Photoresist compositions

Abstract

A method for manufacturing a semiconductor device includes forming a photoresist layer from a photoresist composition above a substrate. The photoresist layer is selectively exposed to photochemical radiation to form a latent pattern, and the latent pattern is developed by adding a developer to the selectively exposed photoresist layer to form a patterned photoresist. The photoresist composition includes photoactive compounds and thiol-containing polymers including aryl and acid-indestabilized groups. The thiol groups can crosslink the polymer through disulfide oxidation and / or thiol ene / yne "click" reactions.

Description

Thiol-containing photoresist compositions for extreme ultraviolet lithography none The semiconductor integrated circuit (IC) industry has experienced exponential growth. Technological advances in IC materials and design have produced successive generations of ICs, each with smaller and more complex circuits than the previous one. Over the course of IC evolution, functional density (the number of interconnected devices per chip area) has generally increased, while geometry size (the smallest component (or circuit) that can be created using a manufacturing process) has decreased. This process of shrinking dimensions generally provides benefits by increasing production efficiency and reducing associated costs. However, this shrinking size also increases the complexity of IC processing and manufacturing. none The following disclosure provides many different embodiments or examples for implementing the different features of the provided subject matter. Specific examples of components and configurations are described below to simplify the present disclosure. Of course, these components and configurations are merely examples and are not intended to be limiting. For example, in the following description, the formation of a first feature above or on a second feature may include an embodiment in which the first and second features are formed in direct contact, and may also include an embodiment in which additional features may be formed between the first and second features so that the first and second features may not be in direct contact. In addition, the present disclosure may repeatedly reference numbers and / or letters in various examples. This repetition is for simplicity and clarity purposes and does not, in itself, indicate the relationship between the various embodiments and / or configurations discussed. Additionally, spatially relative terms such as "below," "beneath," "lower," "above," "upper," "top," and the like may be used herein for ease of description to describe the relationship of one or more elements or features to another element or features as illustrated in the figures. The 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 device may be otherwise oriented (rotated 90 degrees or at other orientations), and the spatially relative descriptors used herein should be interpreted accordingly. "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 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 attached to the remainder of the molecule by a single bond, for example, methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, n-pentyl, 1,1-dimethylethyl (tert-butyl), 3-methylhexyl, 1,2-methylhexyl, or the like. Unless otherwise specifically stated in the specification, an alkyl group may be optionally substituted. As used herein, "alkylene" refers to a straight or branched divalent hydrocarbon chain that connects the rest of the molecule to a free radical group, consisting solely of carbon and hydrogen, containing no unsaturation, and having 1 to 12 carbon atoms, such as methyl, ethyl, propyl, n-butyl, or similar materials. The alkylene chain is connected to the rest of the molecule and to the free radical group through a single bond. Multiple connections between the alkylene chain and the rest of the molecule and to the free radical can be through one carbon or any two carbons in the chain. Unless otherwise specifically stated in the specification, the alkylene group may be optionally substituted. As used herein, "alkene" refers to a linear or branched hydrocarbon chain consisting solely of carbon and hydrogen, containing at least one carbon-carbon double bond, and having 2 to 12 carbon atoms, such as ethylene, propylene, n-butene, or similar materials. Unless otherwise specifically stated in the specification, an alkene may be optionally substituted. As used herein, "alkenylene" refers to a straight or branched divalent hydrocarbon chain connecting the rest of the molecule to a free radical group, which consists solely of carbon and hydrogen, contains at least one double bond, and has 2 to 12 carbon atoms, such as ethenylene, propenylene, n-butenylene, or similar materials as described above. The alkenylene chain is connected to the rest of the molecule through a single bond and to the free radical group through a double bond or a single bond. The multiple connections of the alkenylene chain to the rest of the molecule and to the free radical can be achieved through one carbon or any two carbons in the chain. Unless otherwise specifically stated in the specification, alkenylene can be optionally substituted. As used herein, "alkyne" refers to a straight or branched hydrocarbon chain consisting solely of carbon and hydrogen, containing at least one carbon-carbon triple bond, and having 2 to 12 carbon atoms, such as ethynyl, propynyl, n-butynyl, or similar materials. As used herein, "alknylene" refers to a straight or branched divalent hydrocarbon chain connecting the rest of the molecule to a radical group, consisting solely of carbon and hydrogen, including at least one triple bond, and having 2 to 12 carbon atoms, such as ethynyl, propynyl, n-butynyl, or similar materials. The alknylene chain is connected to the rest of the molecule through a single bond and to the radical group through a triple bond or a single bond. The multiple connections of the alknylene chain to the rest of the molecule and to the radical group can be through one carbon or any two carbons in the chain. Unless otherwise specifically stated in the specification, an alknylene group may be optionally substituted. As used herein, "alkoxy" refers to an O-alkyl group, wherein alkyl is as defined above. Unless otherwise specified in the specification, an alkoxy group may be optionally substituted. As used herein, "alkyl ether" refers to any alkyl group as defined above in which at least one carbon-carbon bond is replaced by a carbon-oxygen bond. The carbon-oxygen bond can be terminal (as in an alkoxy group) or internal (i.e., COC). Alkyl ethers include at least one carbon-oxygen bond, but may include more than one. For example, polyethylene glycol (PEG) is included within the meaning of an alkyl ether. Unless specifically stated otherwise in the specification, an alkyl ether may be optionally substituted. As used herein, "cycloalkyl" refers to a stable, non-aromatic, monocyclic or polycyclic carbocyclic group composed solely of carbon and hydrogen atoms, which may include fused or bridged ring systems, having 3 to 15 carbon atoms, preferably 3 to 10 carbon atoms, 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, decalinyl, 7,7-dimethylbicyclo[2.2.1]heptanyl, or similar materials. "Cycloalkylene" is a divalent or polyvalent cycloalkyl group that typically links a portion of the molecule to a free radical or to two or more free radical groups. Unless otherwise specified in the specification, a cycloalkyl (or cycloalkylene) group may be optionally substituted. As used herein, "heteroalkyl" refers to an alkyl group as defined above that includes 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 includes at least one carbon-[heteroatom] x -carbon bond, where x is 1, 2, or 3). In other embodiments, the heteroatom is at the end of the alkyl group and thus serves to connect the alkyl group to the rest of the molecule (e.g., M1-HA, where M1 is part of the molecule, H is a heteroatom, and A is an alkyl group). Unless otherwise specifically stated in the specification, the heteroalkyl group may be optionally substituted. A plurality of exemplary heteroalkyl groups include ethylene oxide (e.g., polyethylene oxide), optionally including a phosphorus-oxygen bond, such as a phosphodiester bond. As used herein, "heteroalkylene" refers to an alkylene group as defined above that includes at least one heteroatom (e.g., N, O, P, or S) within the alkylene chain or at the terminus of the alkylene chain. In some embodiments, the heteroatom is within the alkylene chain (i.e., the heteroalkylene includes at least one carbon-heteroatom-carbon bond). In other embodiments, the heteroatom is at the terminus of the alkylene group and thus serves to link the alkylene group 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 group). Unless specifically stated otherwise in the specification, a heteroalkylene group may be optionally substituted. As used herein, "heteroalkenyl" refers to a heteroalkylene group as defined above that includes at least one carbon-carbon double bond. Unless otherwise specified in the specification, a heteroalkenyl group may be optionally substituted. As used herein, "heteroalkynyl" refers to a heteroalkylene group containing at least one carbon-carbon triple bond. Unless otherwise specified in the specification, a heteroalkynyl group may be optionally substituted. "Carbocyclic" refers to a stable 3- to 18-membered aromatic or non-aromatic ring comprising 3 to 18 carbon atoms. Unless otherwise specified in the specification, a carbocyclic group can be a monocyclic, bicyclic, tricyclic, or tetracyclic ring system, which can include fused or bridged ring systems and can be partially or fully saturated. Non-aromatic carbocyclic groups include cycloalkyl groups, while aromatic carbocyclic groups include aryl groups. Unless otherwise specified in the specification, a carbocyclic group may be optionally substituted. "Aryl," used alone or in combination with other terms (e.g., aryloxy, arylalkyl), refers to a ring system comprising at least one carbocyclic aromatic ring. In some embodiments, the aryl group comprises from 6 to 18 carbon atoms. The aryl ring can be a monocyclic, bicyclic, tricyclic, or tetracyclic ring system, which can include fused or bridged ring systems. Plural aryl groups include, but are not limited to, aceanthrylene, acenaphthylene, acephenanthrylene, anthracene, azulene, benzene, chrysene, fluoranthene, fluorene, asymmetric dicyclopentadienyl acene, acenaphth ... acenaphthylene, acenaphthylene, anthracene, azulene, benzene, chrysene, fluoranthene, fluorene, asymmetric dicyclopentadienyl acene, acenaphthyl as-indacene), symmetrical dicyclopentadiene acene ( The aryl groups include, but are not limited to, s-indacene, indane, indene, naphthalene, phenalene, phenanthrene, pleiadene, pyrene and triphenylene. Unless stated otherwise specifically in the specification, aryl groups may be optionally substituted. As used herein, "arylene" refers to a bifunctional aromatic moiety containing 1 to 5 aromatic rings. Unless otherwise specified in the specification, an arylene group may be optionally substituted. As used herein, "heterocycle" refers to a stable 3- to 18-membered aromatic or non-aromatic ring comprising 1 to 12 carbon atoms and 1 to 6 heteroatoms selected from nitrogen, oxygen, and sulfur. Unless otherwise specifically stated in the specification, the heterocycle may be a monocyclic, bicyclic, tricyclic, or tetracyclic ring system, which may include a fused or bridged ring system, and the nitrogen, carbon, or sulfur atoms in the heterocycle may be optionally oxidized, the nitrogen atom may be optionally quaternized, and the heterocycle may be partially or fully saturated. Examples of aromatic heterocycles are listed below in the definition of heteroaryl (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, and piperidinyl. 1-oxothiomorpholinyl, 1-oxothiomorpholinyl, and 1,1-dioxothiomorpholinyl. Unless otherwise specifically stated in the specification, the heterocyclic group may be optionally substituted. As used herein, "heteroaryl" refers to a 5- to 14-membered ring system comprising 1 to 13 carbon atoms, 1 to 6 heteroatoms selected from nitrogen, oxygen, and sulfur, and at least one aromatic ring. For the purposes of certain embodiments of the present disclosure, a heteroaryl group can be a monocyclic, bicyclic, tricyclic, or tetracyclic ring system, which can include fused or bridged ring systems, and the nitrogen, carbon, or sulfur atoms in the heteroaryl group can be selectively oxidized, and the nitrogen atoms can be selectively quaternized. Examples include, but are not limited to, azepinyl, acridinyl, benzmidazolyl, benzthiazolyl, benzindolyl, benzodioxolyl, benzofuranyl, benzooxazolyl, benzothiazolyl, benzothiadiazolyl, benzo[ b][1,4] dioxepenyl (benzo[ b][1,4]dioxepinyl), 1,4-benzodioxanyl, benzonaphthofuranyl, benzoxazolyl, benzodioxinyl, benzopyranyl, benzopyranonyl, benzofuranonyl, benzothienyl or benzothiophenyl, benzotriazolyl, benzo[4,6]imidazo[1,2- a]pyridyl(benzo[4,6]imidazo[1,2- a]pyridinyl), benzoxazolinonyl, benzimidazolthionyl, carbazolyl, cinnolinyl, dibenzofuranyl, dibenzothiophenyl, furanyl, furanonyl, isothiazolyl, imidazolyl, indazolyl, indolyl, isoindolyl, indolinyl, isoindole isoindolinyl, isoquinolyl, indolizinyl, isoxazolyl, naphthyridinyl, oxadiazolyl, 2-oxoazepinyl, oxazolyl, oxiranyl, 1-oxidopyridinyl, 1-oxidopyrimidinyl, 1-oxidopyrazinyl, 1-oxidopyridazinyl, 1-phenyl-1- H-pyrrolyl (1-phenyl-1 H-pyrrolyl), phenazinyl, phenothiazinyl, phenoxazinyl, phthalazinyl, pteridinyl, pteridinonyl, purinyl, pyrrolyl, pyrazolyl, pyridinyl, pyridinonyl, pyrazinyl, pyrimidinyl, pryrimidinonyl, pyridazinyl, pyrido[2,3- d]pyrimidinylnonyl (pyrido[2,3- d]pyrimidinonyl), quinazolinyl, quinazolinonyl, quinoxalinyl, quinoxalinonyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, thiazolyl, thiadiazolyl, thieno[3,2- d]pyrimidin-4-one (thieno[3,2- d]pyrimidin-4-onyl), thieno[2,3- d]pyrimidin-4-one (thieno[2,3- d]pyrimidin-4-onyl), triazolyl, tetrazolyl, triazinyl, and thiophenyl (i.e., thienyl). Unless otherwise specifically stated in the specification, a heteroaryl group may be optionally substituted. As used herein, "heteroarylene" refers to a divalent aromatic hydrocarbon containing nitrogen, sulfur, oxygen or phosphorus and having 6 to 20 carbon atoms. As used herein, "halogen" includes fluorine, chlorine, bromine and iodine. As used herein, "halogenated" refers to having one or more halogen atoms bonded to the above group, such as fluorine, chlorine, bromine or iodine atoms. "Fluorinated" means having one or more fluorine atoms incorporated into the group. For example, when a fluoroalkyl group is indicated, the group includes a single fluorine atom, a difluoromethylene group, a trifluoromethyl group, a combination of the foregoing, or a perfluorinated group (e.g., CF 3. C 2F 5. C 3F 7. C 4F 9, etc.). As used herein, the term "substituted" refers to any of the above groups (e.g., alkyl, alkylene, alkenyl, alkynyl, heteroalkylene, heteroalkenyl, heteroalkynyl, alkoxy, heteroalkyl, carbocyclyl, cycloalkyl, aryl, arylene, heterocyclyl, heteroaryl, and / or heteroarylene) wherein 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, e.g., F, Cl, Br, and I, an oxygen atom in a group such as a hydroxyl group, an alkoxy group, and an ester group, a thiol group, a thioalkyl group, a sulfone group, a sulfonyl group, a sulfoxide group, a thioalkylene group, a sulfonyl ... group), a sulfur atom in a group such as an amine, an amide, an alkylamine, a dialkylamine, an arylamine, an alkylarylamine, a diarylamine, an N-oxide, an imide, and an enamine, a silicon atom in a group such as a trialkylsilyl group, a dialkylarylsilyl group, an alkyldiarylsilyl group, and a triarylsilyl group, and other heteroatoms in various other groups. "Substituted" also refers to any of the above groups in which one or more hydrogen atoms are replaced by a higher order bond (e.g., a double bond or a triple bond) to a heteroatom, such as by an oxygen atom in an oxo group, a carbonyl group, a carboxyl group, and an ester group, and by a nitrogen atom in an imine group, an oxime group, a hydrazone group, and a nitrile group. For example, "substituted" includes any of the above groups in which 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 SO 2R h 、-OC(=O)NR g R h 、-OR g 、-SR g 、-SOR g 、-SO 2R g 、-OSO 2R g 、-SO 2OR g 、=NSO 2R g and-SO 2NR g R h Substituted. "Substituted" also refers to any of the above groups in which one or more hydrogen atoms are replaced by -C(=O)R g 、-C(=O)OR g , to C(=O)NR g R h 、-CH 2SO 2R g and -CH 2SO 2NR g R h In the above, R g and R hThe same or different and independently hydrogen, alkyl, alkoxy, alkylamino, thioalkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, haloalkyl, heterocyclyl, N-heterocyclyl ( N-heterocyclyl), heterocyclylalkyl, heteroaryl, N-heteroaryl ( "Substituted" further refers to any of the above groups wherein one or more hydrogen atoms are replaced by amino, cyano, hydroxy, imino, nitro, oxo, thio, halo, alkyl, alkoxy, alkylamino, thioalkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, haloalkyl, heterocyclyl, N-heterocyclyl, heterocyclylalkyl, heteroaryl, In addition, each of the aforementioned substituents may also be optionally substituted with one or more of the above substituents. IC manufacturing uses one or more lithography processes to transfer multiple geometric patterns onto a film or substrate. The geometric shapes and patterns on a semiconductor create complex structures that enable dopants, electrical properties, and wiring to complete circuits and achieve technological goals. In lithography, a photoresist is applied as a thin film to a substrate 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 of the photoresist exposed to light through the photomask are either soluble or insoluble in a specific type of solution, called a developer. If the exposed areas are soluble, a positive image of the photoresist is created 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 created in the photoresist, and this type of photoresist is called a negative photoresist. The developer removes the more soluble areas, leaving behind the patterned photoresist. The photoresist 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 photoresist pattern in the underlying material layer. Alternatively, the ion deposition mask is then used as an etching mask in a subsequent ion deposition process and applied to a material layer below, such as an epitaxial semiconductor layer. The quality of photoresist patterns impacts the quality of the final IC. As the critical dimension (CD) of integrated circuits continues to shrink, the ability of photoresist to accurately replicate mask features becomes increasingly challenging due to image blurring caused by photoacid diffusion during the lithography process. Specifically, photogenerated acids can migrate from exposed to unexposed areas during the lithography process, triggering unwanted reactions. Increasing the glass transition temperature (Tg) of a photoresist polymer generally reduces the acid diffusion length. This is because the diffusion rate of acid in the photoresist polymer decreases when the photoresist polymer is in a glassy state. Therefore, photoresists with higher Tg characteristics are more suitable for suppressing acid diffusion, thereby improving pattern resolution and reducing line width roughness (LWR). Crosslinking has been shown to effectively increase the molecular weight and Tg of multiple photoresist polymers. Phenolic groups are commonly used as crosslinking groups in existing photoresist polymers. However, the weak acidity of phenolic groups (pKa = 9.95) requires an additional baking step to initiate the crosslinking reaction between phenolic groups within a temperature range of 100°C to 150°C. Furthermore, the baking temperature needs to be below the decomposition temperature of the acid labile groups (ALGs) in the photoresist polymer to prevent ALG cleavage during the crosslinking stage. Because higher baking temperatures lead to higher crosslinking efficiency, this control of the baking temperature can limit the efficiency of the crosslinking reaction between phenolic groups. In an embodiment of the present disclosure, a plurality of photoresist compositions including thiol-containing polymers or thiol-containing crosslinkers are provided to improve the crosslinking efficiency of extreme ultraviolet radiation (EUV) lithography. Thiol has a pKa value of 6.62 and exhibits higher acidity compared to phenolic compounds. Thiol is commonly used as a crosslinking group in existing EUV photoresist compositions. At the same baking temperature, the higher acidity of thiol results in a more complete thiol-thiol crosslinking reaction compared to a phenol-phenol crosslinking reaction. The increased crosslinking efficiency leads to an increase in the molecular weight of the crosslinked photoresist polymer, resulting in a higher glass transition temperature. The increase in the glass transition temperature of the crosslinked photoresist polymer effectively limits the diffusion length of the photoacid during the lithography process. In turn, this enables the production of patterned features with higher resolution and lower line width roughness (LWR). Therefore, the quality of the photoresist pattern is improved, which helps to improve the yield and reliability of the IC. FIG1 is a flow chart of a method 100 for manufacturing a semiconductor device 200 according to some embodiments of the present disclosure. FIG2A through FIG2G are cross-sectional views of the semiconductor device 200 at various stages of manufacture according to some embodiments of the present disclosure. The method 100 is described below in conjunction with FIG1 and FIG2A through FIG2G , wherein the semiconductor device 200 is manufactured using embodiments of the method 100. It should be understood that additional steps may be provided before, during, and after the method 100, and that some of the steps described below may be replaced or removed for additional embodiments of the method. It should further be understood that additional features may be added to the semiconductor device 200, and that some of the features described below may be replaced or removed for additional embodiments of the semiconductor device 200. Semiconductor device 200 may be an intermediate structure during the manufacturing process of an integrated circuit (IC) or a portion thereof. An IC may include a plurality of logic circuits, a plurality of memory structures, a plurality of passive components (e.g., resistors, capacitors, and inductors), and a plurality of active components, such as 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. Semiconductor device 200 may include a plurality of interconnected semiconductor devices (e.g., transistors). 1 and 2A, according to some embodiments, method 100 includes operation 102, wherein a material layer 210 is deposited on substrate 202. FIG2A is a cross-sectional view of semiconductor device 200 after depositing material layer 210 on substrate 202, according to some embodiments. 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 may consist entirely of silicon. In some embodiments, substrate 202 may include one or more epitaxial layers formed on a top surface of a bulk semiconductor substrate. In some embodiments, one or more epitaxial layers in substrate 202 introduce strain to enhance performance. For example, the epitaxial layers may include a semiconductor material different from that of the bulk semiconductor substrate, such as a silicon germanium layer overlying bulk silicon or a silicon layer overlying bulk silicon germanium. In some embodiments, the epitaxial layers in bonded substrate 202 are formed by selective epitaxial growth, such as metal organic 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. 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 insulating layer. In some embodiments, the insulating layer is a buried oxide (BOX) layer including silicon oxide or silicon germanium oxide. The insulating layer is disposed on a handle substrate, such as a silicon substrate. In some embodiments, the SOI substrate is formed using separation by implanted oxygen (SIMOX) or other suitable techniques, such as wafer bonding and grinding. In some embodiments, substrate 202 may further include a dielectric substrate, such as silicon oxide, silicon nitride, silicon oxynitride, a low-k dielectric, silicon carbide, and / or other suitable layers. In some embodiments, 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 channels with various doping profiles, and are configured to form various IC devices, such as complementary metal-oxide-semiconductor (COMOS) transistors, image sensors, and / or light-emitting diodes (LEDs). Substrate 202 may also include other functional features, such as resistors and / or capacitors formed in and / or on substrate 202. In some embodiments, substrate 202 may also include various isolation features. Isolation features separate various device regions in substrate 202. Isolation features include different structures formed using different processing techniques. For example, isolation features may include shallow trench isolation (STI) features. The formation of STI may include etching trenches in substrate 202 and filling the trenches with insulating materials such as silicon oxide, silicon nitride, and / or silicon oxynitride. The filled trenches may have a multi-layer structure, such as a thermal oxide liner layer with silicon nitride filling the trenches. Chemical mechanical polishing (CMP) may then be performed to polish away excess insulating material and planarize the top surface of the isolation features. In some embodiments, the substrate 202 may also include a gate stack formed of a plurality of dielectric layers and a plurality of electrode layers. The dielectric layer may include an interface 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 interface layer may include silicon dioxide, and the high-k dielectric layer may include LaO, AlO, ZrO, TiO, Ta, or a combination thereof. 2O 5. Y 2O 3. SrTiO 3. BaTiO 3. BaZrO, HfZrO, HfLaO, HfSiO, LaSiO, AlSiO, HfTaO, HfTiO, (Ba,Sr)TiO 3(BST), Al 2O 3. Si 3N 4. SiON and / or other suitable materials. The electrode layer may include a single layer or, alternatively, a multilayer structure, such as various combinations of a metal layer having a work function to enhance device performance (work function metal layer), a liner layer, a wetting layer, an adhesion layer, and a conductive layer of a metal, metal alloy, or 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. In some embodiments, the substrate 202 may also include multiple inter-level dielectric (ILD) layers and conductive features that are integrated to form interconnect structures that are configured to couple various p-type and n-type doped regions and other functional features (e.g., gate electrodes) to create a functional integrated circuit. In one example, the substrate 202 may include a portion of an 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). Metal lines provide horizontal electrical wiring. Contacts provide vertical connections between the silicon substrate and the metal lines, while through-hole features provide vertical connections between metal lines in different metal layers. A material layer 210 is disposed on substrate 202. Material layer 210 is a layer processed by method 100, such as a patterned or implanted layer. In some embodiments, material layer 210 is a patterned hard mask layer. In some embodiments, material layer 210 comprises a dielectric material, such as silicon oxide, silicon nitride, or silicon oxynitride. In some other embodiments, material layer 210 comprises a metal oxide such as titanium oxide or a metal nitride such as titanium nitride. In some embodiments, material layer 210 also serves as an anti-reflection coating (ARC), the composition of which can be selected to minimize reflectivity of radiation applied to photoresist layer 220 during exposure. For example, in some embodiments, 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. 1 and 2B , according to some embodiments, method 100 proceeds to operation 104, where a photoresist composition is coated on material layer 210 to form photoresist layer 220. FIG. 2B is a cross-sectional view of semiconductor device 200 after photoresist layer 220 is formed on material layer 210, according to some embodiments. 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. In some embodiments, the photoresist composition includes a thiol-containing polymer. 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 acrylic esters, methacrylic esters, crotonic esters, vinyl esters, maleic diesters, fumaric diesters, itaconic diesters, (meth)acrylonitrile, (meth)acrylamide, styrene, hydroxystyrene, vinyl ether, novolac, combinations thereof, or similar materials. In some embodiments, the thiol-containing polymer has a thiol group attached to the polymer backbone, and the thiol group is a C6 to C20 thiol-benzyl group, a C1 to C20 thiol-alkyl group, a C3 to C20 thiol-cycloalkyl group, a C1 to C20 thiol-hydroxyalkyl group, a C2 to C20 thiol-alkoxy group, a C3 to C20 thiol-alkoxyalkyl group, a C1 to C20 thiol-acetyl group, a C2 to C20 thiol-acetylalkyl group, a C1 to C20 thiol-carboxyl group, a C2 to C20 thiol-alkylcarboxyl group, a C4 to C20 thiol-cycloalkylcarboxyl group, a C3 to C20 saturated or unsaturated thiol-hydrocarbon ring, or a C3 to C20 thiol-heterocyclic group. In some embodiments, the thiol group is substituted with one, two, three, or more thiol atoms. The thiol groups in the thiol-containing polymer can be crosslinked by any suitable method. In some embodiments, the thiol-containing polymer can be crosslinked by acid-catalyzed oxidation of the thiol groups in the presence of an oxidizing agent to form interchain disulfide bonds between polymer chains ( FIG. 3A ). In some embodiments, the thiol-containing polymer can be crosslinked using a crosslinking agent that includes a crosslinking group that reacts with the thiol groups to form multiple bridges between polymer chains via a light- or heat-triggered "click" reaction, such as a thiol-ene or thiol-yne reaction ( FIG. 3B ). In some embodiments, the thiol-containing polymer also includes free radically reactive functional groups, such as alkene or alkynyl groups, allowing the thiol-containing polymer to be crosslinked via oxidative disulfide formation or via a thiol-ene or thiol-yne "click" reaction ( FIG. 3C ). Crosslinking increases molecular weight, thereby increasing the glass transition temperature (Tg) of the crosslinked thiol-containing polymer. This increase in glass transition temperature helps limit acid diffusion length, resulting in improved pattern resolution and reduced line width roughness (LWR). In some embodiments, the thiol-containing polymer has the following structure (I): (I) Where: L 1. L 2 and L 3 is independently at each occurrence a direct bond or a plurality of linking chains, which are oxy (—O—), carbonyl (—C(═O)—), carbonyloxy (—C(═O)—O—), oxycarbonyl (—O—C(═O)—), carbonate (—O—C(═O)—O—), C1 to C20 alkylene, C1 to C20 heteroalkylene, C4 to C20 cycloalkylene, C4 to C20 heterocycloalkylene, C5 to C20 arylene, or C5 to C20 heteroarylene; R 1 is independently C5 to C20 aryl at each occurrence, wherein aryl is unsubstituted or substituted with halogen, carbonyl, hydroxyl or R s1 Replace; R 2 is independently an acid-labile group at each occurrence, wherein the acid-labile group is unsubstituted or substituted with R s1 Replace; R 3 is independently at each occurrence C1 to C20 alkyl, C1 to C20 heteroalkyl, C4 to C20 cycloalkylene, C2 to C30 heterocycloalkylene, C5 to C20 aryl, C5 to C20 heteroaryl, or R sl Base; R s1 is SH, C1 to C20 thioalkyl, C3 to C20 thiocycloalkyl, C1 to C20 thiohydroxyalkyl, C2 to C20 thioalkoxy, C3 to C20 thioalkoxyalkyl, C1 to C20 thioacetyl, C2 to C20 thioacetylalkyl, thiocarboxyl, C2 to C20 thioalkylcarboxyl, C4 to C20 thiocycloalkylcarboxyl, C3 to C20 thiocarbocyclic, or C3 to C20 heterothiocyclic; a 、R b and R c is independently H or C1 to C3 alkyl at each occurrence; and 0<x≤1, 0<y≤1 and 0≤z≤1, provided that R 1. R 2 and R One or more of 3 including R s1 , such that the compound of structure (I) includes at least one Rs1. In some embodiments, each L 1. L 2 and L 3 are all direct keys. In some embodiments, L l It is a direct key, L 2 is phenylene, and L 3 is a carbonyloxy group (-COO-). In some embodiments, each L l and L 3 are all carbonyloxy (-COO-), and L 2 is the direct key. R 1 is a sensitizer group suitable for absorbing actinic radiation. l is independently unsubstituted or substituted at each occurrence s1 Substituted hydroxyphenyl, unsubstituted or R s1 Substituted hydroxynaphthalenyl, unsubstituted or R s1 Substituted hydroxyanthracenyl, unsubstituted or R s1 Substituted phenyl, unsubstituted or R s1 Substituted naphthyl (naphatahlenyl), unsubstituted or R s1 Substituted anthracenyl group. In some embodiments, R l Is unsubstituted or R s1 Substituted hydroxyphenyl groups. In some embodiments, R l Is unsubstituted or R s1 Substituted phenyl. Acid labile groups (ALGs) are groups that decompose and cleave from thiol-containing polymers by reaction with an acid. 2 is independently unsubstituted or substituted at each occurrence s1 Substituted C4 to C12 alkyl, unsubstituted or R s1 Substituted C4 to C12 cycloalkyl, unsubstituted or R s1 Substituted C4 to C12 hydroxyalkyl, unsubstituted or R s1 Substituted C4 to C12 alkoxy, unsubstituted or R s1 Substituted C4 to C12 alkoxyalkyl or unsubstituted or R s1 Substituted three-dimensional (3D) ring structure. In some embodiments, R 2 is a tertiary alkyl group, such as a tertiary butyl group or a tertiary pentyl group, wherein the tertiary butyl group or the tertiary pentyl group is unsubstituted or substituted with R s1 replace. In some embodiments, R 2 is a cycloalkyl group, such as cyclopentyl, cyclohexylmethyl or cyclohexylethyl, wherein cyclopentyl, cyclohexylmethyl or cyclohexylethyl is unsubstituted or substituted with R s1 replace. In some embodiments, the 3D cyclic structure is an adamantyl, cedryl, norbornyl, or tricyclodecyl structure, wherein the adamantyl, cedryl, norbornyl, or tricyclodecyl structure is unsubstituted or substituted with R s1 replace. In some embodiments, R 2 has one of the following structures: 、 、 、 、 、 、 or . In some embodiments, R 3 is a lactone group, which is suitable for helping to reduce the amount of line edge roughness. In some embodiments, R 3 is a C1 to C12 alkyl group or a C4 to C12 cycloalkyl group. In some embodiments, R 3 is a methyl group. In some embodiments, R 3 is R sl . In some embodiments, R sl It’s SH. In some embodiments, R a 、R b and R c At least one of is H. In some embodiments, each R a 、R b and R c All are H. 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 groups. 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. In some embodiments, the polymer of structure (I) has a weight average molecular weight in the range of 0.5 to 1,000 kDa. In some embodiments, the polymer has a weight average molecular weight in the range of 2 to 250 kDa. In some more specific embodiments, L 1. L 2 and L 3 are independently direct bonds, R 1 is R s1 Substituted hydroxyphenyl, and R 3 is a methyl group. In some related embodiments, the thiol-containing polymer of structure (I) has the following structure (Ia): (Ia) Where: R 2 is independently at each occurrence a C4 to C12 alkyl group, a C4 to C12 cycloalkyl group, a C4 to C12 hydroxyalkyl group, a C4 to C12 alkoxy group, a C4 to C12 alkoxyalkyl group, or a three-dimensional (3D) cyclic structure. In some more specific embodiments, R sl is SH, and the thiol-containing polymer of structure (Ia) has the following structure (Ia-1): (Ia-1). In some more specific embodiments, L 1. L 2 and L 3 are independently direct bonds, R 1 is hydroxyphenyl, R 2 is R s1 substituted acid-labile group, and R 3 is a methyl group. In some related embodiments, the thiol-containing polymer of structure (I) has the following structure (Ib): (Ib) Where: R 2 is independently at each occurrence a C4 to C12 alkyl group, a C4 to C12 cycloalkyl group, a C4 to C12 hydroxyalkyl group, a C4 to C12 alkoxy group, a C4 to C12 alkoxyalkyl group, or a three-dimensional (3D) cyclic structure. In some more specific embodiments, R sl is SH, and the thiol-containing polymer of structure (Ib) has the following structure (Ib-1): (Ib-1). In some more specific embodiments, L 1. L 2 and L 3 are independently direct bonds, R 1 is a hydroxyphenyl group, and R 3 is R s1 In some related embodiments, the thiol-containing polymer has the following structure (Ic): (Ic) where: R 2 is independently at each occurrence a C4 to C12 alkyl group, a C4 to C12 cycloalkyl group, a C4 to C12 hydroxyalkyl group, a C4 to C12 alkoxy group, a C4 to C12 alkoxyalkyl group, or a three-dimensional (3D) cyclic structure. In some more specific embodiments, R sl is SH, and the thiol-containing polymer of structure (Ic) has the following structure (Ic-1): (Ic-1). In some more specific embodiments, L 1. L 2 and L 3 are independently direct bonds, R 1 is R s1 Substituted phenyl, and R 3 is a methyl group. In some related embodiments, the thiol-containing polymer of structure (I) has the following structure (Id): (Id) Where: R 2 is independently at each occurrence a C4 to C12 alkyl group, a C4 to C12 cycloalkyl group, a C4 to C12 hydroxyalkyl group, a C4 to C12 alkoxy group, a C4 to C12 alkoxyalkyl group, or a three-dimensional (3D) cyclic structure. In some more specific embodiments, R sl is SH, and the thiol-containing polymer of structure (Id) has the following structure (Id-1): (Id-1). In some embodiments, the thiol-containing polymer has the following structure (II): (II) Where: L 1. L 2. L 3 and L 4 is independently at each occurrence a direct bond or a plurality of linking chains, which are oxo (—O—), carbonyl (—C(═O)—), carbonyloxy (—C(═O)—O—), oxycarbonyl (—O—C(═O)—), carbonate (—O—C(═O)—O—), C1 to C20 alkylene, C1 to C20 heteroalkylene, C4 to C20 cycloalkylene, C4 to C20 heterocycloalkylene, C5 to C20 arylene, or C5 to C20 heteroarylene; R 1 is independently C5 to C20 aryl at each occurrence, wherein aryl is unsubstituted or substituted with halogen, carbonyl, hydroxyl or R s1 Replace; R 2 is independently an acid-labile group at each occurrence; R 3 is independently at each occurrence C1 to C20 alkyl, C1 to C20 heteroalkyl, C4 to C20 cycloalkylene, C2 to C30 heterocycloalkylene, C5 to C20 aryl, C5 to C20 heteroaryl, or R s1 Base; R 4 is independently a free radical active functional group at each occurrence; R s1 is SH, C1 to C20 thioalkyl, C3 to C20 thiocycloalkyl, C1 to C20 thiohydroxyalkyl, C2 to C20 thioalkoxy, C3 to C20 thioalkoxyalkyl, C1 to C20 thioacetyl, C2 to C20 thioacetylalkyl, thiocarboxyl, C2 to C20 thioalkylcarboxyl, C4 to C20 thiocycloalkylcarboxyl, C3 to C20 thiocarbocyclyl, or C3 to C20 thioheterocyclyl; a 、R b and R c is independently H or C1 to C3 alkyl at each occurrence; and 0<x≤1, 0<y≤1, and 0≤z≤1, provided that R 1. R 3 or both including R s1 , such that the compound of structure (II) includes at least one R s1 . In some embodiments, each L 1. L 2. L 3 and L 4 are all direct keys. In some embodiments, each L 1. L 2 and L 3 are all direct keys, and L 4 is an oxo group (-O-), a carbonyl group (-CO-), a carbonyloxy group (-COO-) or a methyl group (-CH 2-). In some embodiments, each L 1 and L 4 are direct keys, L 2 is phenylene, L 3 is a carbonyloxy group (-COO-). In some embodiments, each L 1. L 3 and L 4 are all carbonyl groups (-COO-), and L 2 is the direct key. R 1 is a sensitizer group suitable for absorbing actinic radiation. l Each occurrence is independently unsubstituted or substituted with 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. In some embodiments, R l Is unsubstituted or R sl Substituted hydroxyphenyl groups. Acid labile groups (ALGs) are groups that decompose and cleave from thiol-containing polymers by reaction with an acid. 2 is independently unsubstituted or substituted at each occurrence s1 Substituted C4 to C12 alkyl, unsubstituted or R s1 Substituted C4 to C12 cycloalkyl, unsubstituted or R s1 Substituted C4 to C12 hydroxyalkyl, unsubstituted or R s1 Substituted C4 to C12 alkoxy, unsubstituted or R s1 Substituted C4 to C12 alkoxyalkyl or unsubstituted or R s1 Substituted three-dimensional (3D) ring structure. In some embodiments, R 2 is a tertiary alkyl group, such as a tertiary butyl group or a tertiary pentyl group, wherein the tertiary butyl group or the tertiary pentyl group is unsubstituted or substituted with R s1 replace. In some embodiments, R 2 is a cycloalkyl group, such as cyclopentyl, cyclohexylmethyl or cyclohexylethyl, wherein cyclopentyl, cyclohexylmethyl or cyclohexylethyl is unsubstituted or substituted with R s1 replace. In some embodiments, the 3D cyclic structure is an adamantyl, cedaryl, norbornyl or tricyclodecyl structure, wherein the adamantyl, cedaryl, norbornyl or tricyclodecyl structure is unsubstituted or substituted with R s1 replace. In some embodiments, R 2 has one of the following structures: 、 、 、 、 、 、 or . In some embodiments, R 3 is a lactone group, which is suitable for helping to reduce the amount of line edge roughness. In some embodiments, R 3 is a C1 to C12 alkyl group or a C4 to C12 cycloalkyl group. In some embodiments, R 3 is a methyl group. In some embodiments, R 3 is R sl . The free radical active functional group is a group that is activated by a free radical and undergoes a thiol-ene / yne reaction with a thiol group. 4 is alkenyl or alkynyl. In some embodiments, R sl It’s SH. In some embodiments, R a 、R b and R c At least one of them is H. In some embodiments, each R a 、R b and R c All are H. 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 groups. 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. In some embodiments, the polymer of structure (II) has a weight average molecular weight in the range of 0.5 to 1,000 kDa. In some embodiments, the polymer has a weight average molecular weight in the range of 2 to 250 kDa. In some more specific embodiments, L 1. L 2 and L 3 are independently direct bonds, R 1 is R s1 Substituted hydroxyphenyl, R 3 is methyl, and R In some related embodiments, the thiol-containing polymer of structure (II) has the following structure (IIa): (IIa) Where: R 2 is independently at each occurrence a C4 to C12 alkyl group, a C4 to C12 cycloalkyl group, a C4 to C12 hydroxyalkyl group, a C4 to C12 alkoxy group, a C4 to C12 alkoxyalkyl group, or a three-dimensional (3D) cyclic structure. In some more specific embodiments, R sl is SH, and the thiol-containing polymer of structure (IIa) has the following structure (IIa-1): (IIa-1). In some more specific embodiments, L 1. L 2 and L 3 are independently direct bonds, R 1 is hydroxyphenyl and R 3 is R s1 In some related embodiments, the thiol-containing polymer of structure (II) has the following structure (IIb): (IIb) Where: R 2 is independently at each occurrence a C4 to C12 alkyl group, a C4 to C12 cycloalkyl group, a C4 to C12 hydroxyalkyl group, a C4 to C12 alkoxy group, a C4 to C12 alkoxyalkyl group, or a three-dimensional (3D) cyclic structure. In some more specific embodiments, R sl is SH, and the thiol-containing polymer of structure (IIb) has the following structure (IIb-1): (IIb-1). In some more specific embodiments, L 1. L 2 and L 3 are independently direct bonds, R 1 is R s1 Substituted phenyl and R 3 is a methyl group. In some related embodiments, the thiol-containing polymer of structure (II) has the following structure (IIc): (IIc) where: R 2 is independently at each occurrence a C4 to C12 alkyl group, a C4 to C12 cycloalkyl group, a C4 to C12 hydroxyalkyl group, a C4 to C12 alkoxy group, a C4 to C12 alkoxyalkyl group, or a three-dimensional (3D) cyclic structure. In some more specific embodiments, R slis SH, and the thiol-containing polymer of structure (IIc) has the following structure (IIc-1): (IIc-1). In some embodiments, the thiol-containing polymer of structure (I) is a compound selected from Table 1. Table 1. Exemplary sulfur-containing polymers of structure (I) or (II) In some embodiments, an oxidizing agent and an acid catalyst may be added to the photoresist composition. The oxidizing agent and the acid catalyst cause oxidation of the thiol groups in the polymer of structure (I) or (II), thereby forming disulfide bonds between the polymer chains to crosslink the polymers (Figures 3A and 3C). The formation of oxidized disulfide bonds increases the glass transition temperature (Tg) of the resulting crosslinked polymer, which helps to improve pattern resolution and LWR. Suitable oxidizing agents that can be used include, but are not limited to, oxygen, H 2O 2. LiBrO 3. NaBrO 3. KBrO 3. O 3.I 2 or a combination thereof. The acid catalyst is selected to have a pKa greater than 1. If the acidity of the acid catalyst is too strong, the acid-labile groups R 2 may decompose, which may cause the photoresist to fail. Suitable acid catalysts that can be used include but are not limited to acetic acid (CH 3COOH), hydrochloric acid (HCl), carbonic acid (H 2CO 3) or a combination thereof. Alternatively, in some embodiments, in addition to adding an oxidant and an acid catalyst to the photoresist composition, a crosslinking agent may be added to the photoresist composition, or a crosslinking agent may be added to the photoresist composition instead of the oxidant and the acid catalyst. The crosslinking agent includes a crosslinking group that can react with the thiol group of the thiol-containing polymer of structure (I) to bond the two polymer chains together (Figure 3B). This bonding increases the glass transition temperature (Tg) of the resulting crosslinked polymer, which helps to improve pattern resolution and LWR. In some embodiments, the crosslinking agent includes two to six crosslinking groups, including, for example, epoxy, hydroxyl, melamine, olefin, alkyne, or vinyl ether. FIG4 shows an example of a plurality of cross-linking agents that can be used in the present disclosure. The cross-linking agent may include two or more cross-linking groups that provide cross-linking sites. In some embodiments, as shown in FIG4 , the cross-linking agent includes a core group C and two or more cross-linking groups covalently bonded to the core group C through a plurality of linking chains B. The linking chain length is controlled so that the linking chain B can rotate to achieve a high cross-linking reaction efficiency in the exposed area. The high cross-linking efficiency between the thiol groups in the thiol-containing polymer (I) and the cross-linking agent enables lithographic patterning to be performed using a lower EUV exposure dose. In some embodiments, the core group C may include a divalent or multivalent C1 to C20 alkyl group, a C3 to C20 divalent or multivalent cycloalkyl group, a divalent or multivalent C2 to C20 heteroalkyl group, a C3 to C20 divalent or multivalent cycloheteroalkyl group, a C5 to C20 divalent or multivalent aryl group, or a C3 to C20 divalent or multivalent heteroaryl group. The connecting chain A coupling the core group C to the crosslinking group may include a C2 to C20 alkylene group, a C3 to C20 cycloalkylene group, a C2 to C20 heteroalkylene group, a C2 to C20 hydroxyalkylene group, a C2 to C20 ethynyl group, a C2 to C20 acetylalkylene group, a C2 to C20 carbonyl group, a C2 to C20 alkylene carbonyl group, a C4 to C20 cycloalkylene carbonyl group, a C3 to C20 saturated or unsaturated hydrocarbon ring, or a C2 to 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, C1 to C8 alkyl, C3 to C8 cycloalkyl, C1 to C8 hydroxyalkyl, C1 to C8 alkoxy, C2 to C8 alkoxyalkyl, C1 to C8 acetyl, C2 to C8 acetylalkyl, C1 to C8 carbonyl, C2 to C8 alkylcarbonyl, C4 to C8 cycloalkylcarbonyl, C3 to C8 saturated or unsaturated hydrocarbon ring, or C3 to C8 heterocyclic group. In some embodiments, the core group C has one of the following structures: 、 、 、 、 、 、 、 、 or . In some embodiments, the linker chain A is O, an alkylene oxide, or polyethylene oxide. In some embodiments, the cross-linking agent has one of the following structures: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 or . In some embodiments, the concentration of the crosslinker in the photoresist composition is in the range of 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 crosslinker in the photoresist composition is in the range of about 5 wt % to about 20 wt % based on the total weight of the crosslinker and the polymer. A photoresist composition having less than about 0.1 wt % of the crosslinker may experience insufficient crosslinking during photoresist patterning. A photoresist composition having a crosslinker content exceeding 50 wt % may result in reduced photoresist pattern resolution or increased line width roughness (LWR). In embodiments where crosslinking is achieved by reactions between multiple crosslinking groups (e.g., thiol-thiol or thiol-alkenyl) attached to the polymer backbone, the addition of a crosslinking agent is not necessary. In some embodiments, as shown in FIG. 5 , instead of using a thiol-containing polymer, the photoresist composition includes a polymer cross-linkable with alkenyl or alkyne groups and a thiol-containing cross-linker, such that the polymer cross-links via a "click" reaction (e.g., a thiol-ene / yne reaction) upon ultraviolet (UV) irradiation or heating. In some embodiments, the thiol-free polymer has the following structure (III): (III) Where: L 1. L 2. L 3 and L 4 is independently at each occurrence a direct bond or a plurality of connecting chains, which are oxo (—O—), carbonyl (—C(═O)—), carbonyloxy (—C(═O)—O—), oxycarbonyl (—O—C(═O)—), carbonate (—O—C(═O)—O—), C1 to C20 alkylene, C1 to C20 heteroalkylene, C4 to C20 cycloalkylene, C4 to C20 heterocycloalkylene, C5 to C20 arylene or C5 to C20 heteroarylene; R 5 is independently C5 to C20 aryl at each occurrence, wherein aryl is unsubstituted or substituted with halogen, carbonyl or hydroxy; R 6 is independently an acid-labile group at each occurrence; R 7 is independently at each occurrence C1 to C20 alkyl, C1 to C20 heteroalkyl, C4 to C20 cycloalkylene, C2 to C30 heterocycloalkylene, C5 to C20 aryl or C5 to C20 heteroaryl; R 8 is independently a free radical active functional group at each occurrence; R a 、R b and R c is independently at each occurrence H or C1 to C3 alkyl; and 0<x≤1, 0<y≤1, and 0≤z≤1. In some embodiments, each L 1. L 2. L 3 and L 4 are all direct keys. In some embodiments, each L 1. L 2 and L 3 are all direct keys, and L 4 is an oxo group (-O-), a carbonyl group (-CO-), a carbonyloxy group (-COO-) or a methyl group (-CH 2-). In some embodiments, each L 1 and L 4 are direct keys, L 2 is phenylene, L 3 is a carbonyloxy group (-COO-). In some embodiments, each L 1. L 3 and L 4 are all carbonyloxy groups (-COO-), and L 2 is the direct key. R 5 is a sensitizer group suitable for absorbing actinic radiation. 5 is independently at each occurrence hydroxyphenyl, hydroxynaphthyl, hydroxyanthryl, phenyl, naphthyl or anthracenyl. In some embodiments, R 5 is a hydroxyphenyl group. Acid labile groups (ALGs) are groups that decompose and cleave from thiol-containing polymers by reaction with an acid. 6 is independently at each occurrence a C4 to C12 alkyl group, a C4 to C12 cycloalkyl group, a C4 to C12 hydroxyalkyl group, a C4 to C12 alkoxy group, a C4 to C12 alkoxyalkyl group, or a three-dimensional (3D) cyclic structure. In some embodiments, R 6 is a tertiary alkyl group, such as a tertiary butyl group or a tertiary pentyl group. In some embodiments, R 6 is a cycloalkyl group, such as cyclopentyl or cyclohexylalkyl. In some embodiments, the 3D cyclic structure is an adamantyl, cedaryl, norbornyl, or tricyclodecanyl structure. In some embodiments, R 6 has one of the following structures: 、 、 、 、 、 、 or . In some embodiments, R 7 is a lactone group, which is suitable for helping to reduce the amount of line edge roughness. In some embodiments, R 7 is a C1 to C12 alkyl group or a C4 to C12 cycloalkyl group. In some embodiments, R 7 is a methyl group. The free radical active functional group is a group that is activated by a free radical and undergoes a thiol-ene / yne reaction with a thiol group. 8 is alkenyl or alkynyl. In some embodiments, R a 、R b and R c At least one of R is H. In some embodiments, each R a 、R b and R c All are H. In some embodiments, R a 、R b and R cIn some embodiments, each R a 、R b and R c All are methyl groups. 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. In some embodiments, the polymer of structure (III) has a weight average molecular weight in the range of 0.5 to 1,000 kDa. In some embodiments, the polymer has a weight average molecular weight in the range of 2 to 250 kDa. In some more specific embodiments, L 1. L 2 and L 3 are independently direct bonds, R 5 is hydroxyphenyl, R 7 is methyl, and R 8 is an olefin. In some related embodiments, the polymer of structure (III) has the following structure (IIIa): (IIIa) wherein for polymers of structure (III), L 4. R 2. R a 、R b and R c Each occurrence is independently as defined above. In some specific embodiments, the thiol-containing polymer of structure (III) is a compound selected from Table 2. Table 2. Exemplary non-sulfur-containing polymers of structure (III) In some embodiments, the thiol-containing cross-linking agent is a polythiol having the following structure (IV): (IV) Where: R s2 is a C1 to C20 alkylene group, a C1 to C20 alkylenecarboxyl group, a C3 to C20 cycloalkylenecarboxyl group, a C3 to C20 saturated or unsaturated carbocyclic group, or a C3 to C20 heterocyclic group; and n is an integer of 2 to 6. In some embodiments, n is 2, 3, 4, 5, or 6. In some embodiments, the thiol-containing crosslinking 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 hexakis(3-mercaptopropionate) (DPHMP), trimethylolpropane tris(3-mercaptopropionate) (TMPTMP), tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate ... isocyanurate) and pentaerithritol tetrakis(3-mercaptopropionate, PETMP). In some embodiments, the photoresist composition includes one or more photoactive compounds (PACs). PACs are photoacid generators (PAGs), photobase generators (PBGs), photodecomposable bases (PDBs), free radical generators (also known as photoinitiators), or similar materials. PACs can be positive-type or negative-type. In some embodiments where the PAC is a photoacid generator (PAG), the PAG includes a triazine halide, an onium salt, a diazonium salt, an aromatic diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt, an imide sulfonate, an oxime sulfonate, a diazodisulfone, a disulfone, an o-nitrobenzylsulfonate, a sulfonated ester, a halogenated sulfonyloxydimethylimide, or a sulfonated ester. dicarboximide), α-cyanooxyamine-sulfonate, ketodiazosulfone, sulfonyldiazoester, 1,2-di(arylsulfonyl)hydrazine, nitrobenzyl ester, s-triazine derivatives, combinations thereof, or similar materials. Specific examples of the photoacid generator include α-(trifluoromethylsulfonyloxy)-bicyclo[2.2.1]hept-5-ene-2,3-dicarb-o-ximide (MDT), N-hydroxy-naphthalimide (DDSN), benzoin tosylate, t-butylphenyl-α-(p-toluenesulfonyloxy)-acetate and t-butyl-α-(p-toluenesulfonyloxy)-acetate, triarylsulfonium and diaryliodonium hexafluoroantimonate, hexafluoroarsenate, trifluoromethanesulfonate, iodonium perfluorooctanesulfonate perfluorooctanesulfonate), N-camphorsulfonyloxynaphthalimide, N-pentafluorophenylsulfonyloxynaphthalimide, ionic iodonium sulfonates such as diaryl iodonium (alkyl or aryl) sulfonate and bis-(di-t-butylphenyl) iodonium camphorsulfonate. camphanylsulfonate), perfluoroalkanesulfonates such as perfluoropentanesulfonate, perfluorooctanesulfonate, perfluoromethanesulfonate, aryl (e.g., phenyl or benzyl) triflates such as triphenylsulfonium triflate or bis-(t-butylphenyl)iodonium triflate, pyrogallol derivatives (e.g., trimesylate of pyrogallol), trifluoromethanesulfonate esters of hydroxyimides, α,α′-bissulfonyldiazomethane (α,α′-bis-sulfonyl-diazomethane), sulfonate ester of nitro-substituted benzyl alcohol, naphthoquinone-4-diazide, alkyl disulfone or similar materials. In some embodiments where the PAC is a free radical generator, the free radical generator includes: n-phenylglycine; aromatic ketones including benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone; diaminobenzophenone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzo-phenone, 3,3'-dimethyl-4-methoxybenzophenone, p,p'-bis(dimethylamino)benzo-phenone, p,p'-bis(diethylamino)benzophenone; anthraquinone, 2-ethylanthraquinone; naphthaquinone ); phenanthraquinone; benzoins including benzoin, benzoinmethylether, benzoinisopropylether, benzoin-n-butylether, benzoin-phenylether, methylbenzoin, and ethylbenzoin; benzyl derivatives including dibenzyl, benzyldiphenyldisulfide, and benzyldimethylketal; acridine derivatives including 9-phenylacridine and 1,7-bis(9-acridinyl)heptane;Thioxanthone, including 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, and 2-isopropylthioxanthone; acetophenone, including 1,1-dichlorobenzene; 1,1-dichloroacetophenone, pt-butyldichloro-acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 2,2-dichloro-4-phenoxyacetophenone;2,4,5-triarylimidazole dimer includes 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di-(m-Methoxyphenyl) imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimid ...fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(o- 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 thereof or similar materials. In some embodiments, the PAC comprises a photobase generator (PBG) and a photodecomposition base (PDB). In embodiments where the PAC is a photobase generator (PBG), the PBG comprises a quaternary ammonium dithiocarbamate, an α-aminoketone, an oxime-urethane-containing molecule such as dibenzophenoneoxime hexamethylene diurethane, an ammonium tetraorganylborate salt, and N-(2-nitrobenzyloxycarbonyl) cyclic amine, combinations thereof, or similar materials. In some embodiments where the PAC is a photodecomposable base (PDB), the PDB includes triphenylsulfonium hydroxide, triphenylsulfonium antimony hexafluoride, and triphenylsulfonium triflyl. The photoresist composition may include about 0.1 wt% to 10 wt% of PAC, based on the total weight of the polymer as 100%. 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 a low crosslinking reaction rate. Photoresist compositions with more than 10 wt% of PAC may result in reduced photoresist pattern resolution or increased line width roughness (LWR). In some embodiments, instead of using a free radical-generating photoinitiator, the photoresist composition may alternatively or additionally include a thermal initiator capable of generating a plurality of free radicals for initiating a crosslinking reaction under heating. 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, 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)-3,3,5-trimethylcyclohexane), tert-butyl hydroxyperoxide, tert-butyl peracetate peracetate), tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy isopropyl carbonate, cumene hydroperoxide, cyclohexanone peroxide, dicumyl peroxide, lauroyl peroxide, 2,4-pentanedione peroxide, peracetic acid, potassium persulfate, derivatives thereof, and combinations thereof.In some embodiments, the thermal initiator includes azobisisobutyronitrile, 2,2'-azodi(2-methylbutyronitrile), or a combination thereof. In some embodiments, the photoresist composition comprises 0 to 10 wt % of the thermal initiator based on the total weight of the polymer. In some embodiments, the photoresist composition comprises 0.1 to 5 wt % of the thermal initiator. The photoresist composition may also include a number of other optional additives. In some embodiments, a quencher is added to the photoresist composition to inhibit the diffusion of acids / bases / free radicals generated within the photoresist. The quencher improves the photoresist pattern structure and the stability of the photoresist over time. In some embodiments, the quencher is an amine, such as a secondary lower aliphatic amine, a tertiary lower aliphatic amine, or similar materials as described above. Specific examples of amines include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tripentylamine, diethanolamine, triethanolamine, alkanolamine, or similar materials as described above. 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, phosphorous oxyacids and their derivatives, such as phosphoric acid and its derivatives such as esters, di-n-butyl phosphate and diphenyl phosphate; phosphonic acid and its derivatives, including its esters, such as dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate and dibenzyl phosphonate; and phosphinic acid and its derivatives, including its esters, such as phenylphosphinic acid. In some embodiments, a stabilizer is added to the photoresist composition to help prevent undesirable diffusion of acids generated during photoresist exposure. In some embodiments, the stabilizer includes: nitrogen-containing compounds, including aliphatic primary, secondary, and tertiary amines; cyclic amines, including piperidine, pyrrolidine, and morpholine; aromatic heterocycles, including pyridine, pyrimidine, and purine; imines, including diazabicyclononene, guanidine, imide, and amide, or similar materials described above. Alternatively, in some embodiments, ammonium salts can also be used as stabilizers, including ammonium alkoxides, primary, secondary, tertiary, and quaternary alkyl and aryl ammonium salts, including hydroxides, phenolates, carboxylates, aryl and alkyl sulfonates, sulfonamides, or similar materials described above. In some embodiments, other cationic nitrogen-containing compounds are used, including pyridinium salts and other salts of heterocyclic nitrogen-containing compounds with anions, such as alkoxides, including hydroxides, phenolates, carboxylates, aryl and alkyl sulfonates, sulfonamides, or similar materials described above. 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, t-butyl deoxycholate, t-butyl lithocholate, and t-butyl-3-acetyl lithocholate. Another additive in some embodiments of the photoresist composition is a plasticizer. Plasticizers can be used to reduce delamination and cracking between the photoresist layer and the underlying layer (e.g., the material layer to be patterned). Plasticizers include monomeric, oligomeric, and polymeric plasticizers, such as oligomeric and polyethylene glycol ethers, cycloaliphatic esters, and non-acid reactive steroidal-derived materials. In some embodiments, specific examples of materials used as plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerine, or similar materials. Colorants are another additive included in some embodiments of photoresists. A colorant observer inspects the photoresist and identifies any defects that may need to be remedied before further processing. In some embodiments, the colorant is a triarylmethane dye or a fine-particle organic pigment. In some embodiments, specific examples of the material 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-t-butylphenyl salicylate. salicylate); phenylacrylate compounds, such as ethyl-2-cyano-3,3-diphenylacrylate and 2-ethylhexyl-2-cyano-3,3-diphenylacrylate; benzotriazole compounds, such as 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole; benzotriazole and 2-(3-t-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, naphthalic acid compounds, azo dyes, phthalocyanine blue, phthalocyanine green, iodine green, Victoria blue, naphthalene black, photopia methyl violet, bromphenol blue, and bromcresol green; laser dyes, such as Rhodamine G6, Coumarin 500, DCM (4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H pyran), Kiton Red 620, and pyrrolidine 580 (Pyrromethene 580), etc. In addition, one or more colorants may be used in combination to provide the desired coloring. In some embodiments of the photoresist composition, an adhesion additive may be added 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 carbonyl group, a methacryloyl group, an isocyanate group, or an epoxy group. Specific examples of the adhesive component include trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyl triethoxy silane, γ-glycidoxypropyl trimethoxy silane, β-(3,4-epoxycyclohexyl)ethyl trimethoxy silane, silane), benzimidazole and polybenzimidazole, pyridine derivatives substituted with lower hydroxyalkyl groups, nitrogen heterocyclic compounds, urea, thiourea, organophosphorus compounds, 8-hydroxyquinoline, 4-hydroxypteridine and derivatives, 1,10-phenanthroline and derivatives, 2,2'-bipyridine (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 benzothiazoleamine salts having a cyclohexyl ring and a morpholine ring, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxy silane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxy silane silane), 3-methacryloyloxypropyltrimethoxysilane, vinyl trimethoxysilane, a combination thereof, or similar materials thereof. A surface leveling agent may be added to some embodiments of the photoresist composition to help maintain a flat top surface of the photoresist layer 220 so that incident light is not adversely modified by an uneven surface. In some embodiments, the surface leveling agent includes a fluoroaliphatic ester, a hydroxyl-terminated fluorinated polyether, a fluorinated glycol polymer, a silane oxide, an acrylic polymer leveler, combinations thereof, or similar compounds thereof. The various components, such as the polymer, PAC, and crosslinker, along with any desired additives or reagents, are placed in a solvent to facilitate mixing and dispensing the photoresist composition. The solvent selected to facilitate mixing and dispensing the photoresist composition is based at least in part on the materials selected for the polymer and PAC. In some embodiments, the solvent is selected so that the polymer and PAC can be uniformly dissolved in the solvent and dispensed onto the patterned layer. In some embodiments, the solvent is one or more selected from the group consisting of propylene glycol methyl ether acetate (PGME), 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), isopropanol (IPA), tetrahydrofuran (THF), methyl isobutyl carbinol (MIBC), n-butyl acetate (nBA), and 2-heptanone (MAK). The amount of solvent in the photoresist composition may be about 80 wt % to about 99 wt % based on 100% total weight of the composition. In some embodiments, the amount of solvent in the photoresist composition may be about 95 wt % to about 99 wt %. Once added, the mixture is then mixed in order to achieve 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. Once prepared, the photoresist composition is then applied to the layer to be patterned, such as forming photoresist layer 220 on material layer 210. Application can be accomplished by any suitable method, including spin coating, spray coating, dip coating, tape casting, or similar methods described above. In some embodiments, application of the photoresist composition is accomplished using a coating track, wherein the photoresist composition is dispensed onto a rotating substrate 202. During dispensing, substrate 202 can be rotated at a speed of up to about 4,000 rpm, such as from about 500 rpm to about 3,000 rpm or from about 1,000 rpm to about 2,500 rpm. In some embodiments, the thickness of photoresist layer 220 can be in the range of about 10 nm to about 300 nm. 1 and 2C , according to some embodiments, method 100 proceeds to operation 106, where a first bake process 230 is performed on the photoresist layer 220. According to some embodiments, FIG. 2C is a cross-sectional view of the semiconductor device 200 shown in FIG. 2B after the first bake process 230 is performed on the photoresist layer 220. Because this first bake process 230 is performed to cure and dry the photoresist layer 220 before exposing it to radiation, the first bake process 230 may also be referred to as a pre-exposure bake process. Curing and drying the photoresist layer 220 removes residual solvent and free volume from the film, making the photoresist layer 220 uniform and dense. In some embodiments, the first bake process 230 is performed at a temperature and for a 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. 1 and 2D , according to some embodiments, method 100 proceeds to operation 108, where an exposure process 240 is performed on the photoresist layer 220. According to some embodiments, FIG. 2D is a cross-sectional view of the semiconductor device 200 shown in FIG. 2C after the exposure process 240 is performed on the photoresist layer 220. In some embodiments, the exposure process 240 is performed by placing the photoresist-coated substrate in a lithography tool that includes a photomask 250, optical elements, a light source for providing exposure radiation, and a movable stage for supporting and moving the substrate 202 under the exposure radiation. During the exposure process 240, the photoresist layer 220 is exposed to radiation from the light source through the mask 250. In some embodiments, the mask 250 is a transmissive mask. In some other embodiments, the mask 250 is a reflective mask. The mask 250 has a predefined pattern designed for the IC based on the specifications of the IC to be manufactured. The pattern of the mask 250 corresponds to the pattern of the materials that make up the various elements of the IC device to be manufactured. For example, a portion of the IC design layout includes various IC features such as active regions of the material layer 210 to be formed in and / or deposited on the substrate 202, gate electrodes, source and drain electrodes, through holes for metal lines or interlayer interconnects, and openings for bonding pads. 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 photoresist layer 250 to reach the photoresist layer 220. Therefore, the portion of the photoresist layer 220 below the second region 254 receives radiation, which 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, which is referred to as an unexposed region 220U. 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). When selectively (or patterned) exposed to actinic radiation, the photoacid generator (PAG) in the exposed areas 220E of the photoresist layer 220 absorbs the radiation, which triggers the PAG to generate acid in the exposed areas 220E. As shown in FIG. 6A , the generated acid cleaves the acid-labile group R from the polymer (e.g., a polymer of structure (I), (II), or (III)). 2, thereby forming carboxyl groups in the exposed regions 220E, as shown in FIG6B, while the polymer (e.g., polymer of structure (I), (II), or (III)) and the unexposed regions 220U remain intact. The formation of carboxyl groups in the exposed regions 220E makes the exposed regions 220E more soluble in an aqueous developer, such as a tetramethylammonium hydroxyl solution. In some embodiments, the photoactive compound includes a photoinitiator that generates free radicals upon exposure to actinic radiation, such as EUV radiation having a wavelength of 13.5 nm or UV radiation having a wavelength in the range of about 100 nm to about 1000 nm. The free radicals generated by the exposed photoinitiator cause a free radical-reactive functional group on one polymer chain to react with a thiol group on another polymer chain, cause a free radical-reactive functional group in the crosslinker to react with a thiol group on two adjacent polymer chains, or cause a thiol group in the crosslinker to react with a free radical-reactive functional group on two adjacent polymer chains, thereby crosslinking adjacent polymer chains in the exposed region 220E during a subsequent baking process. This crosslinking reaction increases the molecular weight of the polymer, making the exposed region 220E less soluble in the developer. The increase in molecular weight also results in an increase in the glass transition temperature (Tg), which helps reduce acid diffusivity. 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 acid to cleave the acid-labile groups R on the polymer. 2, and the photoinitiator generates free radicals to cause crosslinking of 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 photoinitiator that generates free radicals. In some embodiments, when the photoactive compound (PAC) is a photoacid generator and the photoresist composition includes a thermal initiator for initiating the crosslinking reaction, an additional baking step is required to activate the thermal initiator. 1 and 2E , according to some embodiments, method 100 proceeds to operation 110 by performing a second baking process 260 on photoresist layer 220. According to some embodiments, FIG. 2E is a cross-sectional view of semiconductor device 200 shown in FIG. 2D after performing the second baking process 260. Because the second bake process 260 is performed after the exposure process 240 in which the photoresist layer 220 is exposed to radiation, the second bake process 260 may also be referred to as a post-exposure bake (PEB) process. The second bake process 260 helps disperse and react the acid / base / free radicals generated by the radiation impacting the PAC during exposure. This thermal assistance helps create or enhance the chemical difference between the exposed regions 220E and the unexposed regions 220U within the photoresist layer 220, resulting in a solubility difference between the exposed regions 220E and the unexposed regions. In addition, this thermal assistance promotes the crosslinking reaction, thereby helping to further increase the crosslink density and molecular weight of the crosslinked polymer in the exposed regions 220E or the unexposed regions 220U of the photoresist layer 220. The high glass transition temperature generated by the thiol crosslinking can effectively suppress the acid diffusion length in the photoresist lithography process, which helps to reduce the line width roughness (LWR) of the photoresist pattern. In the case where the photoresist composition includes a crosslinking agent and the crosslinking of the polymer is 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 groups R in the polymer will 2 may decompose, causing the photoresist to fail. In the case where the photoresist composition includes an oxidizing agent and the crosslinking of the polymer is formed by oxidizing disulfide, 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 groups R in the polymer will 2 may decompose, causing the photoresist to fail. 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 groups on the polymer, thereby forming a crosslinked polymer in the unexposed area 220U. The second baking process 260 can be performed at a temperature range of about 50°C to about 150°C. If the temperature is higher than 150°C, the acid-labile groups R in the polymer will be 2 may decompose, causing the photoresist to fail. 1 and 2F , according to some embodiments, method 100 proceeds to operation 112 , where a development process 270 is performed on the photoresist layer 220 . FIG. 2F is a cross-sectional view of the semiconductor device 200 shown in FIG. 2E after the development process 270 is performed on the photoresist layer 220 , according to some embodiments. 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 irradiated exposed regions 220E of the positive-tone photoresist composition that expose the surface of the material layer 210, and leaves behind well-defined unexposed regions 220U having an improved LWR compared to the LWR provided by conventional phenol-based photoresists. In some embodiments, the developer dissolves the irradiated unexposed regions 220U of the negative-tone photoresist composition, exposing the surface of the material layer 210, and leaves behind well-defined exposed regions 220E having an improved LWR compared to the LWR provided by conventional phenol-based photoresists. As shown in FIG. 2F (B), after the development process, a patterned photoresist layer 220P is formed. The patterned photoresist layer 220P includes an unexposed region 220U of the photoresist layer (not shown) or an exposed region 220E of the photoresist layer 220. In some embodiments, the developer comprises a solvent and an acid or base. In some embodiments, the concentration of the solvent in the developer is from about 60 wt % to about 99 wt % based on the total weight of the developer. The concentration of the acid or base is from about 0.001 wt % to about 20 wt % based on the total weight of the developer. In certain embodiments, the concentration of the acid or base in the developer is from about 0.01 wt % to about 15 wt % 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. In some embodiments, a 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 spinning. 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 spinning at a rate 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 for about 30 seconds to about 10 minutes. Although a spin coating operation is one suitable method for developing the photoresist layer 220 after exposure, it is intended to be illustrative and not limiting of the embodiments. Rather, any suitable developing operation may be used instead, including a dip process, a puddle process, and spray-on methods. All of these developing operations are included within the scope of the embodiments. 1 and 2G , according to some embodiments, method 100 proceeds to operation 114, where material layer 210 is etched using patterned photoresist layer 220P as an etching mask. FIG. 2F is a cross-sectional view of semiconductor device 200 after material layer 210 is etched using patterned photoresist layer 220P as an etching mask, according to some embodiments. As shown in FIG2G (A), the material layer 210 is patterned using the patterned photoresist layer 220P as an etching mask as shown in FIG2F (A), forming the patterned material layer 210P including the groove 210a. Alternatively, as shown in FIG2G (B), the patterned photoresist layer 220P is used as an etching mask as shown in FIG2F (B), forming the patterned material layer 210P including the groove 210b. 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 employed is an isotropic etching, such as dry etching, although any suitable etching process may be utilized. In some embodiments, the dry etching is reactive ion etching (RIE) or plasma etching. In some embodiments, the dry etching may be performed by a fluorine-containing gas (e.g., CF 4. SF 6. CH 2F 2. CHF 3 and / or C 2F 6) Chlorine-containing gases (e.g., Cl 2. CHCl 3. CCl 4 and / or BCl 3) Bromine-containing gases (such as HBr and / or CHBr 3) Dry etching is performed using an oxygen-containing gas, an iodine-containing gas, other suitable gases, and / or plasma, or a combination thereof. In some embodiments, oxygen plasma is used to etch the material layer 210. In some embodiments, the anisotropic etching is performed at a temperature of about 250° C. to 450° C. for a time of about 20 seconds to about 300 seconds. If not completely consumed during the etching process, the patterned photoresist layer 220P is removed after the patterned material layer 210P is formed, for example, by plasma ashing or wet stripping. In the present disclosure, cross-linking polymers using a thiol oxidation reaction or a thiol-based free radical "click" reaction can improve cross-linking efficiency compared to traditional phenol-based cross-linking reactions. The improvement in cross-linking efficiency promotes an increase in the glass transition temperature (Tg) of the cross-linked polymer. Therefore, the photoresist composition of the present disclosure can effectively suppress the acid diffusion length, which leads to an improvement in line width roughness (LWR) and enhanced resolution, and the enhanced resolution can reach feature sizes below 22nm. Therefore, the photoresist composition and method according to the present disclosure provide improved semiconductor device feature resolution and density, and have the advantage of reducing defects in a more efficient process. One aspect of the present invention relates to a photoresist composition. The photoresist composition includes a photoactive compound and a thiol-containing polymer having the following structure (I): L 1. L 2 and L 3 is independently at each occurrence a direct bond or a plurality of connecting chains, which are oxo (—O—), carbonyl (—C(═O)—), carbonyloxy (—C(═O)—O—), oxycarbonyl (—O—C(═O)—), carbonate (—O—C(═O)—O—), C1 to C20 alkylene, C1 to C20 heteroalkylene, C4 to C20 cycloalkylene, C4 to C20 heterocycloalkylene, C5 to C20 arylene or C5 to C20 heteroarylene; R 1 is independently C5 to C20 aryl at each occurrence, wherein aryl is unsubstituted or substituted with halogen, carbonyl, hydroxyl or R s1 Replacement; R 2 is independently an acid-labile group at each occurrence, wherein the acid-labile group is unsubstituted or substituted with R s1 Replacement; R 3 is independently at each occurrence C1 to C20 alkyl, C1 to C20 heteroalkyl, C4 to C20 cycloalkylene, C2 to C30 heterocycloalkylene, C5 to C20 aryl, C5 to C20 heteroaryl, or R s1 Base; R s1 is SH, C1 to C20 thioalkyl, C3 to C20 thiocycloalkyl, C1 to C20 thiohydroxyalkyl, C2 to C20 thioalkoxy, C3 to C20 thioalkoxyalkyl, C1 to C20 thioacetyl, C2 to C20 thioacetylalkyl, thiocarboxyl, C2 to C20 thioalkylcarboxyl, C4 to C20 thiocycloalkylcarboxyl, C3 to C20 thiocarbocyclyl, or C3 to C20 thioheterocyclyl; R a 、R b and R c is independently H or C1 to C3 alkyl at each occurrence; and 0<x≤1, 0<y≤1, and 0≤z≤1, provided that R 1. R 2 and R One or more of 3 including R s1 , such that the compound of structure (I) comprises at least one R s1 . Another aspect of the present invention relates to a photoresist composition comprising an initiator, a photoacid generator, and a thiol-containing polymer having the following structure (II): L 1. L 2. L 3 and L 4 is independently at each occurrence a direct bond or a plurality of connecting chains, which connecting chains are oxo (—O—), carbonyl (—C(═O)—), carbonyloxy (—C(═O)—O—), oxycarbonyl (—O—C(═O)—), carbonate (—O—C(═O)—O—), C1 to C20 alkylene, C1 to C20 heteroalkylene, C4 to C20 cycloalkylene, C4 to C20 heterocycloalkylene, C5 to C20 arylene or C5 to C20 heteroarylene; R 1 is independently C5 to C20 aryl at each occurrence, wherein aryl is unsubstituted or substituted with halogen, carbonyl, hydroxyl or R s1 Replacement; R 2 is independently an acid-labile group at each occurrence; R 3 is independently at each occurrence C1 to C20 alkyl, C1 to C20 heteroalkyl, C4 to C20 cycloalkylene, C2 to C30 heterocycloalkylene, C5 to C20 aryl, C5 to C20 heteroaryl, or R s1 Base; R 4 is independently at each occurrence a free radically active functional group including an alkenyl or alkynyl group; R s1is SH, C1 to C20 thioalkyl, C3 to C20 thiocycloalkyl, C1 to C20 thiohydroxyalkyl, C2 to C20 thioalkoxy, C3 to C20 thioalkoxyalkyl, C1 to C20 thioacetyl, C2 to C20 thioacetylalkyl, thiocarboxyl, C2 to C20 thioalkylcarboxyl, C4 to C20 thiocycloalkylcarboxyl, C3 to C20 thiocarbocyclyl, or C3 to C20 thioheterocyclyl; R a 、R b and R c is independently H or C1 to C3 alkyl at each occurrence; and 0<x≤1, 0<y≤1, and 0≤z≤1, provided that R 1. R 3 or both including R s1 , such that the compound of structure (II) includes at least one R s1 . Another aspect of the present disclosure relates to a photoresist composition comprising 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): Among them L 1. L 2. L 3 and L 4 is independently at each occurrence a direct bond or a plurality of connecting chains, which connecting chains are oxo (—O—), carbonyl (—C(═O)—), carbonyloxy (—C(═O)—O—), oxycarbonyl (—O—C(═O)—), carbonate (—O—C(═O)—O—), C1 to C20 alkylene, C1 to C20 heteroalkylene, C4 to C20 cycloalkylene, C4 to C20 heterocycloalkylene, C5 to C20 arylene or C5 to C20 heteroarylene; R 5 is independently C5 to C20 aryl at each occurrence, wherein aryl is unsubstituted or substituted with halogen, carbonyl or hydroxy; R 6 is independently an acid-labile group at each occurrence; R 7 is independently at each occurrence C1 to C20 alkyl, C1 to C20 heteroalkyl, C4 to C20 cycloalkylene, C2 to C30 heterocycloalkylene, C5 to C20 aryl or C5 to C20 heteroaryl; R 8 is independently at each occurrence a free radically active functional group selected from alkenyl or alkynyl; R a 、R b and R c is independently at each occurrence H or C1 to C3 alkyl; and 0<x≤1, 0<y≤1, and 0≤z≤1. The foregoing summarizes the features of several embodiments so that those skilled in the art may better understand the aspects of the present disclosure. Those skilled in the art will appreciate that they may readily use this disclosure as a basis for designing or modifying other processes and structures for implementing the same purposes and / or achieving the same advantages of the embodiments introduced herein. Those skilled in the art will also recognize that such equivalent constructions do not depart from the spirit and scope of the present disclosure, and that various changes, substitutions, and replacements may be made herein for such equivalent constructions without departing from the spirit and scope of the present disclosure. 100: Method 102: Operation 104: Operation 106: Operation 108: Operation 110: Operation 112: Operation 114: Operation 200: Semiconductor Device 202: Substrate 210: Material Layer 210a: Recess 210b: Recess 210P: Patterned Material Layer 220: Photoresist Layer 220E: Exposure Area 220U: Unexposed Area 220P: Patterned Photoresist Layer 230: First Bake Process 240: Exposure Process 250: Mask 252: First Area 254: Second Area 260: Second Bake Process 270: Development Process A: Linker B: Linker C: Core Group Aspects of the present disclosure are best understood from the following detailed description when read in conjunction with the accompanying drawings. Please note that, in accordance with standard industry practice, various features are not drawn to scale. In fact, the dimensions of various features may be arbitrarily increased or decreased for clarity of discussion. FIG1 is a flow chart of a method for fabricating a semiconductor device according to some embodiments of the present disclosure. FIG2A through FIG2G are cross-sectional views of a semiconductor device fabricated using the method of FIG1 according to some embodiments of the present disclosure. FIG3A illustrates a first exemplary illustration of crosslinking a thiol-containing polymer through formation of an oxidized disulfide according to some embodiments of the present disclosure. FIG3B illustrates a second exemplary illustration of using a crosslinking agent for crosslinking a thiol-containing polymer according to some embodiments of the present disclosure. FIG3C illustrates a third exemplary illustration of crosslinking a thiol-ene polymer according to some embodiments of the present disclosure. FIG4 illustrates an exemplary crosslinking agent according to some embodiments of the present disclosure. FIG5 illustrates an exemplary illustration of crosslinking a thiol-free polymer through a thiol-ene reaction according to some embodiments of the present disclosure. FIG6A illustrates the structure of a polymer in an exposed region of a photoresist layer according to some embodiments of the present disclosure. FIG. 6B illustrates the structure of the polymer in the unexposed regions of the photoresist layer of FIG. 6A according to some embodiments of the present disclosure. Domestic deposit information (please note in the order of deposit organization, date, and number) None Foreign deposit information (please note in the order of deposit country, organization, date, and number) None 100: Method 102: Operation 104: Operation 106: Operation 108: Operation 110: Operation 112: Operation 114: Operation

Claims

1. A photoresist composition, comprising: A photoactive compound; And a thiol-containing polymer having the following structure (I); (I) Wherein: L1, L2, and L3 are each independently a direct bond or a plurality of connecting chains, which are oxo (—O—), carbonyl (—C(═O)—), carbonyloxy (—C(═O)—O—), oxycarbonyl (—O—C(═O)—), carbonate (—O—C(═O)—O—), C1 to C20 alkyl, C1 to C20 heteroalkyl, C4 to C20 cycloalkyl, C4 to C20 heterocycloalkyl, C6 to C20 aryl, or C5 to C20 heteroaryl; R1 is each independently a C6 to C20 aryl, wherein the aryl is unsubstituted or substituted with a halogen, a hydroxyl, or Rs1; R2 is each independently an acid-unstable group, wherein the acid-unstable group is unsubstituted or substituted with Rs1; R3, each time it appears, is independently a C1 to C20 alkyl, C1 to C20 heteroalkyl, C4 to C20 cycloalkyl, C2 to C30 heterocycloalkyl, C6 to C20 aryl, C5 to C20 heteroaryl, or Rs1 group; Rs1 is SH, C1 to C20 thioalkyl, C3 to C20 thiocycloalkyl, C1 to C20 thiohydroxyalkyl, C2 to C20 thioalkoxy, C3 to C20 thioalkoxyalkyl, thiocarboxyl, C2 to C20 thioalkylcarboxyl, C4 to C20 thiocycloalkylcarboxyl, C3 to C20 thiocarbocycloalkyl, or C3 to C20 thioheterocyclic group; Ra, Rb, and Rc are independently H or a C1 to C3 alkyl group each time they appear; and 0 < x < 1, 0 < y < 1, and 0 ≤ z < 1, provided that one or more of R1, R2, and R3 include Rs1, such that compounds of structure (I) include at least one Rs1.

2. The photoresist composition as claimed in claim 1, wherein R1 is an unsubstituted or Rs1-substituted hydroxyphenyl, an unsubstituted or Rs1-substituted hydroxynaphthyl, an unsubstituted or Rs1-substituted hydroxyanthrayl, an unsubstituted or Rs1-substituted phenyl, an unsubstituted or Rs1-substituted naphthyl, or an unsubstituted or Rs1-substituted anthraceneyl.

3. The photoresist composition as claimed in claim 1, wherein R2, each time it appears, is independently an unsubstituted or Rs1-substituted C4 to C12 alkyl, an unsubstituted or Rs1-substituted C4 to C12 cycloalkyl, an unsubstituted or Rs1-substituted C4 to C12 hydroxyalkyl, an unsubstituted or Rs1-substituted C4 to C12 alkoxy, an unsubstituted or Rs1-substituted C4 to C12 alkoxyalkyl, or an unsubstituted or Rs1-substituted three-dimensional cyclic structure.

4. The photoresist composition as claimed in claim 1, wherein the thiol-containing polymer has one of the following structures (Ia), (Ib), (Ic), and (Id): (Ia), (Ib), (Ic), or (Id), wherein R2 is independently C4 to C12 alkyl, C4 to C12 cycloalkyl, C4 to C12 hydroxyalkyl, C4 to C12 alkoxy, C4 to C12 alkoxyalkyl, or a three-dimensional cyclic structure each time it appears.

5. The photoresist composition as claimed in claim 4, wherein R2 has one of the following structures: , , , , , or.

6. A photoresist composition, comprising: One initiator; Acid-producing agent; And a thiol-containing polymer having the following structure (II); (II) Wherein: L1, L2, L3 and L4 are each independently a direct bond or a plurality of connecting chains, which are oxo (—O—), carbonyl (—C(═O)—), carbonyloxy (—C(═O)—O—), oxycarbonyl (—O—C(═O)—), carbonate (—O—C(═O)—O—), C1 to C20 alkyl, C1 to C20 heteroalkyl, C4 to C20 cycloalkyl, C4 to C20 heterocycloalkyl, C6 to C20 aryl or C5 to C20 heteroalkyl; R1 is each independently a C6 to C20 aryl, wherein the aryl is unsubstituted or substituted with a halogen, a hydroxyl or Rs1; R2 is each independently an acid-unstable group; R3, each time it appears, is independently a C1 to C20 alkyl, C1 to C20 heteroalkyl, C4 to C20 cycloalkyl, C2 to C30 heterocycloalkyl, C6 to C20 aryl, C5 to C20 heteroaryl, or Rs1 group; R4, each time it appears, is independently a free radical active functional group including an alkenyl or alkynyl group; Rs1 is SH, C1 to C20 thioalkyl, C3 to C20 thiocycloalkyl, C1 to C20 thiohydroxyalkyl, C2 to C20 thioalkoxy, C3 to C20 thioalkoxyalkyl, thiocarboxyl, C2 to C20 thioalkylcarboxyl, C4 to C20 thiocycloalkylcarboxyl, C3 to C20 thiocarbocycloalkyl, or C3 to C20 thioheterocyclic group; Ra, Rb, and Rc are independently H or a C1 to C3 alkyl group each time they appear; and 0 < x < 1, 0 < y < 1, and 0 ≤ z < 1, provided that R1, R3, or both include Rs1, such that compounds of structure (II) include at least one Rs1.

7. The photoresist composition as claimed in claim 6, wherein R2, each time it appears, is independently an unsubstituted or Rs1-substituted C4 to C12 alkyl, an unsubstituted or Rs1-substituted C4 to C12 cycloalkyl, an unsubstituted or Rs1-substituted C4 to C12 hydroxyalkyl, an unsubstituted or Rs1-substituted C4 to C12 alkoxy, an unsubstituted or Rs1-substituted C4 to C12 alkoxyalkyl, or an unsubstituted or Rs1-substituted three-dimensional cyclic structure.

8. The photoresist composition as claimed in claim 6, wherein the thiol-containing polymer has one of the following structures (IIa), (IIb) and (IIc): (IIa), (IIb) or (IIc), wherein R2 is independently C4 to C12 alkyl, C4 to C12 cycloalkyl, C4 to C12 hydroxyalkyl, C4 to C12 alkoxy, C4 to C12 alkoxyalkyl or a three-dimensional cyclic structure each time it appears.

9. A photoresist composition, comprising: One initiator; one photoacid generator; A thiol-containing crosslinking agent, comprising two or more thiol groups; And a thiol-free polymer having the following structure (III): (III) wherein: L1, L2, L3 and L4 are each independently a direct bond or a plurality of connecting chains, which are oxo (—O—), carbonyl (—C(═O)—), carbonyloxy (—C(═O)—O—), oxycarbonyl (—O—C(═O)—), carbonate (—O—C(═O)—O—), C1 to C20 alkylene, C1 to C20 heteroalkylene, C4 to C20 cycloalkylene, C4 to C20 heterocycloalkylene, C6 to C20 arylene or C5 to C20 heteroalkylene; R5 is each independently a C6 to C20 aryl group, wherein the aryl group is unsubstituted or substituted with a halogen or a hydroxyl group; R6 is each independently an acid-instable group; R7 is independently C1 to C20 alkyl, C1 to C20 heteroalkyl, C4 to C20 cycloalkyl, C2 to C30 heterocycloalkyl, C6 to C20 aryl, or C5 to C20 heteroaryl in each occurrence; R8 is independently a free radical active functional group selected from an alkenyl or alkynyl group in each occurrence; Ra, Rb, and Rc are independently H or a C1 to C3 alkyl group in each occurrence; and 0 < x < 1, 0 < y < 1, and 0 ≤ z < 1.

10. The photoresist composition as claimed in claim 9, wherein the thiol-free polymer has the following structure (IIIa): (IIIa) wherein R6 is a C4 to C12 alkyl, C4 to C12 cycloalkyl, C4 to C12 hydroxyalkyl, C4 to C12 alkoxy, C4 to C12 alkoxyalkyl or a three-dimensional cyclic structure.

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