[0017] Other embodiments of the present invention relate to a photoresist composition, comprising:

[0018] Initiator;

[0019] Photoacid generators; and

[0020] A thiol-containing polymer having the following structure (II):

[0021]

[0022] in:

[0023] L1, L2, L3 and L4 are independently, at each occurrence, a direct bond or an oxy (—O—), carbonyl (—C(═O)—), carbonyloxy (—C(═O)—O—), oxycarbonyl (—OC(═O)—), carbonate (—OC(═O)—O—), C1-C20 alkylene, C1-C20 heteroalkylene, C4-C20 cycloalkylene, C4-C20 heterocycloalkylene, C5-C20 arylene or C5-C20 heteroarylene linker;

[0024] R1 is independently a C5-C20 aryl group at each occurrence, wherein the aryl group is unsubstituted or substituted by halogen, carbonyl group, hydroxyl group or R s1 replace;

[0025] R2, at each occurrence, is independently a divalent acid-labile group;

[0026] R3 is independently C1-C20 alkyl, C1-C20 heteroalkyl, C4-C20 cycloalkyl, C2-C30 heterocycloalkyl, C5-C20 aryl, C5-C20 heteroaryl or R s1 Group;

[0027] R4, at each occurrence, is independently a free radically active functional group comprising an alkenyl or alkynyl group;

[0028] R s1 is SH, a C1-C20 sulfanyl group, a C3-C20 sulfadyl group, a C1-C20 thiolalkyl group, a C2-C20 sulfadyloxy group, a C3-C20 sulfadyloxyalkyl group, a C1-C20 thioacetyl group, a C2-C20 thioacetylalkyl group, a thiocarboxyl group, a C2-C20 sulfanylcarboxyl group, a C4-C20 sulfadylcarboxyl group, a C3-C20 sulfadylcarbocycle group or a C3-C30 heterosulfur ring group;

[0029] R a , R b and R c is independently at each occurrence H or a C1-C3 alkyl group; and

[0030] 0<x≤1, 0<y≤1, and 0≤z≤1, provided that R1, R3, or both contain R s1 , such that the compound of structure (I) comprises at least one R s1 .

[0031] Still other embodiments of the present invention relate to a photoresist composition comprising:

[0032] Initiator;

[0033] Photoacid generators;

[0034] a thiol-containing cross-linking agent comprising two or more thiol groups; and

[0035] A thiol-free polymer having the following structure (III):

[0036]

[0037] in:

[0038] L1, L2, L3, and L4 are each independently, upon each occurrence, a direct bond or an oxy group (-O-), a carbonyl group (-C(═O)-), a carbonyl oxy group (-C(═O)-O-), an oxycarbonyl group (-O-C(═O)-), a carbonate group (-O-C(═O)-O-), a C1-C20 alkylene group, a C1-C20 heteroalkylene group, a C4-C20 cycloalkylene group, a C4-C20 heterocycloalkylene group, a C5-C20 arylene group, or a C5-C20 heteroarylene linker;

[0039] R5 is, upon each occurrence, independently a C5-C20 aryl group, wherein the arylene is unsubstituted or substituted with a halogen, a carbonyl group, or a hydroxyl group;

[0040] R6 is, upon each occurrence, independently a divalent acid-labile group;

[0041] R7 is, upon each occurrence, independently a C1-C20 alkyl group, a C1-C20 heteroalkyl group, a C4-C20 cycloalkyl group, a C2-C30 heterocycloalkyl group, a C5-C20 aryl group, or a C5-C20 heteroaryl group;

[0042] R8 is, upon each occurrence, independently a free radical active functional group selected from an alkenyl or alkynyl group;

[0043] R a 、R b and R c are each independently, upon each occurrence, H or a C1-C3 alkyl group; and

[0044] 0 < x ≤ 1, 0 < y ≤ 1, and 0 ≤ z ≤ 1. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Aspects of the present disclosure may be best understood from the following detailed description when read in conjunction with the accompanying drawings. It should be noted that, in accordance with standard practice in the industry, various features are not drawn to scale. In fact, for the sake of clarity of discussion, the dimensions of various features may be arbitrarily increased or decreased.

[0046] Figure 1 is a flow chart of a method for manufacturing a semiconductor device according to some embodiments of the present disclosure.

[0047] Figures 2A to 2G is a cross-sectional view of a semiconductor device manufactured by a method using Figure 1 according to some embodiments of the present disclosure.

[0048] Figure 3A illustrates a first exemplary scheme for crosslinking a thiol-containing polymer via disulfide bond formation according to some embodiments of the present disclosure.

[0049] Figure 3BA second exemplary scheme for cross-linking a thiol-containing polymer using a cross-linking agent according to some embodiments of the present disclosure is shown.

[0050] Figure 3C A third exemplary scheme for cross-linking thiol-ene polymers according to some embodiments of the present disclosure is shown.

[0051] Figure 4 Exemplary cross-linking agents according to some embodiments of the present disclosure are shown.

[0052] Figure 5 An exemplary scheme for crosslinking thiol-free polymers via a thiol-ene reaction is shown according to some embodiments of the present disclosure.

[0053] Fig. 6A The structure of the polymer in the exposed area of ​​the photoresist layer according to some embodiments of the present disclosure is shown.

[0054] Figure 6B According to some embodiments of the present disclosure, Fig. 6A The structure of the polymer in the non-exposed areas of the photoresist layer. DETAILED DESCRIPTION

[0055] The following disclosure provides many different embodiments or examples for realizing the different features of the provided subject matter. Specific examples of components, values, operations, materials, arrangements, etc. are described below to simplify the present disclosure. Of course, these are merely examples and are not intended to be limiting. Other components, values, operations, materials, arrangements, etc. can be envisioned. For example, forming a first feature above or on a second feature in the following description may include an embodiment in which the first feature and the second feature are formed as direct contacts, and may also include an embodiment in which additional features may be formed between the first feature and the second feature so that the first feature and the second feature may not be in direct contact. In addition, the present disclosure may repeat reference numerals and / or letters in various examples. This repetition is for the purpose of simplicity and clarity, and does not itself specify the relationship between the various embodiments and / or configurations discussed.

[0056] Further, for ease of description, spatially relative terms such as "below," "below," "lower," "above," "upper," etc. may be used herein to describe the relationship of one element or feature to another element or features as shown in the figures. Spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. The system may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein should be interpreted accordingly.

[0057] "Alkyl" by itself or as part of another substituent refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from 1 to 20 carbon atoms (C1-C20 alkyl), 1 to 12 carbon atoms (C1-C12 alkyl), 1 to 8 carbon atoms (C1-C8 alkyl), or 1 to 6 carbon atoms (C1-C6 alkyl), and which is attached to the rest of the molecule via a single bond, for example, methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, n-pentyl, 1,1-dimethylethyl (tert-butyl), 3-methylhexyl, 2-methylhexyl, etc. Unless specifically stated otherwise in the specification, an alkyl group is optionally substituted.

[0058] As used herein, "alkylene" refers to a straight or branched divalent hydrocarbon chain that connects the rest of the molecule to a group, which consists only of carbon and hydrogen, contains no unsaturation, and has 1 to 12 carbon atoms, such as methylene, ethylene, propylene, n-butylene, etc. The alkylene chain is attached to the rest of the molecule and to the group through a single bond. The attachment point of the alkylene chain to the rest of the molecule and to the group can be through one carbon or any two carbons within the chain. Unless otherwise specifically stated in this specification, alkylene groups are optionally substituted.

[0059] As used herein, "olefin" refers to a straight or branched hydrocarbon chain consisting only of carbon and hydrogen, containing at least one carbon-carbon double bond and having 2 to 12 carbon atoms, for example, ethylene, propylene, n-butene, etc. Unless otherwise specifically stated in the specification, the olefin group is optionally substituted.

[0060] As used herein, "alkenylene" refers to a straight or branched divalent hydrocarbon chain that connects the rest of the molecule to a certain group, which consists only of carbon and hydrogen, contains at least one double bond, has 2 to 12 carbon atoms, such as vinylene, propenylene, n-butenylene, etc. The alkenylene chain is attached to the rest of the molecule by a single bond and to the group by a double bond or a single bond. The attachment point of the alkenylene chain to the rest of the molecule and to the group can be through one carbon or any two carbons within the chain. Unless otherwise specifically stated in this specification, alkenylene is optionally substituted.

[0061] As used herein, "alkyne" refers to a straight or branched hydrocarbon chain consisting only of carbon and hydrogen, containing at least one carbon-carbon triple bond and having 2 to 12 carbon atoms, for example, acetylene, propyne, n-butyne, and the like.

[0062] As used herein, "alkynylene" refers to a straight or branched divalent hydrocarbon chain that connects the rest of the molecule to a group, which consists only of carbon and hydrogen, contains at least one triple bond, has 2 to 12 carbon atoms, such as ethynylene, propynylene, n-butynylene, etc. The alkynylene chain is attached to the rest of the molecule by a single bond and to the group by a triple bond or a single bond. The attachment point of the alkynylene chain to the rest of the molecule and to the group can be through one carbon or any two carbons in the chain. Unless otherwise specifically stated in this specification, alkynylene is optionally substituted.

[0063] As used herein, "alkoxy" refers to an O-alkyl group, wherein alkyl is as defined above. Unless stated otherwise specifically in the specification, an alkoxy group is optionally substituted.

[0064] As used herein, "alkyl ether" refers to any alkyl as defined above, wherein at least one carbon-carbon bond is replaced by a carbon-oxygen bond. The carbon-oxygen bond can be on the terminal (such as alkoxy) or the carbon-oxygen bond can be internal (i.e., COC). Alkyl ethers contain at least one carbon-oxygen bond, but may contain more than one carbon-oxygen bond. For example, polyethylene glycol (PEG) is included in the meaning of alkyl ethers. Unless otherwise specifically stated in this specification, alkyl ether groups are optionally substituted.

[0065] As used herein, "cycloalkyl" refers to a stable non-aromatic monocyclic or polycyclic carbocyclic group consisting only of carbon and hydrogen atoms, which may include a fused ring system or a bridged ring system, having 3 to 15 carbon atoms, preferably 3 to 10 carbon atoms, and which is saturated or unsaturated and attached to the rest of the molecule by a single bond. Monocyclic groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Polycyclic groups include, for example, adamantyl, norbornyl, decahydronaphthyl, 7,7-dimethyl-bicyclo [2.2.1] heptyl, etc. "Cycloalkylene" is a divalent or polyvalent cycloalkyl group, which typically connects a portion of a molecule to a certain group or connects two or more groups. Unless otherwise specifically stated in the specification, cycloalkyl (or cycloalkylene) is optionally substituted.

[0066] As used herein, "heteroalkyl" refers to an alkyl group as defined above that contains at least one heteroatom (e.g., N, O, P, or S) within the alkyl group or at the terminus of the alkyl group. In some embodiments, the heteroatom is within the alkyl group (i.e., the heteroalkyl group contains at least one carbon-[heteroatom] x-carbon bond, wherein x is 1, 2 or 3). In other embodiments, the heteroatom is located at the end of the alkyl group and is therefore used to join the alkyl group to the rest of the molecule (e.g., M1-HA), wherein M1 is part of the molecule, H is a heteroatom and A is an alkyl group). Unless otherwise specifically stated in this specification, heteroalkyl groups are optionally substituted. Exemplary heteroalkyl groups include ethylene oxide (e.g., polyethylene oxide), optionally including a phosphorus-oxygen bond, such as a phosphodiester bond.

[0067] As used herein, "heteroalkylene" refers to an alkylene group as defined above, which contains at least one heteroatom (e.g., N, O, P, or S) within the alkylene chain or at the end of the alkylene chain. In some embodiments, the heteroatom is within the alkylene chain (i.e., the heteroalkylene contains at least one carbon-heteroatom-carbon bond). In other embodiments, the heteroatom is at the end of the alkylene and thus serves to join the alkylene to the rest of the molecule (e.g., M1-HA-M2, where M1 and M2 are part of the molecule, H is a heteroatom and A is an alkylene). Unless otherwise specifically stated in the specification, heteroalkylene groups are optionally substituted.

[0068] As used herein, "heteroalkenyl" is a heteroalkyl group as defined above containing at least one carbon-carbon double bond. Unless stated otherwise specifically in the specification, a heteroalkenyl group is optionally substituted.

[0069] As used herein, "heteroalkynyl" is a heteroalkyl group containing at least one carbon-carbon triple bond. Unless stated otherwise specifically in the specification, a heteroalkynyl group is optionally substituted.

[0070] "Carbocycle" refers to a stable 3 to 18-membered aromatic or non-aromatic ring containing 3 to 18 carbon atoms. Unless otherwise specifically stated in the specification, the carbocycle can be a monocyclic, bicyclic, tricyclic or tetracyclic ring system, which can include a fused ring system or a bridged ring system, and can be partially or completely saturated. Non-aromatic carbocyclic groups include cycloalkyl, while aromatic carbocyclic groups include aryl. Unless otherwise specifically stated in the specification, the carbocyclic group is optionally substituted.

[0071] "Aryl" used alone or in combination with other terms (e.g., aryloxy, aralkyl) refers to a ring system containing at least one carbocyclic aromatic ring. In some embodiments, the aryl group contains 6 to 18 carbon atoms. The aryl ring can be a monocyclic, bicyclic, tricyclic or tetracyclic ring system, which can include a fused ring system or a bridged ring system. Aryl groups include, but are not limited to, aceanthrylene, acenaphthylene, acephenanthrylene, anthracene, azulene, benzene, The aryl groups include chrysene, fluoranthene, fluorene, as-indacene, s-indacene, indane, indene, naphthalene, phenalene, phenanthrene, pleiadene, pyrene and triphenylene. Unless otherwise specifically stated in the specification, the aryl group is optionally substituted.

[0072] As used herein, "arylene" refers to a bifunctional aromatic moiety containing 1 to 5 aromatic rings. Unless specifically stated otherwise in the specification, an arylene group is optionally substituted.

[0073] As used herein, "heterocycle" refers to a stable 3- to 18-membered aromatic or non-aromatic ring containing 1 to 12 carbon atoms and 1 to 6 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur. Unless otherwise specifically stated in this specification, the heterocycle can be a monocyclic, bicyclic, tricyclic or tetracyclic ring system, which can include a fused ring system or a bridged ring system; and the nitrogen, carbon or sulfur atoms in the heterocycle can be optionally oxidized; the nitrogen atom can be optionally quaternized; and the heterocycle can be partially or fully saturated. Examples of aromatic heterocycles are listed in the definition of heteroaryl below (i.e., heteroaryl is a subset of heterocycle). Examples of non-aromatic heterocycles include, but are not limited to, dioxolanyl, thienyl[1,3]dithianyl, decahydroisoquinolyl, imidazolinyl, imidazolidinyl, isothiazolidinyl, isoxazolidinyl, morpholinyl, octahydroindolyl, octahydroisoindolyl, 2-oxopiperazinyl, 2-oxopiperidinyl, 2-oxopyrrolidinyl, oxazolidinyl, piperidinyl The heterocyclyl group may be substituted with any of the following: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 61, 62, 63, 64, 65, 66, 67, 68, 69, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 101, 114, 125, 130, 131, 146, 159, 161, 172, 183, 194, 105, 116

[0074] As used herein, "heteroaryl" refers to a 5- to 14-membered ring system containing 1 to 13 carbon atoms, 1 to 6 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, and at least one aromatic ring. For the purposes of certain embodiments of the present disclosure, the heteroaryl group can be a monocyclic, bicyclic, tricyclic or tetracyclic ring system, which can include a fused ring system or a bridged ring system; and the nitrogen, carbon or sulfur atoms in the heteroaryl group can be optionally oxidized; the nitrogen atom can be optionally quaternized. Examples include, but are not limited to, azepinyl, acridinyl, benzimidazolyl, benzothiazolyl, benzoindolyl, benzodioxolyl, benzofuranyl, benzooxazolyl, benzothiazolyl, benzothiadiazolyl, benzo[b][1,4]dioxepinyl, 1,4-benzodioxa nyl), benzonaphthofuranyl, benzoxazolyl, benzodioxolyl, benzodioxinyl, benzopyranyl, benzopyranonyl, benzofuranyl, benzofuranonyl, benzothienyl / benzothiophenyl, benzotriazolyl, benzo[4,6]imidazo[1,2-a]pyridinyl,2-a]pyridinyl), benzoxazolinonyl, benzimidazolthionyl, carbazolyl, cinnolinyl, dibenzofuranyl, dibenzothiophenyl, furanyl, furanonyl, isothiazolyl, imidazolyl, indazolyl azolyl), indolyl, indazolyl, isoindolyl, indolinyl, isoindolinyl, isoquinolyl, indolizinyl, isoxazolyl, naphthyridinyl, oxadiazolyl, 2-oxoazepinyl, oxazolyl, oxirane oxiranyl, 1-oxidopyridinyl, 1-oxidopyrimidinyl, 1-oxidopyrazinyl, 1-oxidopyridazinyl, 1-phenyl-1H-pyrrolyl, phenazinyl, phenothiazinyl, phenoxazinyl, phthalazinyl nyl), pteridinyl, pteridinonyl, purinyl, pyrrolyl, pyrazolyl, pyridinyl, pyridinonyl, pyrazinyl, pyrimidinyl, pryrimidinonyl, pyridazinyl, pyrrolyl, pyrido[2,3-d]pyrimidinyl, pyrido[2,3-d]pyrimidinonyl), quinazolinyl, quinazolinonyl, quinoxalinyl, quinoxalinonyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, thiazolyl, thiadiazolyl, thieno[3,2-d]pyrimidin-4-onyl, thieno[2,3-d]pyrimidin-4-onyl, triazolyl, tetrazolyl, triazinyl, and thiophenyl (i.e., thienyl). Unless stated otherwise specifically in the specification, a heteroaryl group is optionally substituted.

[0075] As used herein, "heteroarylene" refers to a divalent aromatic hydrocarbon of 6 to 20 carbon atoms containing N, S, O or P.

[0076] "Halo" or "halogen" as used herein includes fluorine, chlorine, bromine and iodine.

[0077] "Halogenated" means having one or more halogen atoms, such as fluorine, chlorine, bromine or iodine atoms, incorporated into the above-mentioned group.

[0078] "Fluorinated" means having one or more fluorine atoms incorporated into the above-mentioned group, for example, when a fluoroalkyl group is indicated, the group contains a single fluorine atom, a difluoromethylene group, a trifluoromethyl group, a combination of these, or is a perfluorinated group (e.g., CF3, C2F5, C3F7, C4F9, etc.).

[0079] As used herein, the term "substituted" means any of the above groups (e.g., alkyl, alkylene, alkenyl, alkynyl, heteroalkylene, heteroalkenyl, heteroalkynyl, alkoxy, heteroalkyl, carbocycle, cycloalkyl, aryl, arylene, heterocycle, heteroaryl and / or heteroarylene) in which at least one hydrogen atom (e.g., 1, 2, 3 or all of the hydrogen atoms) is replaced by a bond to a non-hydrogen atom, such as, but not limited to, a halogen atom, such as F, Cl, Br, I; such as a hydroxyl group, an alkoxy group Oxygen atoms in groups such as thiol groups, sulfanyl groups, sulfone groups, sulfonyl groups, and sulfoxide groups; Nitrogen atoms in groups such as amines, amides, alkylamines, dialkylamines, arylamines, alkylarylamines, diarylamines, N-oxides, imides, and enamines; Silicon atoms in groups such as trialkylsilyl groups, dialkylarylsilyl groups, alkyldiarylsilyl groups, and triarylsilyl groups; And other heteroatoms in various other groups. "Substituted" also means any of the above-mentioned groups, wherein one or more hydrogen atoms are replaced by higher-order bonds (e.g., double bonds or triple bonds) to heteroatoms, such as oxygen in oxo groups, carbonyl groups, carboxyl groups, and ester groups; And nitrogen in groups such as imines, oximes, hydrazones, and nitriles. For example, "substituted" includes any of the above-mentioned groups, wherein one or more hydrogen atoms are replaced by -NR g R h 、-NR g C(=O)R h 、-NR g C(=O)NR g R h 、-NR g C(=O)OR h 、-NR g S02R h 、-OC(=O)NR g R h 、-OR g 、-SR g 、-SOR g 、-SO2R g 、-OSO2R g 、-SO2OR g , =NSO2R g and -SO2NR g R h "Substituted" also means any of the above groups in which one or more hydrogen atoms are replaced by -C(=O)R g 、-C(=O)OR g 、-C(=O)NR g R h 、-CH2SO2R gand -CH2SO2NR g R h In the above, R g and R h The same or different, and independently hydrogen, alkyl, alkoxy, alkylamino, sulfanyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, haloalkyl, heterocyclyl, N-heterocyclyl, heterocyclylalkyl, heteroaryl, N-heteroaryl and / or heteroarylalkyl. "Substituted" also means any of the above groups, wherein one or more hydrogen atoms are replaced by a bond to: amino, cyano, hydroxy, imino, nitro, oxo, oxo, halo, alkyl, alkoxy, alkylamino, sulfanyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, haloalkyl, heterocyclyl, N-heterocyclyl, heterocyclylalkyl, heteroaryl, N-heteroaryl and / or heteroarylalkyl. In addition, each of the above substituents may also be optionally substituted by one or more of the above substituents.

[0080] IC manufacturing uses one or more photolithography processes to transfer geometric patterns onto a film or substrate. The geometric shapes and patterns on the semiconductor form complex structures that allow dopants, electrical properties, and wires to complete the circuit and achieve technical goals. In the photolithography process, a photoresist is applied to the substrate as a thin film and then exposed to one or more types of radiation or light through a photomask. The photomask contains transparent and opaque features that define the pattern to be created in the photoresist layer. The areas in the photoresist that are exposed to the light transmitted through the photomask are soluble or insoluble in a specific type of solution called a developer. In the case where the exposed areas are soluble, a positive image of the photomask is produced in the photoresist, and this type of photoresist is called a positive photoresist. On the other hand, if the unexposed areas are dissolved by the developer, a negative image is produced in the photoresist, and this type of photoresist is called a negative photoresist. The developer removes the more soluble areas, leaving the patterned photoresist in place. The resist pattern is then used as an etch mask in a subsequent etching process to transfer the pattern to the underlying material layer, thereby replicating the mask pattern in the underlying material layer. Alternatively, the resist pattern is then used as an ion implantation mask in a subsequent ion implantation process applied to the underlying material layer (e.g., an epitaxial semiconductor layer).

[0081] The quality of the resist pattern affects the quality of the final IC. As the critical dimensions (CD) of integrated circuits continue to shrink, the ability of the photoresist to accurately replicate the features of the photomask becomes increasingly challenging due to image blurring caused by photoacid diffusion during the photolithography process. Specifically, photogenerated acid may migrate away from the exposed areas during photolithography and into unexposed areas where it can trigger undesirable reactions.

[0082] Increasing the glass transition temperature (Tg) of a photoresist polymer generally shortens the acid diffusion length. This is because the diffusion rate of the acid in the photoresist polymer decreases when the photoresist polymer is in the glassy solid state. Therefore, photoresist polymers characterized by higher glass transition temperatures are more suitable for inhibiting acid diffusion, thereby improving pattern resolution and reducing line width roughness (LWR). Crosslinking has been shown to effectively increase the molecular weight and glass transition temperature of resist polymers.

[0083] Phenolic groups are commonly used as crosslinking groups in existing photoresist polymers. However, the weak acidity (pKa = 9.95) of the phenolic groups requires an additional baking step to initiate a crosslinking reaction between the phenolic groups at a temperature in the range of 100°C to 150°C. In addition, the baking temperature needs to be lower than the decomposition temperature of the acid-labile groups (ALG) in the photoresist polymer to prevent the ALG from cleaving during the crosslinking stage. Since higher baking temperatures lead to higher crosslinking reaction efficiency, such control of the baking temperature may limit the efficiency of the crosslinking reaction between the phenolic groups.

[0084] In an embodiment of the present invention, a photoresist composition comprising a thiol-containing polymer or a thiol-containing crosslinking agent is provided to improve the crosslinking efficiency of EUV lithography. A thiol having a pKa value of 6.62 has a higher acidity than phenol, which is commonly used as a crosslinking group in an existing EUV photoresist composition. At the same baking temperature, the higher acidity of thiol leads to a more complete thiol-thiol crosslinking reaction compared to the phenol-phenol crosslinking reaction. The enhanced crosslinking efficiency leads to an increase in the molecular weight of the crosslinked photoresist polymer, thereby leading to a higher glass transition temperature. The increased glass transition temperature of the crosslinked photoresist polymer allows the photoacid diffusion length to be effectively limited during the photolithography process. This in turn enables patterning features to be manufactured with higher resolution and lower line width roughness (line width roughness, LWR). Therefore, the quality of the resist pattern is improved, which helps to improve the yield and reliability of ICs.

[0085] Figure 1 is a flow chart illustrating a method 100 of fabricating a semiconductor device 200 according to some embodiments of the present disclosure. Figures 2A to 2G 2 is a cross-sectional view of a semiconductor device 200 at various stages of manufacture according to some embodiments of the present disclosure. Figure 1 and Figures 2A to 2GThe method 100 is described, wherein a semiconductor device 200 is fabricated by using an embodiment of the method 100. It should be understood that for additional embodiments of the method, additional steps may be provided before, during, and after the method 100, and some of the steps described below may be replaced or eliminated. It should also be understood that for additional embodiments of the semiconductor device 200, additional features may be added in the semiconductor device 200, and some of the features described below may be replaced or eliminated.

[0086] The semiconductor device 200 may be an intermediate structure during the manufacture of an IC or a portion thereof. The IC may include logic circuits, memory structures, passive components (e.g., resistors, capacitors, and inductors) and active components (e.g., diodes, field-effect transistors (FETs), metal-oxide semiconductor field effect transistors (MOSFETs), complementary metal-oxide semiconductor (CMOS) transistors, bipolar transistors, high-voltage transistors, high-frequency transistors, fin-like FETs (FinFETs), other three-dimensional (3D) FETs, and combinations thereof. The semiconductor device 200 may include a plurality of semiconductor devices (e.g., transistors) that may be interconnected.

[0087] Reference Figure 1 and Figure 2A According to some embodiments, method 100 includes operation 102 in which a material layer 210 is deposited on a substrate 202 . Figure 2A is a cross-sectional view of the semiconductor device 200 after depositing a material layer 210 on the substrate 202 according to some embodiments.

[0088] In some embodiments, substrate 202 may be a bulk semiconductor substrate comprising one or more semiconductor materials. In some embodiments, substrate 202 may comprise silicon, silicon germanium, carbon-doped silicon (Si:C), silicon germanium carbide, or other suitable semiconductor materials. In some embodiments, substrate 202 is composed entirely of silicon.

[0089] In some embodiments, substrate 202 may include one or more epitaxial layers formed on the top surface of a bulk semiconductor substrate. In some embodiments, the one or more epitaxial layers introduce strain in substrate 202 to enhance performance. For example, the epitaxial layer comprises a semiconductor material different from the bulk semiconductor substrate, such as a silicon germanium layer covering bulk silicon or a silicon layer covering bulk silicon germanium. In some embodiments, the epitaxial layer incorporated into substrate 202 is formed by selective epitaxial growth, such as metalorganic vapor phase epitaxy (MOVPE), molecular beam epitaxy (MBE), hydride vapor phase epitaxy (HVPE), liquid phase epitaxy (LPE), metal-organic molecular beam epitaxy (MOMBE), or a combination thereof.

[0090] In some embodiments, substrate 202 may be a semiconductor-on-insulator (SOI) substrate. In some embodiments, the SOI substrate includes a semiconductor layer, such as a silicon layer formed on an insulator layer. In some embodiments, the insulator layer is a buried oxide (BOX) layer comprising silicon oxide or silicon germanium oxide. The insulator layer is disposed on a processing substrate (e.g., a silicon substrate). In some embodiments, the SOI substrate is formed using separation by implanted oxygen (SIMOX) or other suitable techniques (e.g., wafer bonding and grinding).

[0091] In some embodiments, substrate 202 may also include a dielectric substrate, such as silicon oxide, silicon nitride, silicon oxynitride, low-k dielectrics, silicon carbide, and / or other suitable layers.

[0092] In some embodiments, the substrate 202 may also include various p-type doped regions and / or n-type doped regions implemented by processes such as ion implantation and / or diffusion. These doped regions include n-wells, p-wells, lightly doped regions (LDDs), and various channel doping distributions configured to form various IC devices (e.g., COMOS transistors, image sensors, and / or light emitting diodes (LEDs)). The substrate 202 may further include other functional features, such as resistors and / or capacitors formed in and / or on the substrate 202.

[0093] In some embodiments, the substrate 202 may also include various isolation features. The isolation features separate the various device regions in the substrate 202. The isolation features include different structures formed by using different processing techniques. For example, the isolation features may include shallow trench isolation (STI) features. The formation of STI may include etching trenches in the substrate 202 and filling the trenches with insulator materials such as silicon oxide, silicon nitride and / or silicon oxynitride. The filled trenches may have a multilayer structure, such as a thermal oxide liner layer with silicon nitride filling the trenches. Chemical mechanical polishing (CMP) may be performed to polish away excess insulator material and flatten the top surface of the isolation features.

[0094] In some embodiments, the substrate 202 may further include a gate stack formed of a dielectric layer and an electrode layer. The dielectric layer may include an interfacial layer and a high-k dielectric layer deposited by a suitable technique, such as chemical vapor deposition (CVD), atomic layer deposition (ALD), physical vapor deposition (PVD), thermal oxidation, combinations thereof, and / or other suitable techniques. The interfacial layer may include silicon dioxide, and the high-k dielectric layer may include LaO, AlO, ZrO, TiO, Ta2O5, Y2O3, SrTiO3, BaTiO3, BaZrO, HfZrO, HfLaO, HfSiO, LaSiO, AlSiO, HfTaO, HfTiO, (Ba, Sr)TiO3 (BST), Al2O3, Si3N4, SiON, and / or other suitable materials. The electrode layer may include a single layer or alternatively a multilayer structure, such as a metal layer having a work function that enhances device performance (work function metal layer), a liner layer, a wetting layer, an adhesion layer, and various combinations of a conductive layer of a metal, a metal alloy, or a metal silicide. The electrode layer may include Ti, Ag, Al, TiAlN, TaC, TaCN, TaSiN, Mn, Zr, TiN, TaN, Ru, Mo, Al, WN, Cu, W, any suitable material, and / or combinations thereof.

[0095] In some embodiments, the substrate 202 may also include multiple interlayer dielectric (ILD) layers and conductive features, which are integrated to form an interconnect structure, which is configured to couple various p-type and n-type doped regions and other functional features (such as gate electrodes) to form a functional integrated circuit. In one example, the substrate 202 may include a portion of the interconnect structure, and the interconnect structure may include a multi-layer interconnect (MLI) structure and an ILD layer integrated with the MLI structure to provide electrical wiring to couple various devices in the substrate 202 to input / output power and signals. The interconnect structure includes various metal lines, contacts, and through-hole features (or through-hole plugs). The metal lines provide horizontal electrical wiring. The contacts provide vertical connections between the silicon substrate and the metal lines, and the through-hole features provide vertical connections between metal lines in different metal layers.

[0096] A material layer 210 is disposed on the substrate 202. The material layer 210 is a layer to be processed (e.g., to be patterned or to be implanted) by the method 100. In some embodiments, the material layer 210 is a hard mask layer to be patterned. In some embodiments, the material layer 210 comprises a dielectric material, such as silicon oxide, silicon nitride, or silicon oxynitride. In some other embodiments, the material layer 210 comprises a metal oxide (e.g., titanium oxide) or a metal nitride (e.g., titanium nitride). In some embodiments, the material layer 210 also serves as an anti-reflection coating (ARC) layer, the composition of which is selected to minimize the reflection of radiation achieved during exposure of the photoresist layer 220. For example, in some embodiments, the material layer 210 comprises silicon oxide, silicon oxycarbide, or plasma enhanced chemical vapor deposited silicon oxide. The material layer 210 may be formed by any suitable process including chemical vapor deposition (CVD), physical vapor deposition (PVD), plasma enhanced chemical vapor deposition (PECVD), atomic layer deposition (ALD), or spin coating, and may be formed to any suitable thickness.

[0097] Reference Figure 1 and Figure 2B According to some embodiments, the method 100 proceeds to operation 104 where a photoresist composition is coated on the material layer 210 to form a photoresist layer 220 . Figure 2B is a cross-sectional view of the semiconductor device 200 after forming a photoresist layer 220 on the material layer 210 according to some embodiments.

[0098] The photoresist layer 220 is a photosensitive layer that can be patterned by exposure to actinic radiation. In some embodiments, the photoresist layer 220 is sensitive to ultraviolet radiation. In some embodiments, the ultraviolet radiation is deep ultraviolet (DUV) radiation. In some embodiments, the ultraviolet radiation is extreme ultraviolet (EUV) radiation. In some embodiments, the radiation is an electron beam.

[0099] In some embodiments, the photoresist composition includes a thiol-containing polymer.

[0100] In some embodiments, the thiol-containing polymer is a copolymer comprising two or more hydrocarbon monomer units forming the polymer backbone. The monomer units can be derived from acrylates, methacrylates, crotonates, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconate diesters, (meth) acrylonitrile, (meth) acrylamide, styrene, hydroxystyrene, vinyl ethers, novolacs, combinations of these, and the like.

[0101] In some embodiments, the thiol-containing polymer has a thiol group attached to the polymer backbone, and the thiol group is a C6-C20 thiol-benzyl group, a C1-C20 thiol-alkyl group, a C3-C20 thiol-cycloalkyl group, a C1-C20 thiol-hydroxyalkyl group, a C2-C20 thiol-alkoxy group, a C3-C20 thiol-alkoxyalkyl group, a C1-C20 thiol-acetyl group, a C2-C20 thiol-acetylalkyl group, a C1-C20 thiol-carboxyl group, a C2-C20 thiol-alkylcarboxyl group, a C4-C20 thiol-cycloalkylcarboxyl group, a C3-C20 saturated or unsaturated thiol-hydrocarbon ring, or a C3-C20 thiol-heterocyclic group. In some embodiments, the thiol group is substituted by one, two, three or more thiol atoms.

[0102] The thiol groups in the thiol-containing polymers can be cross-linked by any suitable method. In some embodiments, the thiol-containing polymers can be cross-linked by forming interchain disulfide bonds between polymer chains via acid-catalyzed oxidation of the thiol groups in the presence of an oxidizing agent ( Figure 3A In some embodiments, thiol-containing polymers can be cross-linked using a cross-linking agent comprising a cross-linking group that reacts with the thiol group to create bridges between polymer chains via a light or heat-triggered "click" reaction (such as a thiol-ene or thiol-yne reaction). Figure 3B In some embodiments, the thiol-containing polymer also contains free radically active functional groups, such as olefin or alkyne groups, such that the thiol-containing polymer can be cross-linked via oxidative disulfide bond formation or via thiol-ene or thiol-alkyne "click" reactions ( Figure 3C). Crosslinking increases the molecular weight, thereby increasing the glass transition temperature Tg of the crosslinked thiol-containing polymer. This increase in glass transition temperature helps limit the acid diffusion length, which leads to improved pattern resolution and reduced line width roughness (LWR).

[0103] In some embodiments, the thiol-containing polymer has the following structure (I):

[0104]

[0105] in:

[0106] L1, L2 and L3 are independently, at each occurrence, a direct bond or an oxy (—O—), carbonyl (—C(═O)—), carbonyloxy (—C(═O)—O—), oxycarbonyl (—OC(═O)—), carbonate (—OC(═O)—O—), C1-C20 alkylene, C1-C20 heteroalkylene, C4-C20 cycloalkylene, C4-C20 heterocycloalkylene, C5-C20 arylene or C5-C20 heteroarylene linker;

[0107] R1 is independently a C5-C20 aryl group at each occurrence, wherein the aryl group is unsubstituted or substituted by halogen, carbonyl group, hydroxyl group or R s1 replace;

[0108] R2 is independently an acid-labile group at each occurrence, wherein the acid-labile group is unsubstituted or replaced by R s1 replace;

[0109] R3 is independently C1-C20 alkyl, C1-C20 heteroalkyl, C4-C20 cycloalkyl, C2-C30 heterocycloalkyl, C5-C20 aryl, C5-C20 heteroaryl or R s1 Group;

[0110] R s1 is SH, a C1-C20 sulfanyl group, a C3-C20 sulfadyl group, a C1-C20 thiolalkyl group, a C2-C20 sulfadyloxy group, a C3-C20 sulfadyloxyalkyl group, a C1-C20 thioacetyl group, a C2-C20 thioacetylalkyl group, a thiocarboxyl group, a C2-C20 sulfanylcarboxyl group, a C4-C20 sulfadylcarboxyl group, a C3-C20 sulfadylcarbocycle group or a C3-C20 heterosulfur ring group;

[0111] R a , R b and R c is independently at each occurrence H or a C1-C3 alkyl group; and

[0112] 0<x≤1, 0<y≤1, and 0≤z≤1, provided that one or more of R1, R2 and R3 contains R s1 , such that the compound of structure (I) comprises at least one R s1 .

[0113] In some embodiments, L1, L2, and L3 are all direct bonds.

[0114] In some embodiments, L1 is a direct bond, L2 is a phenylene group, and L3 is a carbonyloxy group (—COO—).

[0115] In some embodiments, L1 and L3 are both carbonyl oxygen (-COO-), and L2 is a direct bond.

[0116] R1 is a sensitizer group suitable for absorbing actinic radiation. In some embodiments, R1 is independently unsubstituted at each occurrence or is replaced by R s1 Substituted hydroxyphenyl, unsubstituted or R s1 Substituted hydroxynaphthyl, unsubstituted or R s1 Substituted hydroxyanthracenyl, unsubstituted or R s1 Substituted phenyl, unsubstituted or R s1 substituted naphthyl, or unsubstituted or R s1 Substituted anthracenyl groups.

[0117] In some embodiments, R1 is unsubstituted or replaced by R s1 Substituted hydroxyphenyl.

[0118] In some embodiments, R1 is unsubstituted or replaced by R s1 Substituted phenyl.

[0119] Acid labile groups (ALGs) are groups that decompose and are cleaved from the thiol-containing polymer by reaction with an acid. s1 Substituted C4-C12 alkyl, unsubstituted or replaced by R s1 Substituted C4-C12 cycloalkyl, unsubstituted or replaced by R s1 Substituted C4-C12 hydroxyalkyl, unsubstituted or R s1 Substituted C4-C12 alkoxy, unsubstituted or R s1 Substituted C4-C12 alkoxyalkyl groups, or unsubstituted or replaced by R s1 Substituted three-dimensional (3D) ring structure.

[0120] In some embodiments, R2 is a tertiary alkyl group, such as a tert-butyl or tert-pentyl group, wherein the tert-butyl or tert-pentyl group is unsubstituted or replaced by Rs1 replaced.

[0121] In some embodiments, R2 is a cycloalkyl group, such as a cyclopentyl, cyclohexylmethyl or cyclohexylethyl group, wherein the cyclopentyl, cyclohexylmethyl or cyclohexylethyl group is unsubstituted or replaced by R s1 replaced.

[0122] In some embodiments, the 3D ring structure is an adamantyl, cedryl, norbornyl, or tricyclodecyl structure, wherein the adamantyl, cedryl, norbornyl, or tricyclodecyl structure is unsubstituted or replaced by R s1 replaced.

[0123] In some embodiments, R2 has one of the following structures:

[0124]

[0125] In some embodiments, R3 is a lactone group in an amount suitable to help reduce line edge roughness.

[0126] In some embodiments, R3 is a C1-C12 alkyl or C4-C12 cycloalkyl group.

[0127] In some embodiments, R3 is methyl.

[0128] In some embodiments, R3 is R s1 .

[0129] In some embodiments, R s1 It's SH.

[0130] In some embodiments, R a , R b and R c At least one of is H. In some embodiments, R a , R b and R c Each of them is H.

[0131] In some embodiments, R a , R b and R c In some embodiments, at least one of R a , R b and R c All are methyl.

[0132] In some embodiments, 0.1≤x / (x+y+z)≤0.5, 0.2≤y / (x+y+z)≤0.7, and 0.05≤z / (x+y+z)≤0.5.

[0133] In some embodiments, the weight average molecular weight of the polymer of structure (I) ranges from 0.5 kDa to 1,000 kDa. In some embodiments, the weight average molecular weight of the polymer ranges from 2 kDa to 250 kDa.

[0134] In some more specific embodiments, L1, L2 and L3 are independently direct bonds, and R1 is R s1 substituted hydroxyphenyl group, and R3 is methyl. In some related embodiments, the thiol-containing polymer of structure (I) has the following structure (Ia):

[0135]

[0136] in:

[0137] R2, at each occurrence, is independently C4-C12 alkyl, C4-C12 cycloalkyl, C4-C12 hydroxyalkyl, C4-C12 alkoxy, C4-C12 alkoxyalkyl, or a three-dimensional (3D) ring structure.

[0138] In some more specific embodiments, R s1 is SH, and the thiol-containing polymer of structure (Ia) has the following structure (Ia-1):

[0139]

[0140] In some more specific embodiments, L1, L2 and L3 are independently direct bonds, R1 is hydroxyphenyl, R2 is R s1 substituted acid-labile groups, and R3 is methyl. In some related embodiments, the thiol-containing polymer of structure (I) has the following structure (Ib):

[0141]

[0142] in:

[0143] R2, at each occurrence, is independently C4-C12 alkyl, C4-C12 cycloalkyl, C4-C12 hydroxyalkyl, C4-C12 alkoxy, C4-C12 alkoxyalkyl, or a three-dimensional (3D) ring structure.

[0144] In some more specific embodiments, R s1 is SH, and the thiol-containing polymer of structure (Ib) has the following structure (Ib-1):

[0145]

[0146] In some more specific embodiments, L1, L2 and L3 are independently direct bonds, R1 is hydroxyphenyl, and R3 is Rs1 In some related embodiments, the thiol-containing polymer has the following structure (Ic):

[0147]

[0148] in:

[0149] R2, at each occurrence, is independently C4-C12 alkyl, C4-C12 cycloalkyl, C4-C12 hydroxyalkyl, C4-C12 alkoxy, C4-C12 alkoxyalkyl, or a three-dimensional (3D) ring structure.

[0150] In some more specific embodiments, R s1 is SH, and the thiol-containing polymer of structure (Ic) has the following structure (Ic-1):

[0151]

[0152] In some more specific embodiments, L1, L2 and L3 are independently direct bonds, and R1 is R s1 In some related embodiments, the thiol-containing polymer of structure (I) has the following structure (Id):

[0153]

[0154] in:

[0155] R2, at each occurrence, is independently C4-C12 alkyl, C4-C12 cycloalkyl, C4-C12 hydroxyalkyl, C4-C12 alkoxy, C4-C12 alkoxyalkyl, or a three-dimensional (3D) ring structure.

[0156] In some more specific embodiments, R s1 is SH, and the thiol-containing polymer of structure (Id) has the following structure (Id-1):

[0157]

[0158] In some embodiments, the thiol-containing polymer has the following structure (II):

[0159]

[0160] in:

[0161] L1, L2, L3 and L4 are independently, at each occurrence, a direct bond or an oxy (—O—), carbonyl (—C(═O)—), carbonyloxy (—C(═O)—O—), oxycarbonyl (—OC(═O)—), carbonate (—OC(═O)—O—), C1-C20 alkylene, C1-C20 heteroalkylene, C4-C20 cycloalkylene, C4-C20 heterocycloalkylene, C5-C20 arylene or C5-C20 heteroarylene linker;

[0162] R1 is independently a C5-C20 aryl group at each occurrence, wherein the aryl group is unsubstituted or substituted by halogen, carbonyl group, hydroxyl group or R s1 replace;

[0163] R2, at each occurrence, is independently a divalent acid-labile group;

[0164] R3 is independently C1-C20 alkyl, C1-C20 heteroalkyl, C4-C20 cycloalkyl, C2-C30 heterocycloalkyl, C5-C20 aryl, C5-C20 heteroaryl or R s1 Group;

[0165] R4, at each occurrence, is independently a free radical active functional group;

[0166] R s1 is SH, a C1-C20 sulfanyl group, a C3-C20 sulfadyl group, a C1-C20 thiolalkyl group, a C2-C20 sulfadyloxy group, a C3-C20 sulfadyloxyalkyl group, a C1-C20 thioacetyl group, a C2-C20 thioacetylalkyl group, a thiocarboxyl group, a C2-C20 sulfanylcarboxyl group, a C4-C20 sulfadylcarboxyl group, a C3-C20 sulfadylcarbocycle group or a C3-C30 heterosulfur ring group;

[0167] R a , R b and R c is independently at each occurrence H or a C1-C3 alkyl group; and

[0168] 0<x≤1, 0<y≤1, and 0≤z≤1, provided that R1, R3, or both contain R s1 , such that the compound of structure (II) comprises at least one R s1 .

[0169] In some embodiments, L1, L2, L3, and L4 are all direct bonds.

[0170] In some embodiments, L1, L2, and L3 are all direct bonds, and L4 is an oxy group (—O—), a carbonyl group (—CO—), a carbonyloxy group (—COO—), or a methylene group (—CH2—).

[0171] In some embodiments, L1 and L4 are both direct bonds, L2 is phenylene, L 3 It is carbonyl oxygen (-COO-).

[0172] In some embodiments, L1, L3, and L4 are all carbonyl oxygen (—COO—), and L2 is a direct bond.

[0173] R1 is a sensitizer group suitable for absorbing actinic radiation. In some embodiments, R1 is independently unsubstituted at each occurrence or is replaced by R s1 Substituted hydroxyphenyl, unsubstituted or R s1 Substituted hydroxynaphthyl, unsubstituted or R s1 Substituted hydroxyanthracenyl, unsubstituted or R s1 Substituted phenyl, unsubstituted or R s1 substituted naphthyl, or unsubstituted or R s1 Substituted anthracenyl groups.

[0174] In some embodiments, R1 is unsubstituted or replaced by R s1 Substituted hydroxyphenyl.

[0175] Acid labile groups (ALGs) are groups that decompose and are cleaved from the thiol-containing polymer by reaction with an acid. s1 Substituted divalent C4-C12 alkyl, unsubstituted or R s1 Substituted divalent C4-C12 cycloalkyl, unsubstituted or R s1 Substituted divalent C4-C12 hydroxyalkyl, unsubstituted or R s1 Substituted divalent C4-C12 alkoxy, or unsubstituted or R s1 A substituted divalent C4-C12 alkoxyalkyl group, or an unsubstituted or R s1 Substituted divalent three-dimensional (3D) ring structure.

[0176] In some embodiments, R2 is a divalent tertiary alkyl group, such as a divalent tert-butyl or divalent tert-pentyl group, wherein the divalent tert-butyl or divalent tert-pentyl group is unsubstituted or replaced by R s1 replaced.

[0177] In some embodiments, R2 is a divalent cycloalkyl group, such as a divalent cyclopentyl, divalent cyclohexylmethyl or divalent cyclohexylethyl group, wherein the divalent cyclopentyl, divalent cyclohexylmethyl or divalent cyclohexylethyl group is unsubstituted or replaced by R s1 replaced.

[0178] In some embodiments, the 3D ring structure is a divalent adamantyl, divalent cedryl, divalent norbornyl, or divalent tricyclodecyl structure, wherein the divalent adamantyl, divalent cedryl, divalent norbornyl, or divalent tricyclodecyl structure is unsubstituted or replaced by R s1 replaced.

[0179] In some embodiments, R2 has a divalent moiety having one of the following structures ( refers to the linking bonds to the polymer backbone):

[0180]

[0181] In some embodiments, R3 is a lactone group in an amount suitable to help reduce line edge roughness.

[0182] In some embodiments, R3 is a C1-C12 alkyl or C4-C12 cycloalkyl group.

[0183] In some embodiments, R3 is methyl.

[0184] In some embodiments, R3 is R s1 .

[0185] A free radically active functional group is a group that is activated by free radicals and undergoes a thiol-ene / yne reaction with a thiol group. In some embodiments, R4 is an alkene or alkyne group.

[0186] In some embodiments, R s1 It's SH.

[0187] In some embodiments, R a , R b and R c At least one of is H. In some embodiments, R a , R b and R c Each of them is H.

[0188] In some embodiments, R a , R b and R c In some embodiments, at least one of R a , R b and R c All are methyl.

[0189] In some embodiments, 0.1≤x / (x+y+z)≤0.5, 0.2≤y / (x+y+z)≤0.7, and 0.05≤z / (x+y+z)≤0.5.

[0190] In some embodiments, the weight average molecular weight of the polymer of structure (II) ranges from 0.5 kDa to 1,000 kDa. In some embodiments, the weight average molecular weight of the polymer ranges from 2 kDa to 250 kDa.

[0191] In some more specific embodiments, L1, L2 and L3 are independently direct bonds, and R1 is R s1 substituted hydroxyphenyl group, R3 is methyl and R4 is olefinic. In some related embodiments, the thiol-containing polymer of structure (II) has the following structure (IIa):

[0192]

[0193] in:

[0194] R2 is independently, at each occurrence, a divalent C4-C12 alkyl group, a divalent C4-C12 cycloalkyl group, a divalent C4-C12 hydroxyalkyl group, a divalent C4-C12 alkoxy group, a divalent C4-C12 alkoxyalkyl group, or a divalent three-dimensional (3D) ring structure.

[0195] In some more specific embodiments, R s1 is SH, and the thiol-containing polymer of structure (IIa) has the following structure (IIa-1):

[0196]

[0197] In some more specific embodiments, L1, L2 and L3 are independently direct bonds, R1 is hydroxyphenyl, and R3 is R s1 In some related embodiments, the thiol-containing polymer of structure (II) has the following structure (IIb):

[0198]

[0199] in:

[0200] R2 is independently, at each occurrence, a divalent C4-C12 alkyl group, a divalent C4-C12 cycloalkyl group, a divalent C4-C12 hydroxyalkyl group, a divalent C4-C12 alkoxy group, a divalent C4-C12 alkoxyalkyl group, or a divalent three-dimensional (3D) ring structure.

[0201] In some more specific embodiments, R s1 is SH, and the thiol-containing polymer of structure (IIb) has the following structure (IIb-1):

[0202]

[0203]

[0204] In some more specific embodiments, L1, L2 and L3 are independently direct bonds, and R1 is R s1 In some related embodiments, the thiol-containing polymer of structure (II) has the following structure (IIc):

[0205]

[0206] in:

[0207] R2, at each occurrence, is independently C4-C12 alkyl, C4-C12 cycloalkyl, C4-C12 hydroxyalkyl, C4-C12 alkoxy, C4-C12 alkoxyalkyl, or a three-dimensional (3D) ring structure.

[0208] In some more specific embodiments, R s1 is SH, and the thiol-containing polymer of structure (IIc) has the following structure (IIc-1):

[0209]

[0210] In some embodiments, the thiol-containing polymer of structure (I) is a compound selected from Table 1.

[0211] Table 1. Exemplary sulfur-containing polymers of structure (I) or (II)

[0212]

[0213]

[0214] In some embodiments, an oxidant and an acid catalyst may be added to the photoresist composition. The oxidant and the acid catalyst cause oxidation of the thiol groups in the polymer of structure (I) or (II), thereby forming disulfide bridges between polymer chains to crosslink the polymers ( Figure 3A and Figure 3C ). Oxidative disulfide bond formation increases the glass transition temperature Tg of the resulting cross-linked polymer, which helps to improve pattern resolution and LWR. Suitable oxidants that can be used include, but are not limited to, oxygen, H2O2, LiBrO3, NaBrO3, KBrO3, O3, I2, or a combination thereof. An acid catalyst with a pKa greater than 1 is selected. If the acidity of the acid catalyst is too strong, the acid-labile group R2 in the polymer may decompose, which can cause malfunction of the photoresist. Suitable acid catalysts that can be used include, but are not limited to, acetic acid (CH3COOH), hydrochloric acid (HCl), carbonic acid (H2CO3), or a combination thereof.

[0215] Alternatively, as an alternative or in addition to adding an oxidant and an acid catalyst to the photoresist composition, a crosslinking agent is added in some embodiments. The crosslinking agent contains a crosslinking group ( Figure 3B ). This bonding increases the glass transition temperature Tg of the resulting cross-linked polymer, which helps to improve pattern resolution and LWR. In some embodiments, the cross-linking agent comprises two to six cross-linking groups, including, for example, epoxy, hydroxyl, melamine, olefin, alkyne, or vinyl ether groups.

[0216] Figure 4 Examples of crosslinking agents that can be used in the present invention are shown in FIG. The crosslinking agent may include two or more crosslinking groups that provide crosslinking sites. In some embodiments, Figure 4 As shown, the crosslinking agent comprises a core group C and two or more crosslinking groups covalently bonded to the core group C via a linker B. The linker length is controlled so that the B linker can rotate to achieve a high crosslinking reaction efficiency in the exposure area. The high crosslinking efficiency between the thiol groups in the thiol-containing polymer (I) and the crosslinking agent allows photolithography patterning using a lower EUV exposure dose.

[0217] In some embodiments, the core group C may include a divalent or multivalent C1-C20 alkyl group, a divalent or multivalent C3-C20 cycloalkyl group, a divalent or multivalent C2-C20 heteroalkyl group, a divalent or multivalent C3-C20 cycloheteroalkyl group, a divalent or multivalent C5-C20 aryl group, or a divalent or multivalent C3-C20 heteroaryl group. The linker B that couples the core group C to the crosslinking group may include a C2-C20 alkylene group, a C3-C20 cycloalkylene group, a C2-C20 heteroalkylene group, a C2-C20 hydroxyalkylene group, a C2-C20 acetylene group, a C2-C20 acetylene alkyl group, a C2-C20 alkylene carboxyl group, a C4-C20 cycloalkylene carboxyl group, a C3-C20 saturated or unsaturated hydrocarbon ring, or a C2-C20 heteroalkylene group. In some embodiments, the crosslinking group may include an epoxy group, ORd, O(Rd)2, C=C, or C≡C, wherein Rd is H, a C1-C8 alkyl group, a C3-C8 cycloalkyl group, a C1-C8 hydroxyalkyl group, a C1-C8 alkoxy group, a C2-C8 alkoxyalkyl group, a C1-C8 acetyl group, a C2-C8 acetylalkyl group, a C2-C8 alkylcarboxyl group, a C4-C8 cycloalkylcarboxyl group, a C3-C8 saturated or unsaturated hydrocarbon ring, or a C3-C8 heterocyclyl group.

[0218] In some embodiments, the core group C has one of the following structures:

[0219]

[0220] In some embodiments, linker B is O, alkylene oxide, or polyethylene oxide.

[0221] In some embodiments, the cross-linking agent has one of the following structures:

[0222]

[0223]

[0224] In some embodiments, the concentration of the crosslinking agent in the photoresist composition is about 0.1 wt % to about 50 wt % based on the total weight of the polymer as 100%. In some other embodiments, the concentration of the crosslinking agent in the photoresist composition is about 5 wt % to about 20 wt % based on the total weight of the crosslinking agent and the polymer. Photoresist compositions having less than about 0.1 wt % of the crosslinking agent may experience insufficient crosslinking during photoresist patterning. Photoresist compositions having more than 50 wt % of the crosslinking agent may result in reduced photoresist pattern resolution or increased line width roughness (LWR).

[0225] In cases where cross-linking is achieved by reaction between cross-linking groups attached to the polymer backbone (eg, thiol-thiol or thiol-ene groups), the addition of a cross-linking agent is not necessary.

[0226] In some embodiments, instead of using a thiol-containing polymer, the photoresist composition comprises a polymer containing a crosslinkable olefin or alkyne group and a thiol-containing crosslinker to crosslink the polymer via a "click" reaction (e.g., thiol-ene / yne reaction) upon UV irradiation or heating, such as Figure 5 shown.

[0227] In some embodiments, the thiol-free polymer has the following structure (III):

[0228]

[0229] in:

[0230] L1, L2, L3 and L4 are independently, at each occurrence, a direct bond or an oxy (—O—), carbonyl (—C(═O)—), carbonyloxy (—C(═O)—O—), oxycarbonyl (—OC(═O)—), carbonate (—OC(═O)—O—), C1-C20 alkylene, C1-C20 heteroalkylene, C4-C20 cycloalkylene, C4-C20 heterocycloalkylene, C5-C20 arylene or C5-C20 heteroarylene linker;

[0231] R5 is, independently at each occurrence, a C5-C20 aryl group, wherein said arylene is unsubstituted or substituted with a halogen, a carbonyl group or a hydroxyl group;

[0232] R6 is, independently at each occurrence, a divalent acid-labile group;

[0233] R7 is, independently at each occurrence, a C1-C20 alkyl group, a C1-C20 heteroalkyl group, a C4-C20 cycloalkyl group, a C2-C30 heterocycloalkyl group, a C5-C20 aryl group, or a C5-C20 heteroaryl group;

[0234] R8 is, independently at each occurrence, a free radical active functional group;

[0235] R a 、R b and R c are, independently at each occurrence, H or a C1-C3 alkyl group; and

[0236] 0 < x ≤ 1, 0 < y ≤ 1, and 0 ≤ z ≤ 1.

[0237] In some embodiments, L1, L2, L3, and L4 are all direct bonds.

[0238] In some embodiments, L1, L2, and L3 are all direct bonds, and L4 is an oxy group (-O-), a carbonyl group (-CO-), a carbonyloxy group (-COO-), or a methylene group (-CH2-).

[0239] In some embodiments, L1 and L4 are both direct bonds, L2 is a phenylene group, and L 3 is a carbonyloxy group (-COO-).

[0240] In some embodiments, L1, L3, and L4 are all carbonyloxy groups (-COO-), and L2 is a direct bond.

[0241] R5 is a sensitizer group suitable for absorbing actinic radiation. In some embodiments, R5 is, independently at each occurrence, a hydroxyphenyl group, a hydroxynaphthyl group, a hydroxyanthryl group, a phenyl group, a naphthyl group, or an anthryl group.

[0242] In some embodiments, R5 is a hydroxyphenyl group.

[0243] An acid-labile group (ALG) is a group that decomposes upon reaction with an acid and is cleaved from the thiol-containing polymer. In some embodiments, R6 is, independently at each occurrence, a divalent C4-C12 alkyl group, a divalent C4-C12 cycloalkyl group, a divalent C4-C12 hydroxyalkyl group, a divalent C4-C12 alkoxy group, or a divalent C4-C12 alkoxyalkyl group, or a divalent three-dimensional (3D) ring structure.

[0244] In some embodiments, R6 is a divalent tertiary alkyl group, such as a divalent tert-butyl group or a divalent tert-amyl group.

[0245] In some embodiments, R6 is a divalent cycloalkyl group, such as a divalent cyclopentyl or divalent cyclohexylalkyl group.

[0246] In some embodiments, the 3D ring structure is a divalent adamantyl, divalent cedryl, divalent norbornyl, or divalent tricyclodecanyl structure.

[0247] In some embodiments, R6 has a divalent moiety having one of the following structures ( refers to the linker to the polymer backbone):

[0248]

[0249] In some embodiments, R7 is a lactone group in an amount suitable to help reduce line edge roughness.

[0250] In some embodiments, R7 is C1-C12 alkyl or C4-C12 cycloalkyl.

[0251] In some embodiments, R7 is methyl.

[0252] A free radically active functional group is a group that is activated by free radicals and undergoes a thiol-ene / yne reaction with a thiol group. In some embodiments, R8 is an alkenyl or alkynyl group.

[0253] In some embodiments, R a , R b and R c At least one of is H. In some embodiments, R a , R b and R c Each of them is H.

[0254] In some embodiments, R a , R b and R c In some embodiments, at least one of R a , R b and R c All are methyl.

[0255] In some embodiments, 0.1≤x / (x+y+z)≤0.5, 0.2≤y / (x+y+z)≤0.7, and 0.05≤z / (x+y+z)≤0.5.

[0256] In some embodiments, the weight average molecular weight of the polymer of structure (III) ranges from 0.5 kDa to 1,000 kDa. In some embodiments, the weight average molecular weight of the polymer ranges from 2 kDa to 250 kDa.

[0257] In some more specific embodiments, L1, L2 and L3 are independently direct bonds, R5 is hydroxyphenyl, R7 is methyl, and R8 is alkenyl. In some related embodiments, the polymer of structure (III) has the following structure (IIIa):

[0258]

[0259] Among them, L4, R2, R a , R b and R c Each occurrence of is independently defined above for the polymer of structure (III).

[0260] In some embodiments, the thiol-containing polymer of structure (III) is a compound selected from Table 2.

[0261] Table 2. Exemplary sulfur-free polymers of structure (III)

[0262]

[0263]

[0264] In some embodiments, the thiol-containing cross-linking agent is a polythiol having the following structure (IV):

[0265]

[0266] in:

[0267] R s2 is a C1-C20 alkylene, C1-C20 alkylenecarboxyl, C3-C20 cycloalkylenecarboxyl, C3-C20 saturated or unsaturated carbocyclic or C3-C20 heterocyclic group; and

[0268] n is an integer of 2-6.

[0269] In some embodiments, n is 2, 3, 4, 5, or 6.

[0270] In some embodiments, the thiol-containing cross-linking agent includes 1,2-ethanedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, tetra(ethylene glycol)dithiol, ethane-1,1,2-trithiol, ethane-1,1,2,2-tetrathiol, ethylene glycol bis(3-mercaptopropionate) (EGBMP), dipentaerythritol hexa(3-mercaptopropionate) (DPHMP), trimethylolpropane tris(3-mercaptopropionate) (TMPTMP), tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, and pentaerythritol tetrakis(3-mercaptopropionate) (PETMP).

[0271] In some embodiments, the photoresist composition includes one or more photoactive compounds (PAC).PAC is a photoacid generator (PAG), a photobase generator (PBG), a photodecomposable base (PDB), a free radical generator (also referred to as a photoinitiator), etc.PAC can play an active role or a negative role.In some embodiments in which PAC is a photoacid generator (PAG), PAG includes halogenated triazines, onium salts, diazonium salts, aromatic diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imidosulfonates, oximesulfonates, diazonium disulfones, disulfones, o-nitrobenzylsulfonates, sulfonated esters, halogenated sulfonyloxy diformimides, diazonium disulfones, α-cyano oxygen amine sulfonates, imidosulfonates, ketone diazonium sulfones, sulfonyl diazo esters, 1,2-bis (arylsulfonyl) hydrazines, nitrobenzyl esters and s-triazine derivatives, combinations of these, etc.

[0272] Specific examples of the photoacid generator include α-(trifluoromethylsulfonyloxy)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide (MDT), N-hydroxy-naphthalimide (DDSN), benzoin toluenesulfonate, tert-butylphenyl-α-(p-toluenesulfonyloxy)-acetate and tert-butyl-α-(p-toluenesulfonyloxy)-acetate, triarylsulfonium and diaryliodonium hexafluoroantimonates, hexafluoroarsenates, trifluoromethanesulfonates, iodonium perfluorooctanesulfonates, N-camphorsulfonyloxynaphthalimide, N-pentafluorophenylsulfonyloxynaphthalimide, ionic iodonium sulfonates (e.g., Such as diaryliodonium (alkyl or aryl) sulfonates and bis (di-tert-butylphenyl) iodonium camphenyl sulfonate iodide, etc.), perfluoroalkane sulfonates (e.g. perfluoropentane sulfonate, perfluorooctane sulfonate, perfluoromethane sulfonate), trifluoromethanesulfonic acid aryl (e.g. phenyl or benzyl) esters (e.g. triphenylsulfonium trifluoromethanesulfonate or bis (tert-butylphenyl) iodonium trifluoromethanesulfonate); pyrogallol derivatives (e.g., pyrogallol trimesylate), trifluoromethanesulfonates of hydroxyimides, α, α'-bissulfonyldiazomethane, sulfonates of nitro-substituted benzyl alcohols, naphthoquinone-4-diazide, alkyl disulfones, etc.

[0273] In some embodiments where the PAC comprises a free radical generator, the free radical generator comprises n-phenylglycine; aromatic ketones, including benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, p,p'-bis(dimethylamino)benzophenone, p,p'-bis(diethylamino)benzophenone, benzophenone; anthraquinone, 2-ethylanthraquinone; naphthoquinone; and phenanthrenequinone; benzoins, including benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, methyl benzoin and ethyl benzoin; benzyl derivatives, including dibenzyl, benzyl diphenyl disulfide and benzyl dimethyl ketal; acridine derivatives, including 9-phenylacridine and 1,7-bis(9-acridinyl)heptane; thioxanthones, including 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dithioxanthone, ethyl thioxanthone, 2,4-dimethyl thioxanthone and 2-isopropyl thioxanthone; acetophenones, including 1,1-dichloroacetophenone, p-tert-butyldichloroacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone and 2,2-dichloro-4-phenoxyacetophenone; 2,4,5-triarylimidazole dimers, including 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, imidazole dimer, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-di(p-methoxyphenyl)-5-phenylimidazole dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer and 2-(p-methylmercaptophenyl)-4,5-diphenylimidazole dimer; combinations of these, and the like.

[0274] In some embodiments, the PAC includes a photobase generator (PBG) and a photodecomposable base (PDB). In embodiments where the PAC is a photobase generator (PBG), the PBG includes quaternary ammonium dithiocarbamates, aminoketones, molecules containing oxime-carbamates (e.g., benzophenone oxime hexamethylene dicarbamate, tetraorganoboric acid ammonium salts, and N-(2-nitrobenzyloxycarbonyl) cyclic amines, combinations of these, and the like.

[0275] In some embodiments where the PAC is a photodecomposable base (PDB), the PDB includes triphenylsulfonium hydroxide, triphenylsulfonium antimony hexafluoride, and trifluoromethyltriphenylsulfonium.

[0276] Based on the total weight of the polymer as 100%, the photoresist composition may include about 0.1 wt % to 10 wt % of PAC. In some embodiments, the photoresist composition includes about 1 wt % to about 5 wt % of PAC. Photoresist compositions with less than about 0.01 wt % of PAC may result in low crosslinking reaction rates. Photoresist compositions with more than 10 wt % of PAC may result in reduced photoresist pattern resolution or increased line width roughness (LWR).

[0277] In some embodiments, instead of using a photoinitiator that generates free radicals, the photoresist composition may alternatively or additionally include a thermal initiator that can generate free radicals under heat to initiate a crosslinking reaction. In some embodiments, the thermal initiator includes an organic peroxide. In some embodiments, the thermal initiator includes an azo compound, an inorganic peroxide, an organic peroxide, or any combination thereof. In some embodiments, the thermal initiator is selected from the group consisting of tert-amyl peroxybenzoate, 4,4-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobisisobutyronitrile (AIBN), benzoyl peroxide, 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne, bis(1-(tert-butylperoxy)-2,5-dimethyl-3-hexyne), ... The thermal initiator comprises azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,3,5-trimethylcyclohexane, tert-butylhydroxyperoxide, tert-butyl peracetate, tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butylperoxyisopropyl carbonate, cumene hydroperoxide, cyclohexanone peroxide, diisopropylbenzene peroxide, lauroyl peroxide, 2,4-pentanedione peroxide, peracetic acid, potassium persulfate, derivatives thereof, and combinations thereof. In some embodiments, the thermal initiator comprises azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), or combinations thereof.

[0278] In some embodiments, the photoresist composition comprises 0-10 wt % thermal initiator based on the total weight of the polymer. In some embodiments, the photoresist composition comprises 0.1-5 wt % thermal initiator.

[0279] The photoresist composition may also include many other optional additives. In some embodiments, a quencher is added to the photoresist composition to inhibit the diffusion of the generated acid / base / radicals in the photoresist. The quencher improves the construction of the resist pattern and the stability of the photoresist over time. In some embodiments, the quencher is an amine, such as a second lower aliphatic amine, a lower aliphatic tertiary amine, etc. Specific examples of amines include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tripentylamine, diethanolamine and triethanolamine, alkanolamine, combinations thereof, and the like.

[0280] In some embodiments, an organic acid is used as a quencher. Specific embodiments of organic acids include malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid; oxygen-containing phosphorus acids and their derivatives, such as phosphoric acid and its derivatives (such as its esters), di-n-butyl phosphate, diphenyl phosphate; phosphonic acid and its derivatives, including its esters, such as dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, dibenzyl phosphonate, etc.; and phosphinic acid and its derivatives, including its esters, such as phenylphosphinic acid.

[0281] In some embodiments, stabilizers are added to the photoresist composition, which helps prevent the undesired diffusion of acids generated during exposure of the photoresist. In some embodiments, stabilizers include nitrogen-containing compounds, including aliphatic primary, secondary and tertiary amines; cyclic amines, including piperidine, pyrrolidine, morpholine; aromatic heterocycles, including pyridine, pyrimidine, purine; imines, including diazabicycloundecene, guanidine, imide, amide, and the like. Alternatively, in some embodiments, ammonium salts can also be used for stabilizers, including ammonium salts, primary, secondary, tertiary and quaternary alkyl and aryl ammonium ions, including hydroxides, phenolates, carboxylates, aryl and alkyl sulfonates, sulfonamides, and the like. In some embodiments, other cationic nitrogen-containing compounds are used, including pyridinium salts and salts of other heterocyclic nitrogen-containing compounds with anions, such as alkoxides, including hydroxides, phenolates, carboxylates, aryl and alkyl sulfonates, sulfonamides, and the like.

[0282] Another additive in some embodiments of the photoresist composition is a dissolution inhibitor to help control the dissolution of the photoresist during development. In some embodiments, a bile salt ester can be used as a dissolution inhibitor. In some embodiments, specific examples of dissolution inhibitors include cholic acid, deoxycholic acid, lithocholic acid, deoxycholic acid tert-butyl ester, lithocholic acid tert-butyl ester, and lithocholic acid tert-butyl 3-acetyl ester.

[0283] Another additive in some embodiments of photoresist composition is plasticizer.Plasticizer can be used to reduce the delamination and the rupture between photoresist layer and underlying layer (for example, material layer to be patterned).Plasticizer includes monomer, oligomeric and polymeric plasticizer, for example oligoethylene glycol ether and polyglycol ether, alicyclic ester and non-acid reactive steroidal derivative material.In some embodiments, the specific example of the material for plasticizer includes dioctyl phthalate, behenyl phthalate, triethylene glycol dicaprylate, dimethyl phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerol etc.

[0284] Colorants are another additive included in some embodiments of the photoresist. A colorant observer inspects the photoresist and detects any defects that may need to be corrected before further processing. In some embodiments, the colorant is a triarylmethane dye or a fine particle organic pigment. Specific examples of materials in some embodiments include crystal violet, methyl violet, ethyl violet, oil blue, Victoria Pure Blue BOH, malachite green, diamond green, phthalocyanine pigments, azo pigments, carbon black, titanium oxide, brilliant green dye (CI42020), Victoria Pure Blue FGA (Linebrow), Victoria BO (Linebrow) (CI42595), Victoria Blue BO (CI44045), Rhodamine 6G (CI45160), benzophenone compounds (such as 2,4-dihydroxybenzophenone and 2,2',4,4'-tetrahydroxybenzophenone; salicylic acid compounds, such as phenyl salicylate and 4-tert-butylphenyl salicylate; phenyl acrylate compounds, such as ethyl-2-cyano-3,3-diphenyl acrylate, and T-ethylhexyl-2-cyano-3,3-diphenyl acrylate; benzotriazole compounds, such as 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, and 2-(3-tert-butyl- 2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole; coumarin compounds such as 4-methyl-7-diethylamino-1-benzopyran-2-one; thioxanthone compounds such as diethylthioxanthone; stilbene compounds, naphthalene dicarboxylic acid compounds, azo dyes, phthalocyanine blue, phthalocyanine green, iodine green, Victoria blue, naphthalene black, Photopia methyl violet, bromophenol blue and bromocresol green; laser dyes such as rhodamine G6, coumarin 500, DCM (4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H pyran)), Kiton Red 620, pyrromethene 580, etc. In addition, one or more colorants can be used in combination to provide the desired coloration.

[0285] Adhesion additives may be added to some embodiments of the photoresist composition to promote adhesion between the photoresist layer 220 and the material layer 210. In some embodiments, the adhesion additive includes a silane compound having at least one reactive substituent, such as a carboxyl group, a methacryl group, an isocyanate group, or an epoxy group. Specific examples of adhesion components include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, benzimidazoles and polybenzimidazoles, pyridine derivatives substituted with lower hydroxyalkyl groups, nitrogen heterocyclic compounds, urea, thiourea, organophosphorus compounds, 8-hydroxyquinoline, 4-hydroxypteridine and its derivatives, 1,10-phenanthroline and its derivatives, 2,2'-bipyridine and its derivatives, benzotriazole, organophosphorus compounds, phenylenediamine compounds, 2-amino-1-phenylethanol, N-phenylethanolamine, N-ethyldiethanolamine, N-ethylethanolamine and its derivatives, benzothiazole, and benzothiazole amine salts having a cyclohexyl ring and a morpholine ring, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, combinations thereof, and the like.

[0286] A surface leveling agent may be added to some embodiments of the photoresist composition to help level the top surface of the photoresist layer 220 so that incident light is not adversely altered by the non-level surface. In some embodiments, the surface leveling agent includes fluoroaliphatic esters, hydroxyl-terminated fluorinated polyethers, fluorinated glycol polymers, silicones, acrylic polymer leveling agents, combinations thereof, and the like.

[0287] Various components (such as polymer, PAC and cross-linking agent) and any required additive or reagent are placed in a solvent to help mix and distribute the photoresist composition. In order to help the mixing and distribution of the photoresist composition, a solvent is selected based at least in part on the material selected for polymer and PAC. In some embodiments, the solvent is selected so that polymer and PAC can be uniformly dissolved in the solvent and distributed on the layer to be patterned. In some embodiments, the solvent is selected to be selected from propylene glycol methyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 1-ethoxy-2-propanol (PGEE), γ-butyrolactone (GBL), cyclohexanone (CHN), ethyl lactate (EL), methanol, ethanol, propanol, n-butanol, acetone, dimethylformamide (DMF), isopropyl alcohol (IPA), tetrahydrofuran (THF), methyl isobutyl carbinol (MIBC), n-butyl acetate (nBA) and 2-heptanone (MAK) One or more.

[0288] The amount of the solvent in the photoresist composition may be about 80 wt % to about 99 wt % based on 100% of the total weight of the composition. In some embodiments, the amount of the solvent in the photoresist composition may be about 95 wt % to about 99 wt %.

[0289] Once added, the mixture is then mixed to obtain a uniform composition throughout the photoresist composition to ensure that there are no defects caused by uneven mixing or uneven composition of the photoresist. Once mixed together, the photoresist composition can be stored prior to use or immediately stored.

[0290] Once prepared, the photoresist composition is applied to the layer to be patterned, such as the material layer 210, to form a photoresist layer 220. The application can be done by any suitable method, including spin coating, spray coating, dip coating, scraping, etc. In some embodiments, the application of the photoresist composition is done using a coating track, wherein the photoresist composition is dispensed on a spinning substrate 202. During dispensing, the substrate 202 can be spun at a speed of up to about 4,000 rpm, such as about 500 rpm to about 3,000 rpm or about 1,000 rpm to about 2,500 rpm. In some embodiments, the thickness of the photoresist layer 220 can range from about 10 nm to about 300 nm.

[0291] Reference Figure 1 and Figure 2C According to some embodiments, the method 100 proceeds to operation 106 where a first baking process 230 is performed on the photoresist layer 220 . Figure 2C According to some embodiments, after performing the first baking process 230 on the photoresist layer 220 Figure 2B FIG. 2 is a cross-sectional view of a semiconductor device 200 .

[0292] Since such a first baking process 230 is performed before exposing the photoresist layer 220 to radiation to cure and dry the photoresist layer 220, the first baking process 230 may also be referred to as a pre-exposure baking process. The curing and drying of the photoresist layer 220 removes residual solvent and free volume from the film to make the photoresist layer 220 uniform and dense. In some embodiments, the first baking process 230 is performed at a temperature and time sufficient to cure and dry the photoresist layer 220. In some embodiments, the photoresist layer 220 is heated to a temperature in the range of about 40° C. to about 120° C. for about 10 seconds to about 10 minutes.

[0293] Reference Figure 1 and Figure 2D According to some embodiments, the method 100 proceeds to operation 108 where an exposure process 240 is performed on the photoresist layer 220 . Figure 2D According to some embodiments, after performing the exposure process 240 on the photoresist layer 220 Figure 2C FIG. 2 is a cross-sectional view of a semiconductor device 200 .

[0294] In some embodiments, the exposure process 240 is performed by placing the photoresist-coated substrate in a lithography tool. The lithography tool includes a photomask 250, optics, a light source to provide exposure radiation, and a movable stage for supporting and moving the substrate 202 under the exposure radiation.

[0295] During the exposure process 240, the photoresist layer 220 is exposed to radiation from a light source through a photomask 250. In some embodiments, the photomask 250 is a transmissive mask. In some other embodiments, the photomask 250 is a reflective mask. The photomask 250 has a predefined pattern designed for the IC based on the specifications of the IC to be manufactured. The pattern of the photomask 250 corresponds to the pattern of the materials constituting the various components of the IC device to be manufactured. For example, a portion of the IC design layout includes various IC features (e.g., active areas, gate electrodes, source and drain electrodes, metal lines or vias for interlayer interconnects, and openings for bonding pads) to be formed in the substrate 202 and / or the material layer 210 disposed on the substrate 202.

[0296] In some embodiments, the photomask 250 includes a first region 252 and a second region 254. In the first region 252, radiation is blocked by the photomask 250 and cannot reach the photoresist layer 220, while in the second region 254, radiation is not blocked by the photomask 250 and can pass through the photomask 250 to reach the photoresist layer 220. Therefore, the portion of the photoresist layer 220 below the second region 254 receives radiation and is referred to as an exposed region 220E, while the portion of the photoresist layer 220 below the first region 252 does not receive radiation and is referred to as an unexposed region 220U.

[0297] In some embodiments, the radiation is EUV radiation (e.g., 13.5 nm). Alternatively, in some embodiments, the patterning radiation is DUV radiation (e.g., from a 248 nm KrF excimer laser or a 193 nm ArF excimer laser), X-ray radiation, electron beam radiation, ion beam radiation, or other suitable radiation. In some embodiments, the exposure process 240 is performed in a liquid (immersion lithography) or in a vacuum (e.g., for EUV lithography and electron beam lithography).

[0298] When selectively (or pattern-wise) exposed to actinic radiation, the photoacid generator (PAG) in the exposed regions 220E of the photoresist layer 220 absorbs the radiation, which triggers the PAG to generate acid in the exposed regions 220E. The generated acid cleaves the acid-labile group R2 from the polymer (e.g., the polymer of structure (I), (II) or (III)), thereby forming a carboxyl group in the exposed regions 220E, such as Fig. 6A As shown, the polymer in the non-exposed area 220U (eg, the polymer of structure (I), (II) or (III)) remains intact, as shown in FIG. Figure 6B The formation of carboxyl groups in the exposed regions 220E makes the exposed regions 220E more soluble in an aqueous developer, such as tetramethylammonium hydroxide solution.

[0299] In some embodiments, the photoactive compound includes a photoinitiator that generates free radicals when exposed to actinic radiation (e.g., EUV radiation having a wavelength of 13.5 nm, or UV, or radiation having a wavelength range of about 100 nm to about 1000 nm). The free radicals generated by the exposed photoinitiator cause the free radically active functional groups on one polymer chain to react with the thiol groups on another polymer chain, the free radically active functional groups in the cross-linking agent to react with the thiol groups on two adjacent polymer chains, or the thiol groups in the cross-linking agent to react with the free radically active functional groups on two adjacent polymer chains, thereby cross-linking adjacent polymer chains in the exposed area 220E during a subsequent baking process. This cross-linking reaction increases the molecular weight of the polymer, which makes the exposed area 220E less soluble in the developer. The increased molecular weight also results in an increase in the glass transition temperature Tg, which helps to reduce the acid diffusion rate.

[0300] In some embodiments, the photoactive compound (PAC) in the photoresist composition includes two or more PACs, including a photoacid generator and a free radical generating photoinitiator. Exposure to actinic radiation causes the photoacid generator to generate an acid to cleave the acid-labile group R2 on the polymer and causes the photoinitiator to generate free radicals to crosslink the free radical active functional groups. In some embodiments, the photoresist layer 220 is exposed to two different wavelengths of ultraviolet radiation, the first wavelength is used to activate the photoacid generator and the second wavelength is used to activate the free radical generating photoinitiator.

[0301] In some embodiments, when the photoactive compound (PAC) is a photoacid generator and the photoresist composition contains a thermal initiator for initiating the crosslinking reaction, an additional baking step is required to activate the thermal initiator.

[0302] Reference Figure 1 and Figure 2E According to some embodiments, the method 100 proceeds to operation 110 where a second baking process 260 is performed on the photoresist layer 220 . Figure 2E According to some embodiments, after performing the second baking process 260 Figure 2D FIG. 2 is a cross-sectional view of a semiconductor device 200 .

[0303] Since the second baking process 260 is performed after the exposure process 240 of exposing the photoresist layer 220 to radiation, the second baking process 260 may also be referred to as a post-exposure-baking (PEB) process. The second baking process 260 helps to disperse and react the acid / base / radicals generated during exposure due to radiation irradiation on the PAC. This thermal assistance helps to produce or enhance the chemical difference between the exposure region 220E and the non-exposure region 220U in the photoresist layer 220, thereby resulting in a solubility difference between the exposure region 220E and the non-exposure region. In addition, this thermal assistance is conducive to the cross-linking reaction, and therefore helps to further increase the cross-linking density and molecular weight of the cross-linked polymer in the exposure region 220E or the non-exposure region 220U of the photoresist layer 220. The increased molecular weight results in an increase in the (T g ) is further increased. The high glass transition temperature produced by using thiol crosslinking allows for effective suppression of the acid diffusion length during the photoresist lithography process, which helps to reduce the line width roughness (LWR) of the photoresist pattern.

[0304] In the case where the photoresist composition includes a crosslinking agent and the crosslinking of the polymer is performed via a free radical crosslinking reaction, the second baking process 260 may be performed at a temperature ranging from about 60° C. to about 150° C. If the temperature is higher than 150° C., the acid-labile group R2 in the polymer may decompose, which may cause the photoresist to malfunction.

[0305] In the case where the photoresist composition contains an oxidizing agent and cross-linking of the polymer is performed via oxidative disulfide bond formation, the second baking process 260 may be performed at a temperature ranging from about 50° C. to about 150° C. If the temperature is higher than 150° C., the acid-labile group R2 in the polymer may decompose, which may cause malfunction of the photoresist.

[0306] In the case where the photoresist composition includes a thermal initiator, the second baking process 260 generates free radicals from the thermal initiator by exposing the thermal initiator to heat. The generated free radicals initiate a free radical crosslinking reaction between the crosslinking agent and the thiol or free radical active functional group on the polymer, thereby forming a crosslinked polymer in the non-exposed area 220U. The second baking process 260 can be performed at a temperature ranging from about 50°C to about 150°C. If the temperature is higher than 150°C, the acid-labile group R2 in the polymer may decompose, which may cause the photoresist to malfunction.

[0307] Reference Figure 1 and Figure 2F According to some embodiments, the method 100 proceeds to operation 112 where a developing process 270 is performed on the photoresist layer 220 . Figure 2F According to some embodiments, after the photoresist layer 220 is subjected to the development process 270 Figure 2F FIG. 2 is a cross-sectional view of a semiconductor device 200 .

[0308] The development process 270 includes applying a developer to the photoresist layer 220. In some embodiments, during the development process 270, the developer dissolves the radiation exposed areas 220E of the positive photoresist composition, thereby exposing the surface of the material layer 210 and leaving well-defined non-exposed areas 220U with improved LWR compared to that provided by conventional novolac-based photoresists. In some embodiments, the developer dissolves the radiation non-exposed areas 220U of the negative photoresist composition, thereby exposing the surface of the material layer 210 and leaving well-defined exposed areas 220E with improved LWR compared to that provided by conventional novolac-based photoresists.

[0309] After the development process, a patterned photoresist layer 220P is formed. The patterned photoresist layer 220P includes a non-exposed region 220U (not shown) of the photoresist layer or an exposed region 220E of the photoresist layer 220. Figure 2F As shown in (B).

[0310] In some embodiments, the developer comprises a solvent and an acid or a base. In some embodiments, the concentration of the solvent in the developer is about 60% to about 99% by weight based on the total weight of the developer. The concentration of the acid or base is about 0.001% to about 20% by weight based on the total weight of the developer. In certain embodiments, the concentration of the acid or base in the developer is about 0.01% to about 15% by weight based on the total weight of the developer. In some embodiments, the developer is an aqueous developer, such as a tetramethylammonium hydroxide (TMAH) solution. In some embodiments, the developer comprises an organic solvent. In some embodiments, the developer is 2-heptanone or butyl acetate, such as n-butyl acetate.

[0311] In some embodiments, the developer is applied to the photoresist layer 220 using a spin coating process. In the spin coating process, the developer is applied to the photoresist layer 220 from above by a dispenser while the coated substrate 202 is rotated. In some embodiments, the developer is supplied at a rate between about 5 ml / min and about 800 ml / min while the coated substrate 202 is rotated at a speed between about 100 rpm and about 2000 rpm. In some embodiments, the developer is at a temperature of about 10° C. to about 80° C. In some embodiments, the development operation lasts between about 30 seconds to about 10 minutes.

[0312] Although a spin coating operation is a suitable method for developing the photoresist layer 220 after exposure, it is intended to be illustrative and not intended to limit the embodiments. Instead, any suitable developing operation may be used instead, including an immersion process, an immersion process, and a spray coating method. All such developing operations are included within the scope of the embodiments.

[0313] Reference Figure 1 and Figure 2G According to some embodiments, the method 100 proceeds to operation 114 in which the material layer 210 is etched using the patterned photoresist layer 220P as an etching mask. Figure 2G According to some embodiments, after etching the material layer 210 using the patterned photoresist layer 220P as an etching mask, Figure 2F FIG. 2 is a cross-sectional view of a semiconductor device 200 .

[0314] Use as Figure 2F The patterned photoresist layer 220P shown in (A) is used as an etching mask to pattern the material layer 210, thereby forming Figure 2G The patterned material layer 210P including the groove 210a shown in (A) or using Figure 2F The patterned photoresist layer 220P shown in (B) is used as an etching mask to pattern the material layer 210, thereby forming Figure 2G (B) shows a patterned material layer 210P including a groove 210b.

[0315] An etching process may be performed to transfer the pattern in the patterned photoresist layer 220P to the material layer 210. In some embodiments, the etching process used is anisotropic etching, such as dry etching, but any suitable etching process may be used. In some embodiments, dry etching is reactive ion etching (RIE) or plasma etching. In some embodiments, dry etching is achieved by fluorine-containing gas (e.g., CF4, SF6, CH2F2, CHF3, and / or C2F6), chlorine-containing gas (e.g., Cl2, CHCl3, CCl4, and / or BCl3), bromine-containing gas (e.g., HBr and / or CHBr3), oxygen-containing gas, iodine-containing gas, other suitable gas and / or plasma, or a combination thereof. In some embodiments, oxygen plasma is performed to etch the material layer 210. In some embodiments, anisotropic etching is performed at a temperature of about 250° C. to 450° C. for a duration of about 20 seconds to about 300 seconds.

[0316] If the patterned photoresist layer 220P is not completely consumed in the etching process, the patterned photoresist layer is removed after the patterned material layer 210P is formed, for example, by plasma ashing or wet stripping.

[0317] In the present disclosure, the use of a thiol oxidation reaction or a thiol-based free radical "click" reaction to crosslink a polymer allows for improved crosslinking efficiency compared to conventional phenolic-based crosslinking reactions. The improved crosslinking efficiency is beneficial for increasing the glass transition temperature (Tg) of the crosslinked polymer. g ). Therefore, the photoresist composition of the present disclosure can effectively suppress the acid diffusion length, which leads to improved line width roughness (LWR) and enhanced resolution capable of achieving feature sizes below 22nm. Therefore, the photoresist composition and method according to the present disclosure provide improved semiconductor device feature resolution and density and reduced defects with a more efficient process.

[0318] One aspect of the present specification relates to a photoresist composition. The photoresist composition comprises a photoactive compound and a thiol-containing polymer having the following structure (I):

[0319]

[0320] wherein L1, L2 and L3 are independently a direct bond or an oxy (—O—), a carbonyl (—C(═O)—), a carbonyloxy (—C(═O)—O—), an oxycarbonyl (—OC(═O)—), a carbonate (—OC(═O)—O—), a C1-C20 alkylene, a C1-C20 heteroalkylene, a C4-C20 cycloalkylene, a C4-C20 heterocycloalkylene, a C5-C20 arylene or a C5-C20 heteroarylene linker; and R1 is independently a C5-C20 aryl group at each occurrence, wherein the aryl group is unsubstituted or substituted by halogen, a carbonyl group, a hydroxyl group or R s1 R2 is independently an acid-labile group at each occurrence, wherein the acid-labile group is unsubstituted or replaced by R s1 substituted; R3 is independently C1-C20 alkyl, C1-C20 heteroalkyl, C4-C20 cycloalkyl, C2-C30 heterocycloalkyl, C5-C20 aryl, C5-C20 heteroaryl or R s1 Group; R s1 is SH, a C1-C20 sulfanyl group, a C3-C20 sulfanylcycloalkyl group, a C1-C20 thiolalkyl group, a C2-C20 sulfanyloxy group, a C3-C20 sulfanyloxyalkyl group, a C1-C20 thioacetyl group, a C2-C20 thioacetylalkyl group, a thiocarboxyl group, a C2-C20 sulfanylcarboxyl group, a C4-C20 sulfanylcycloalkylcarboxyl group, a C3-C20 sulfanylcarbocycle group or a C3-C20 heterosulfanyl ring group; Ra , R b and R c is independently H or a C1-C3 alkyl group at each occurrence; and 0<x≤1, 0<y≤1, and 0≤z≤1, provided that one or more of R1, R2 and R3 includes R s1 , such that the compound of structure (I) comprises at least one R s1 .

[0321] Another aspect of the present specification relates to a photoresist composition. The photoresist composition comprises an initiator; a photoacid generator; and a thiol-containing polymer having the following structure (II):

[0322]

[0323] wherein L1, L2, L3 and L4 are independently a direct bond or an oxy (—O—), a carbonyl (—C(═O)—), a carbonyloxy (—C(═O)—O—), an oxycarbonyl (—OC(═O)—), a carbonate (—OC(═O)—O—), a C1-C20 alkylene, a C1-C20 heteroalkylene, a C4-C20 cycloalkylene, a C4-C20 heterocycloalkylene, a C5-C20 arylene or a C5-C20 heteroarylene linker; and R1 is independently a C5-C20 aryl group at each occurrence, wherein the aryl group is unsubstituted or substituted by halogen, a carbonyl group, a hydroxyl group or R s1 R2 is independently a divalent acid-labile group at each occurrence; R3 is independently C1-C20 alkyl, C1-C20 heteroalkyl, C4-C20 cycloalkyl, C2-C30 heterocycloalkyl, C5-C20 aryl, C5-C20 heteroaryl or R s1 R4, at each occurrence, is independently a free radically active functional group comprising an alkenyl or alkynyl group; R s1 is SH, a C1-C20 sulfanyl group, a C3-C20 sulfanylcycloalkyl group, a C1-C20 thiolalkyl group, a C2-C20 sulfanyloxy group, a C3-C20 sulfanyloxyalkyl group, a C1-C20 thioacetyl group, a C2-C20 thioacetylalkyl group, a thiocarboxyl group, a C2-C20 sulfanylcarboxyl group, a C4-C20 sulfanylcycloalkylcarboxyl group, a C3-C20 sulfur carbocycle group or a C3-C30 heterosulfur ring group; R a , R b and R c is independently H or a C1-C3 alkyl group at each occurrence; and 0<x≤1, 0<y≤1, and 0≤z≤1, provided that R1, R3, or both contain R s1 , such that the compound of structure (II) comprises at least one R s1 .

[0324] Another aspect of the present specification relates to a photoresist composition. The photoresist composition comprises an initiator; a photoacid generator; a thiol-containing crosslinker comprising two or more thiol groups; and a thiol-free polymer having the following structure (III):

[0325]

[0326] wherein L1, L2, L3 and L4 are each independently, upon each occurrence, a direct bond or an oxy group (-O-), a carbonyl group (-C(═O)-), a carbonyloxy group (-C(═O)-O-), an oxycarbonyl group (-O-C(═O)-), a carbonate group (-O-C(═O)-O-), a C1-C20 alkylene group, a C1-C20 heteroalkylene group, a C4-C20 cycloalkylene group, a C4-C20 heterocycloalkylene group, a C5-C20 arylene group or a C5-C20 heteroarylene linker; R5 is, upon each occurrence, independently a C5-C20 aryl group, wherein the arylene is unsubstituted or substituted with a halogen, a carbonyl group or a hydroxyl group; R6 is, upon each occurrence, independently a divalent acid-labile group; R7 is, upon each occurrence, independently a C1-C20 alkyl group, a C1-C20 heteroalkyl group, a C4-C20 cycloalkyl group, a C2-C30 heterocycloalkyl group, a C5-C20 aryl group, or a C5-C20 heteroaryl group; R8 is, upon each occurrence, independently a radical-active functional group selected from an alkenyl or alkynyl group; R a 、R b and R c are each independently, upon each occurrence, H or a C1-C3 alkyl group; and 0 < x ≤ 1, 0 < y ≤ 1, and 0 ≤ z ≤ 1.

[0327] This application also includes the following exemplary embodiments:

[0328] Embodiment 1. A photoresist composition, the photoresist composition comprising:

[0329] a photoactive compound; and

[0330] a thiol-containing polymer having the following structure (I):

[0331]

[0332] wherein:

[0333] L1, L2 and L3 are independently, at each occurrence, a direct bond or an oxy (—O—), carbonyl (—C(═O)—), carbonyloxy (—C(═O)—O—), oxycarbonyl (—OC(═O)—), carbonate (—OC(═O)—O—), C1-C20 alkylene, C1-C20 heteroalkylene, C4-C20 cycloalkylene, C4-C20 heterocycloalkylene, C5-C20 arylene or C5-C20 heteroarylene linker;

[0334] R1 is independently a C5-C20 aryl group at each occurrence, wherein the aryl group is unsubstituted or substituted by halogen, carbonyl group, hydroxyl group or R s1 replace;

[0335] R2 is independently an acid-labile group at each occurrence, wherein the acid-labile group is unsubstituted or replaced by R s1 replace;

[0336] R3 is independently C1-C20 alkyl, C1-C20 heteroalkyl, C4-C20 cycloalkyl, C2-C30 heterocycloalkyl, C5-C20 aryl, C5-C20 heteroaryl or R s1 Group;

[0337] R s1 is SH, a C1-C20 sulfanyl group, a C3-C20 sulfadyl group, a C1-C20 thiolalkyl group, a C2-C20 sulfadyloxy group, a C3-C20 sulfadyloxyalkyl group, a C1-C20 thioacetyl group, a C2-C20 thioacetylalkyl group, a thiocarboxyl group, a C2-C20 sulfanylcarboxyl group, a C4-C20 sulfadylcarboxyl group, a C3-C20 sulfadylcarbocycle group or a C3-C20 heterosulfur ring group;

[0338] R a , R b and R c is independently at each occurrence H or a C1-C3 alkyl group; and

[0339] 0<x≤1, 0<y≤1, and 0≤z≤1, provided that one or more of R1, R2 and R3 contains R s1 , such that the compound of structure (I) comprises at least one R s1 .

[0340] Embodiment 2. The photoresist composition of embodiment 1, wherein L1, L2, and L3 are all direct bonds.

[0341] Embodiment 3. The photoresist composition according to embodiment 1, wherein R1 is unsubstituted or replaced by R s1 Substituted hydroxyphenyl, unsubstituted or R s1Substituted hydroxynaphthyl, unsubstituted or R s1 Substituted hydroxyanthracenyl, unsubstituted or R s1 Substituted phenyl, unsubstituted or R s1 Substituted naphthyl or unsubstituted or R s1 Substituted anthracenyl groups.

[0342] Embodiment 4. A photoresist composition according to embodiment 1, wherein R2 is independently unsubstituted at each occurrence or is replaced by R s1 Substituted C4-C12 alkyl, unsubstituted or replaced by R s1 Substituted C4-C12 cycloalkyl, unsubstituted or replaced by R s1 Substituted C4-C12 hydroxyalkyl, unsubstituted or R s1 Substituted C4-C12 alkoxy, unsubstituted or R s1 Substituted C4-C12 alkoxyalkyl groups, or unsubstituted or replaced by R s1 Substituted three-dimensional (3D) ring structure.

[0343] Embodiment 5. The photoresist composition of embodiment 1, wherein the thiol-containing polymer has one of the following structures (Ia), (Ib), (Ic), and (Id):

[0344]

[0345] wherein R2 at each occurrence is independently C4-C12 alkyl, C4-C12 cycloalkyl, C4-C12 hydroxyalkyl, C4-C12 alkoxy, C4-C12 alkoxyalkyl or a three-dimensional (3D) ring structure.

[0346] Embodiment 6. The photoresist composition of embodiment 5, wherein R2 has one of the following structures:

[0347]

[0348] Embodiment 7. The photoresist composition of embodiment 6, wherein the thiol-containing polymer has one of the following structures (Ia-1), (Ib-2), (Ic-1), and (Id-1):

[0349]

[0350]

[0351] Embodiment 8. The photoresist composition according to embodiment 1, further comprising an oxidant, wherein the oxidant comprises oxygen, H2O2, LiBrO3, NaBrO3, KBrO3, O3, I2, or a combination thereof.

[0352] Embodiment 9. The photoresist composition according to embodiment 8, further comprising an acid catalyst, wherein the acid catalyst comprises acetic acid (CH3COOH), hydrochloric acid (HCl), carbonic acid (H2CO3), or a combination thereof.

[0353] Embodiment 10. The photoresist composition of embodiment 1, further comprising a crosslinker, wherein the crosslinker has one of the following structures:

[0354]

[0355]

[0356] Embodiment 11. The photoresist composition of embodiment 1, wherein the photoactive compound comprises a photoacid generator, a photoinitiator, or a combination thereof.

[0357] Embodiment 12. A photoresist composition, comprising:

[0358] Initiator;

[0359] Photoacid generators; and

[0360] A thiol-containing polymer having the following structure (II):

[0361]

[0362] in:

[0363] L1, L2, L3 and L4 are independently, at each occurrence, a direct bond or an oxy (—O—), carbonyl (—C(═O)—), carbonyloxy (—C(═O)—O—), oxycarbonyl (—OC(═O)—), carbonate (—OC(═O)—O—), C1-C20 alkylene, C1-C20 heteroalkylene, C4-C20 cycloalkylene, C4-C20 heterocycloalkylene, C5-C20 arylene or C5-C20 heteroarylene linker;

[0364] R1 is independently a C5-C20 aryl group at each occurrence, wherein the aryl group is unsubstituted or substituted by halogen, carbonyl group, hydroxyl group or R s1 replace;

[0365] R2, at each occurrence, is independently a divalent acid-labile group;

[0366] R3 is independently C1-C20 alkyl, C1-C20 heteroalkyl, C4-C20 cycloalkyl, C2-C30 heterocycloalkyl, C5-C20 aryl, C5-C20 heteroaryl or R s1 Group;

[0367] R4, at each occurrence, is independently a free radically active functional group comprising an alkenyl or alkynyl group;

[0368] R s1 is SH, a C1-C20 sulfanyl group, a C3-C20 sulfadyl group, a C1-C20 thiolalkyl group, a C2-C20 sulfadyloxy group, a C3-C20 sulfadyloxyalkyl group, a C1-C20 thioacetyl group, a C2-C20 thioacetylalkyl group, a thiocarboxyl group, a C2-C20 sulfanylcarboxyl group, a C4-C20 sulfadylcarboxyl group, a C3-C20 sulfadylcarbocycle group or a C3-C30 heterosulfur ring group;

[0369] R a , R b and R c is independently at each occurrence H or a C1-C3 alkyl group; and

[0370] 0<x≤1, 0<y≤1, and 0≤z≤1, provided that R1, R3, or both contain R s1 , such that the compound of structure (I) comprises at least one R s1 .

[0371] Embodiment 13. The photoresist composition of embodiment 12, wherein the initiator comprises a photoinitiator, a thermal initiator, or a combination thereof.

[0372] Embodiment 14. The photoresist composition of embodiment 12, wherein L1, L2, L3, and L4 are all direct bonds.

[0373] Embodiment 15. A photoresist composition according to embodiment 12, wherein R2 is independently unsubstituted at each occurrence or is replaced by R s1 Substituted divalent C4-C12 alkyl, unsubstituted or R s1 Substituted divalent C4-C12 cycloalkyl, unsubstituted or R s1 Substituted divalent C4-C12 hydroxyalkyl, unsubstituted or R s1 Substituted divalent C4-C12 alkoxy, unsubstituted or R s1 A substituted divalent C4-C12 alkoxyalkyl group, or an unsubstituted or R s1 Substituted divalent three-dimensional (3D) ring structure.

[0374] Embodiment 16. The photoresist composition of embodiment 12, wherein the thiol-containing polymer has one of the following structures (IIa), (IIb), and (IIc):

[0375]

[0376] wherein R2 at each occurrence is independently a divalent C4-C12 alkyl group, a divalent C4-C12 cycloalkyl group, a divalent C4-C12 hydroxyalkyl group, a divalent C4-C12 alkoxy group, a divalent C4-C12 alkoxyalkyl group, or a divalent three-dimensional (3D) ring structure.

[0377] Embodiment 17. The photoresist composition of embodiment 16, wherein the thiol-containing polymer has one of the following structures (IIa-1), (IIb-1), and (IIc-1):

[0378]

[0379] Embodiment 18. A photoresist composition, comprising:

[0380] Initiator;

[0381] Photoacid generators;

[0382] a thiol-containing cross-linking agent comprising two or more thiol groups; and

[0383] A thiol-free polymer having the following structure (III):

[0384]

[0385] in:

[0386] L1, L2, L3 and L4 are independently, at each occurrence, a direct bond or an oxy (—O—), carbonyl (—C(═O)—), carbonyloxy (—C(═O)—O—), oxycarbonyl (—OC(═O)—), carbonate (—OC(═O)—O—), C1-C20 alkylene, C1-C20 heteroalkylene, C4-C20 cycloalkylene, C4-C20 heterocycloalkylene, C5-C20 arylene or C5-C20 heteroarylene linker;

[0387] R5 is independently, at each occurrence, a C5-C20 aryl group, wherein the aryl group is unsubstituted or substituted by halogen, a carbonyl group or a hydroxyl group;

[0388] R6, at each occurrence, is independently a divalent acid-labile group;

[0389] R7 is independently, each time it appears, a C1-C20 alkyl group, a C1-C20 heteroalkyl group, a C4-C20 cycloalkyl group, a C2-C30 heterocycloalkyl group, a C5-C20 aryl group, or a C5-C20 heteroaryl group;

[0390] R8 is independently, each time it appears, a free radical reactive functional group selected from alkenyl or alkynyl groups;

[0391] R a 、R b and R c are independently, each time they appear, H or a C1-C3 alkyl group; and

[0392] 0 < x ≤ 1, 0 < y ≤ 1, and 0 ≤ z ≤ 1.

[0393] Embodiment 19. The photoresist composition according to Embodiment 18, wherein the thiol-free polymer has the following structure (IIIa):

[0394]

[0395]

[0396] wherein R6 is a divalent C4-C12 alkyl group, a divalent C4-C12 cycloalkyl group, a divalent C4-C12 hydroxyalkyl group, a divalent C4-C12 alkoxy group or a divalent C4-C12 alkoxyalkyl group, or a divalent three-dimensional (3D) ring structure.

[0397] Embodiment 20. The photoresist composition according to Embodiment 18, wherein the crosslinking agent has the following structure (IV):

[0398] HS-R s2 -SH

[0399] (IV)

[0400] wherein R s2 is a C1-C20 alkylene group, a C1-C20 alkylene carboxyl group, a C3-C20 cycloalkylene carboxyl group, a C3-C20 saturated or unsaturated carbocyclic ring or a C3-C20 heterocyclic group.

[0401] The foregoing summarizes the features of several embodiments so that those skilled in the art can better understand the various aspects of the present disclosure. Those skilled in the art will appreciate that they can easily use the present disclosure as a basis for designing or modifying other methods and structures to implement the same purposes and / or achieve the same advantages as the embodiments described herein. Those skilled in the art will also appreciate that such equivalent constructions do not depart from the spirit and scope of the present disclosure, and that they can make various changes, substitutions, and modifications without departing from the spirit and scope of the present disclosure.

Claims

1. A photoresist composition, comprising: photoactive compounds; and A thiol-containing polymer having the following structure (I): in: L1, L2 and L3 are independently, at each occurrence, a direct bond or an oxy (—O—), carbonyl (—C(═O)—), carbonyloxy (—C(═O)—O—), oxycarbonyl (—OC(═O)—), carbonate (—OC(═O)—O—), C1-C20 alkylene, C1-C20 heteroalkylene, C4-C20 cycloalkylene, C4-C20 heterocycloalkylene, C5-C20 arylene or C5-C20 heteroarylene linker; R1 is independently a C5-C20 aryl group at each occurrence, wherein the aryl group is unsubstituted or substituted by halogen, carbonyl group, hydroxyl group or R s1 replace; R2 is independently an acid-labile group at each occurrence, wherein the acid-labile group is unsubstituted or replaced by R s1 replace; R3 is independently C1-C20 alkyl, C1-C20 heteroalkyl, C4-C20 cycloalkyl, C2-C30 heterocycloalkyl, C5-C20 aryl, C5-C20 heteroaryl or R s1 Group; R s1 is SH, a C1-C20 sulfanyl group, a C3-C20 sulfadyl group, a C1-C20 thiolalkyl group, a C2-C20 sulfadyloxy group, a C3-C20 sulfadyloxyalkyl group, a C1-C20 thioacetyl group, a C2-C20 thioacetylalkyl group, a thiocarboxyl group, a C2-C20 sulfanylcarboxyl group, a C4-C20 sulfadylcarboxyl group, a C3-C20 sulfadylcarbocycle group or a C3-C20 heterosulfur ring group; R a , R b and R c is independently at each occurrence H or a C1-C3 alkyl group; and 0<x≤1, 0<y≤1, and 0≤z≤1, provided that one or more of R1, R2 and R3 contains R s1 , such that the compound of structure (I) comprises at least one R s1 .

2. The photoresist composition according to claim 1, wherein L1, L2 and L3 are all direct bonds.

3. The photoresist composition according to claim 1, wherein R1 is unsubstituted or replaced by R s1 Substituted hydroxyphenyl, unsubstituted or R s1 Substituted hydroxynaphthyl, unsubstituted or R s1 Substituted hydroxyanthracenyl, unsubstituted or R s1 Substituted phenyl, unsubstituted or R s1 Substituted naphthyl or unsubstituted or R s1 Substituted anthracenyl groups.

4. The photoresist composition according to claim 1, wherein R2 is independently unsubstituted at each occurrence or is replaced by R s1 Substituted C4-C12 alkyl, unsubstituted or replaced by R s1 Substituted C4-C12 cycloalkyl, unsubstituted or replaced by R s1 Substituted C4-C12 hydroxyalkyl, unsubstituted or R s1 Substituted C4-C12 alkoxy, unsubstituted or R s1 Substituted C4-C12 alkoxyalkyl groups, or unsubstituted or replaced by R s1 Substituted three-dimensional (3D) ring structure.

5. The photoresist composition according to claim 1, wherein the thiol-containing polymer has one of the following structures (Ia), (Ib), (Ic) and (Id): wherein R2 at each occurrence is independently C4-C12 alkyl, C4-C12 cycloalkyl, C4-C12 hydroxyalkyl, C4-C12 alkoxy, C4-C12 alkoxyalkyl or a three-dimensional (3D) ring structure.

6. The photoresist composition of claim 1, further comprising an oxidant, wherein the oxidant comprises oxygen, H2O2, LiBrO3, NaBrO3, KBrO3, O3, I2, or a combination thereof.

7. The photoresist composition according to claim 6, further comprising an acid catalyst, wherein the acid catalyst comprises acetic acid (CH3COOH), hydrochloric acid (HCl), carbonic acid (H2CO3), or a combination thereof.

8. The photoresist composition according to claim 1, further comprising a crosslinking agent, wherein the crosslinking agent has one of the following structures:

9. A photoresist composition, comprising: Initiator; photoacid generators; and A thiol-containing polymer having the following structure (II): in: L1, L2, L3 and L4 are independently, at each occurrence, a direct bond or an oxy (—O—), carbonyl (—C(═O)—), carbonyloxy (—C(═O)—O—), oxycarbonyl (—OC(═O)—), carbonate (—OC(═O)—O—), C1-C20 alkylene, C1-C20 heteroalkylene, C4-C20 cycloalkylene, C4-C20 heterocycloalkylene, C5-C20 arylene or C5-C20 heteroarylene linker; R1 is independently a C5-C20 aryl group at each occurrence, wherein the aryl group is unsubstituted or substituted by halogen, carbonyl group, hydroxyl group or R s1 replace; R2, at each occurrence, is independently a divalent acid-labile group; R3 is independently C1-C20 alkyl, C1-C20 heteroalkyl, C4-C20 cycloalkyl, C2-C30 heterocycloalkyl, C5-C20 aryl, C5-C20 heteroaryl or R s1 Group; R4, at each occurrence, is independently a free radically active functional group comprising an alkenyl or alkynyl group; R s1 is SH, a C1-C20 sulfanyl group, a C3-C20 sulfadyl group, a C1-C20 thiolalkyl group, a C2-C20 sulfadyloxy group, a C3-C20 sulfadyloxyalkyl group, a C1-C20 thioacetyl group, a C2-C20 thioacetylalkyl group, a thiocarboxyl group, a C2-C20 sulfanylcarboxyl group, a C4-C20 sulfadylcarboxyl group, a C3-C20 sulfadylcarbocycle group or a C3-C30 heterosulfur ring group; R a , R b and R c is independently at each occurrence H or a C1-C3 alkyl group; and 0<x≤1, 0<y≤1, and 0≤z≤1, provided that R1, R3, or both contain R s1 , such that the compound of structure (I) comprises at least one R s1 .

10. A photoresist composition, comprising: Initiator; Photoacid generators; a thiol-containing cross-linking agent comprising two or more thiol groups; and A thiol-free polymer having the following structure (III): in: L1, L2, L3 and L4 are each independently, upon each occurrence, a direct bond or an oxy group (-O-), a carbonyl group (-C(═O)-), a carbonyl oxy group (-C(═O)-O-), an oxycarbonyl group (-O-C(═O)-), a carbonate group (-O-C(═O)-O-), a C1-C20 alkylene group, a C1-C20 heteroalkylene group, a C4-C20 cycloalkylene group, a C4-C20 heterocycloalkylene group, a C5-C20 arylene group or a C5-C20 heteroarylene linker; R5 is, upon each occurrence, independently a C5-C20 aryl group, wherein the aryl group is unsubstituted or substituted by a halogen, a carbonyl group or a hydroxyl group; R6 is, upon each occurrence, independently a divalent acid-labile group; R7 is, upon each occurrence, independently a C1-C20 alkyl group, a C1-C20 heteroalkyl group, a C4-C20 cycloalkyl group, a C2-C30 heterocycloalkyl group, a C5-C20 aryl group, or a C5-C20 heteroaryl group; R8 is, upon each occurrence, independently a free radical reactive functional group selected from an alkenyl or alkynyl group; R a , R b and R c is independently at each occurrence H or a C1-C3 alkyl group; and 0 < x ≤ 1, 0 < y ≤ 1, and 0 ≤ z ≤ 1.

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