Method of forming semiconductor device and photoresist component

Abstract

A method of forming a semiconductor device and a photoresist composition are provided. The method includes forming a photoresist layer over a substrate. The photoresist layer includes a polymer and a photoacid generator (PAG). The polymer includes a polymer backbone, an etch resistance promoting group chemically bonded to the polymer backbone, and an acid labile group (ALG) chemically bonded to the etch resistance promoting group. The method further includes exposing a portion of the photoresist layer to radiation to produce an acid at the exposed portion, baking the photoresist layer to cause cleavage of the acid-labile groups, and removing a portion of the photoresist layer to form a patterned photoresist layer.

Description

Technical Field

[0001] The present disclosure relates to photoresist compositions for forming photoresist layers and associated methods of forming semiconductor devices. Background Art

[0002] The semiconductor integrated circuit (IC) industry has experienced exponential growth. Technological advances in integrated circuit materials and design have produced generations of integrated circuits, each generation having smaller and more complex circuits than the previous generation. In the course of integrated circuit development, functional density (i.e., the number of interconnected devices per chip area) has generally increased, while geometry size (i.e., the smallest component (or line) that can be produced using a manufacturing process) has decreased. This process of shrinking generally provides benefits by increasing production efficiency and reducing associated costs. Such shrinking has also increased the complexity of processing and manufacturing integrated circuits. Summary of the invention

[0003] Some embodiments of the present disclosure provide a method for forming a semiconductor device, comprising: forming a photoresist layer above a substrate, the photoresist layer comprising a polymer and a photoacid generator (PAG), the polymer comprising a polymer backbone, an anti-etching promoting group chemically bonded to the polymer backbone, and an acid-labile group (ALG) chemically bonded to the anti-etching promoting group; exposing a portion of the photoresist layer to radiation to generate acid in the exposed portion; baking the photoresist layer to cause cleavage of the acid-labile group; and removing a portion of the photoresist layer to form a patterned photoresist layer.

[0004] Other embodiments of the present disclosure provide a method for forming a semiconductor device, comprising: depositing a material layer over a substrate; forming a photoresist layer over the material layer, the photoresist layer comprising a polymer and a photoacid generator (PAG), the polymer comprising a polymer backbone, an anti-etching promoting group chemically bonded to the polymer backbone, and an acid-labile group (ALG) chemically bonded to the anti-etching promoting group; exposing a portion of the photoresist layer to radiation to generate acid in the exposed portion; baking the photoresist layer to cause cleavage of the acid-labile group; removing a portion of the photoresist layer to form a patterned photoresist layer; and etching the material layer using the patterned photoresist layer as a mask.

[0005] Still other embodiments of the present disclosure provide a photoresist composition comprising a polymer comprising, in polymerized form, a monomer having the following structure (II):

[0006]

[0007] Wherein: L is a direct bond, or an alkylene, heteroalkylene, cycloalkylene ether, arylene ether, -CO-, -C(O)O-, -CONR a -, -O-, -S-, -S(O)-, -SO2-, or -P(O)OH- linker; R 1 It is an anti-etching promoting group; R 2 It is an acid-labile group; R 3 is H or an alkyl group; and R a is H or an alkyl group. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Various aspects of the present disclosure can be seen in the following detailed description and in conjunction with the accompanying Figure 1 Please read together for the best understanding. It is noted that, according to standard practice in the industry, the various features are not drawn to scale. In fact, the size of the various features may be arbitrarily increased or reduced for clarity of discussion.

[0009] Figure 1 The photoresist composition according to some embodiments of the present disclosure is shown, and the photoresist composition can be used to form a photoresist layer;

[0010] Figure 2 is a flow chart of a method for manufacturing a semiconductor device according to some embodiments of the present disclosure;

[0011] FIG. 3A to FIG. 3E According to some embodiments of the present disclosure, using Figure 2 A cross-sectional view of a semiconductor device manufactured by the method.

[0012]

Explanation of symbols

[0013] 100: Photoresist composition

[0014] 104:Polymer

[0015] 110: polymer main chain

[0016] 112: Anti-etching promoting group

[0017] 114: Acid-labile group

[0018] 116: Resistant ingredients

[0019] 118: Photoacid generator

[0020] 120:Solvent

[0021] 200: Method

[0022] 210: Block

[0023] 220: Block

[0024] 230: Block

[0025] 240: Block

[0026] 250: Blocks

[0027] 260: Block

[0028] 300:Semiconductor devices

[0029] 302:Substrate

[0030] 310: Material layer

[0031] 310P: Patterned material layer

[0032] 320: Photoresist layer

[0033] 320A: Exposure part

[0034] 320B: Unexposed part

[0035] 320P: Patterned photoresist layer

[0036] 340: Opening

[0037] ALG: Acid Labile Group

[0038] ERP: Etching resistance promoting group

[0039] PAG: Photoacid Generator DETAILED DESCRIPTION

[0040] The disclosure that follows provides many different implementations or embodiments for implementing different features of the provided subject matter. Specific embodiments of components and arrangements are described below to simplify the disclosure. Of course, these are merely embodiments and are not restrictive. For example, in the subsequent description, a first feature is formed above or on a second feature, and an implementation in which the first feature and the second feature are formed in direct contact may be included, and an additional feature may be formed between the first feature and the second feature, so that the first feature and the second feature may not be in direct contact. In addition, the disclosure may repeat reference numerals and / or letters in various embodiments. Such repetition is for the purpose of simplification and clarity, and the repetition itself does not mean the relationship between the various embodiments and / or configurations discussed.

[0041] Additionally, to facilitate describing the relationship of one element or feature to another element or feature as depicted in the figures, spatially relative terms may be used herein, such as "below," "below," "lower," "above," "upper," and the like. 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 similarly accordingly.

[0042] When describing the compounds, compositions, methods and processes of the present disclosure, the following terms have the following meanings unless otherwise indicated.

[0043] As described herein, the compounds disclosed herein may be optionally substituted with one or more substituents, such as described generally below, or as exemplified by specific classes, subclasses, and species of the present disclosure. It should be understood that the term "optionally substituted" is used interchangeably with the phrase "substituted or unsubstituted". In general, the term "substituted", whether or not preceded by the term "optionally", refers to the replacement of one or more hydrogen radicals in a given structure with a group of a specified substituent. Unless otherwise specified, an optionally substituted group may have a substituent at each substitutable position of the group. When more than one position in a given structure may be substituted with more than one substituent selected from a specified group, the substituent at each position may be the same or different.

[0044] As used herein, the term "polymer" generally refers to a molecule composed of a plurality of repeating structural units linked by covalent chemical bonds, characterized by a large number of repeating units (e.g., equal to or greater than 20 repeating units, typically equal to or greater than 100 repeating units, typically equal to or greater than 300 repeating units) and a number average molecular weight greater than or equal to 5,000 Daltons (Da) or 5 kDa, such as greater than or equal to 10 kDa, 15 kDa, 20 kDa, 30 kDa, 40 kDa, 50 kDa, or 100 kDa. A polymer is typically the polymerization product of one or more monomer precursors. The term polymer includes homopolymers, i.e., polymers composed of repeating units of a single monomer. The term polymer also includes copolymers formed when two or more different types of monomers are linked in the same polymer. Copolymers may contain two or more monomer subunits, and include random, block, alternating, multi-block, graft, tapered, and other copolymers. The term "crosslinked polymer" generally refers to a polymer having one or more links between at least two polymer chains, which may result from multivalent monomers that form crosslinking sites upon polymerization.

[0045] As used herein, the term "group" may refer to a functional group of a chemical compound. A group of a compound of the present disclosure refers to an atom or a collection of atoms that is part of a compound. A group of the present disclosure may be attached to other atoms of the compound via one or more covalent bonds. Groups may also be characterized according to their valence state. The present disclosure includes groups characterized as monovalent, divalent, trivalent, etc.

[0046] As used herein, a wavy line in a chemical structure may be used to indicate a bond to the rest of the molecule. For example In e.g. In the example above, ' may be used to indicate that a given moiety, in this example the cyclohexyl moiety, is attached to the molecule via a bond "terminated" by a wavy line.

[0047] As used herein, "linker" refers to a continuous chain of at least one atom (e.g., carbon, oxygen, nitrogen, sulfur, phosphorus, and combinations thereof) that connects one part of a molecule to another part of the same molecule or to a different molecule, part, or solid support (e.g., a particle). The linker can connect the molecule by covalent bonds or other means, such as ionic bonds or hydrogen bond interactions. In some embodiments, the linker is a heteroatom linker (e.g., comprising 1 to 10 Si, N, O, P, or S atoms), a heteroalkylene (e.g., comprising 1 to 10 Si, N, O, P, or S atoms, and an alkylene chain), or an alkylene linker (e.g., comprising 1 to 12 carbon atoms). In some embodiments, the linker may comprise an ether (-O-), an ester (-OC(=O)-), or a carbonate (-OC(=O)O-) linkage.

[0048] "Hydroxy" or "hydroxyl" refers to an -OH group.

[0049] As used herein, "aromatic" or "aromatic group" refers to a primary group of unsaturated cyclic hydrocarbons containing one or more rings. Aromatic groups may contain carbon (C), nitrogen (N), oxygen (O), sulfur (S), boron (B), or any combination thereof. At least some carbon is included. Aromatics include both aryl rings and heteroaryl rings.

[0050] As used herein, "aliphatic" or "aliphatic group" refers to a straight or branched chain C 1-12 A hydrocarbon chain, either completely saturated or containing one or more unsaturated units but not aromatic, 3-8 Hydrocarbon or bicyclic C 8-12Hydrocarbons (also referred to herein as "cycloalkyls") having a single point of attachment to the rest of the molecule, wherein any individual ring in the bicyclic ring system has from 3 to 7 members. For example, suitable aliphatic groups include, but are not limited to, linear or branched alkyl, alkenyl, alkynyl groups, and mixtures thereof, such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl, or (cycloalkyl)alkenyl.

[0051] "Alkyl" or "alkyl group" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from 1 to 12 carbon atoms (C1-C 12 The term "alkyl" refers to a methyl group (alkyl), 1 to 8 carbon atoms (C1-C8 alkyl) or 1 to 6 carbon atoms (C1-C6 alkyl), and is attached to the rest of the molecule through a single bond, such as methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, n-pentyl, 1,1-dimethylethyl (tert-butyl), 3-methylhexyl, 2-methylhexyl, or the like. Unless otherwise specifically stated in the specification, an alkyl group is optionally substituted.

[0052] "Alkylene" or "alkylene" refers to a straight or branched divalent hydrocarbon chain that connects the rest of the molecule to a radical, consisting solely of carbon and hydrogen, containing no unsaturation, and having from 1 to 12 carbon atoms, such as methylene, ethylene, propylene, n-butylene, or the like. The alkylene chain is attached to the rest of the molecule by a single bond and to the radical group by a single bond. The sites of attachment of the alkylene chain to the rest of the molecule and the radical group may be through one carbon or any two carbons within the chain. Unless otherwise specifically stated in the specification, alkylene is optionally substituted.

[0053] "Aryl" or "aryl group" refers to a ring system comprising at least one carbocyclic aromatic ring. In some embodiments, the aryl group comprises 6 to 18 carbon atoms. The aryl ring can be a monocyclic, bicyclic, tricyclic or tetracyclic system, which may include a fused ring system or a bridged ring system. Aryl includes, but is not limited to, aryl groups derived from anthracene, acenaphthene, phenanthrene, anthracene, azulene, benzene, anthracene, fluoranthene, fluorene, as-indanene, s-indanene, indane, indene, naphthalene, phenanthrene, pyrene, pyrene and triphenylene. Unless otherwise specifically stated in the specification, aryl is optionally substituted.

[0054] "Arylene" or "arylene group" refers to a divalent group derived from an aryl group as defined herein. In some embodiments, an arylene group is a divalent group derived from an aryl group by removing hydrogen atoms from two intra-ring carbon atoms of the aromatic ring of the aryl group. The arylene group in some compounds functions as an attachment group and / or a spacer group. The arylene group in some compounds functions as a chromophore, fluorophore, aromatic antenna, dye, and / or imaging group. The compounds of the present disclosure include substituted and / or unsubstituted C5-C 30 Arylene, C5-C 20 Arylene, and C5-C 10 Arylene groups. "Cycloalkyl" or "cycloalkyl group" refers to a stable non-aromatic monocyclic or polycyclic carbocyclic ring, which may include a fused ring system or a bridged ring system, having from 3 to 15 carbon atoms, preferably from 3 to 10 carbon atoms, and being saturated or unsaturated, attached to the rest of the molecule via a single bond. Monocyclic cycloalkyls include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Polycyclic cycloalkyls include, for example, adamantyl, norbornyl, naphthyl, 7,7 dimethylbicyclo-[2.2.1]heptyl, or the like. Unless otherwise specifically stated in the specification, a cycloalkyl group is optionally substituted.

[0055] "Cycloalkylene" or "cycloalkylene group" refers to a divalent group derived from a cycloalkyl group as defined herein. The cycloalkyl group in some compounds functions as an attachment group and / or a spacer group. The compounds of the present disclosure may have substituted and / or unsubstituted C3-C 20 Cycloalkylene, C3-C 10 cycloalkylene group, and a C3-C5 cycloalkylene group.

[0056] "Heteroalkyl" refers to an alkyl group as defined above, containing at least one heteroatom (e.g., N, O, P, or S) within the alkyl group or at the terminus of the alkyl group. In some embodiments, the heteroatom is within the alkyl group (i.e., the heteroalkyl group contains at least one carbon-[heteroatom] x -carbon bond, wherein x is 1, 2 or 3). In other embodiments, the heteroatom is at the end of the alkyl group, and is therefore used to connect the alkyl group to the rest of the molecule (e.g., M1-HA), wherein M1 is part of the molecule, H is a heteroatom, and A is an alkyl group). Unless otherwise specifically stated in the specification, the heteroalkyl group is optionally substituted. Exemplary heteroalkyl groups include ethylene oxide (e.g., polyethylene oxide), optionally including a phosphorus-oxygen bond, such as a phosphodiester bond.

[0057] "Heteroalkylene" or "heteroalkylene group" refers to an alkylene group as defined above, containing 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 contains at least one carbon-[heteroatom]-carbon bond, where x is 1, 2, or 3). In other embodiments, the heteroatom is at the terminus of the alkylene, thus serving to connect the alkylene to the rest of the molecule (e.g., M1-HA-M2, where M1 and M2 are part of the molecule, H is a heteroatom, and A is an alkylene). Unless otherwise specifically stated in the specification, a heteroalkylene group is optionally substituted.

[0058] The term "heteroatom" as used in the context of a "heteroatom linker" refers to a linker group consisting of one or more heteroatoms. Exemplary heteroatom linkers include single atoms and multiple heteroatoms selected from the group consisting of O, N, P, and S, such as linkers having the formula -P(O-)(=O)O- or -OP(O-)(=O)O-, as well as multimers thereof and combinations thereof.

[0059] "Heteroaryl" or "heteroaryl group" refers to a 5-30 membered ring system comprising 1 to 13 carbon atoms, 1 to 6 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, and at least one aromatic ring. For the purposes of certain embodiments of the present disclosure, heteroaryl can be a monocyclic, bicyclic, tricyclic or tetracyclic system, which can include fused ring systems or bridged ring systems; and the nitrogen, carbon or sulfur atoms in the heteroaryl can be optionally oxidized; the nitrogen atom can be optionally quaternized. Examples include, but are not limited to, acridinyl, acridinyl, benzimidazolyl, benzothiazolyl, benzindolyl, benzodioxolyl, benzofuranyl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl, benzo[b][1,4]dioxepanyl, 1,4-benzodioxanyl, benzonaphthofuranyl, benzoxazolyl, benzodioxolyl, benzodioxinyl, benzopyranyl yl, benzopyrone, benzofuranyl, benzofuranone, benzothiophenyl (benzothiophenyl), benzotriazolyl, benzo[4,6]imidazo[1,2-a]pyridyl, benzoxazolinyl, benzimidazolylsulfonyl, carbazolyl, octinyl, dibenzofuranyl, dibenzothiophenyl, furanyl, furanyl, isothiazolyl, imidazolyl, indazolyl, indolyl, indazolyl, isoindolyl, indolyl, isoindolyl, isoquinolyl, indolizinyl, isoxazolyl, naphthyridinyl, oxadiazolyl, 2-oxoazepinyl, oxazolyl, oxiranyl, 1-pyridyl oxide, 1-pyrimidinyl oxide, 1-pyrazinyl oxide, 1-pyridazinyl oxide, 1-phenyl-1H-pyrrolyl, phenazinyl, phenothiazinyl, phenoxazinyl, phthalazinyl, pteridinyl, pteridinyl, purinyl, pyrrolyl, pyrazolyl, pyridinyl, pyridinyl, Pyrazinyl, pyrimidinyl, pyrimidinyl, pyridazinyl, pyrrolyl, pyrido[2,3-d]pyrimidinyl, quinazolinyl, quinazolinyl, quinoxalinyl, quinoxalinyl, quinolyl, isoquinolyl, tetrahydroquinolyl, thiazolyl, thiadiazolyl, thieno[3,2-d]pyrimidin-4-onyl, thieno[2,3-d]pyrimidin-4-onyl, triazolyl, tetrazolyl, triazinyl, and thiophenyl (i.e., thienyl). Unless stated otherwise specifically in the specification, heteroaryl groups are optionally substituted.

[0060] "Heteroarylene" or "heteroarylene group" refers to a divalent group derived from a heteroaryl group as defined herein. In some embodiments, a heteroarylene group is a divalent group derived from a heteroaryl group by removing hydrogen atoms from two intracyclic carbon atoms or intracyclic nitrogen atoms of a heteroaromatic or aromatic ring of a heteroaryl group. In some compounds, a heteroarylene group functions as an attachment group and / or a spacer group. In some compounds, a heteroarylene group functions as a chromophore, an aromatic antenna, a fluorophore, a dye, and / or an imaging group. The compounds of the present disclosure include substituted and / or unsubstituted C5-C30 Heteroarylene, C5-C 20 Heteroarylene, and C5-C 10 Heteroarylene groups.

[0061] "Heterocyclic" or "heterocyclic group" refers to a stable 3- to 18-membered aromatic or non-aromatic ring containing 1 to 12 carbon atoms and from 1 to 6 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur. Unless otherwise specifically stated in the specification, the heterocycle may be a monocyclic, bicyclic, tricyclic or tetracyclic system, which may include fused ring systems or bridged ring systems; 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. Various examples of aromatic heterocycles are listed below in the definition of heteroaryl (i.e., heteroaryl is a subset of heterocycle). Various examples of non-aromatic heterocycles include, but are not limited to, dioxolanyl, thienyl [1,3] dithienyl, decahydroisoquinolinyl, imidazolinyl, imidazolidinyl, isothiazolidinyl, isoxazolidinyl, morpholinyl, octahydroindolyl, octahydroisoindolyl, 2-oxopiperazinyl, 2-oxopiperidinyl, 2-oxopyrrolidinyl, oxazolidinyl, piperidinyl, piperazinyl, 4-piperidonyl, pyrrolidinyl, pyrazolidinyl, pyrazolopyrimidinyl, quinuclidinyl, thiazolidinyl, tetrahydrofuranyl, trioxanyl, trithianyl, triazinyl, tetrahydropyranyl, thiomorpholinyl, thiomorpholinyl, 1 oxo-thiomorpholinyl, and 1,1-dioxo-thiomorpholinyl. Unless otherwise specifically stated in the specification, heterocyclic groups are optionally substituted.

[0062] As used herein, the term "substituted" refers to any of the above groups in which at least one hydrogen atom (e.g., 1, 2, 3 or all of the hydrogen atoms) is replaced by a bond to a non-hydrogen atom, such as, but not limited to, halogen atoms such as F, Cl, Br and I; oxygen atoms in groups such as hydroxyl, alkoxy and ester groups; sulfur atoms in groups such as thiol, thioalkyl, sulfone, sulfonyl and sulfoxide groups; nitrogen atoms in groups such as amines, amides, alkylamines, dialkylamines, arylamines, alkylarylamines, diarylamines, N-oxides, imides and enamines; silicon atoms in groups such as trialkylsilyl, dialkylarylsilyl, alkyldiarylsilyl, and triarylsilyl groups; 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) with a heteroatom, such as oxygen in oxo, ketone, carboxylic acid, and ester groups; and nitrogen in groups such as imine, oxime, ketal, and nitrile. 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)Rh 、-NR g C(=O)NR g R h 、-NR g C(=O)OR h 、-NR g S02R h 、-OC(=O)NR g R h 、-OR g 、-SR g , -SOR g 、-SO2R g ,-OSO2R g 、-SO2OR g , =NSO2R g , and -SO2NR g R h "Substituted" also 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 、-C(=O)NR g Rh, -CH2SO2R g , and -CH2SO2NR g R h In the above text, R g and R h are the same or different and are independently hydrogen, alkyl, alkoxy, alkylamino, thioalkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, haloalkyl, heterocyclyl, N-heterocyclyl, heterocyclylalkyl, heteroaryl, N-heteroaryl, and / or heteroarylalkyl. "Substituted" also refers to any of the above groups, wherein one or more hydrogen atoms are replaced by bonds to amino, cyano, hydroxy, imino, nitro, oxo, thio, halogen, alkyl, alkoxy, alkylamino, thioalkyl, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, haloalkyl, heterocyclyl, N-heterocyclyl, heterocyclylalkyl, heteroaryl, N-heteroaryl, and / or heteroarylalkyl groups. In addition, each of the above multiple substituents may also be optionally substituted with one or more of the above substituents.

[0063] Integrated circuit manufacturing uses one or more photolithography processes to transfer geometric patterns to a film or substrate. The geometric shapes and patterns on the semiconductor form complex structures that allow dopants, electrical properties, and wires to complete circuits and achieve technological goals. In the photolithography process, 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 mask. The mask contains transparent and opaque features that form a pattern that will be created in the photoresist layer. After the photoresist layer is exposed to radiation, it is developed in a developer (chemical solution). The developer removes multiple portions of the photoresist layer, thereby forming a photoresist pattern, which may include multiple line patterns and / or multiple groove patterns. The photoresist pattern is then used as an etch mask in a subsequent etching process to transfer the pattern to the layer below. There are two types of processes commonly used to develop the exposed photoresist layer: positive tone development (PTD) process and negative tone development (NTD) process. The positive developer process uses a positive developer that selectively dissolves and removes multiple exposed portions of the photoresist layer. The negative developer process uses a negative developer that selectively dissolves and removes multiple unexposed portions of the photoresist layer. The quality of the photoresist pattern directly affects the quality of the integrated circuit device. As integrated circuit technology continues to move toward smaller technology nodes (e.g., down to 14 nm, 10 nm and below), the resolution, roughness (e.g., line edge roughness (LER) and / or line width roughness (LWR)) and / or contrast of the photoresist pattern are highly relevant.

[0064] Advanced photolithography materials, such as chemically amplified resist (CAR) materials, have been introduced to increase the sensitivity of the photoresist layer to radiation, thereby maximizing the utilization of the radiation. The photoresist layer formed by the chemically amplified resist material includes a polymer that is resistant to integrated circuit processes (e.g., etching processes) and an acid generator (e.g., a photoacid generator (PAG)). When exposed to radiation, the photoacid generator generates an acid that functions as a catalyst to cause a chemical reaction that increases (or decreases) the solubility of the exposed portion of the resist layer. For example, in some embodiments, the acid generated by the photoacid generator catalyzes the cleavage of acid labile groups (ALGs) bonded to the polymer, thereby changing the solubility of multiple exposed portions of the photoresist layer. However, chemically amplified resist reactions may cause certain undesirable side effects. For example, photolithography processes typically include a post-exposure bake (PEB) step. The cleaved acid-labile groups are volatile and evaporate in the post-exposure bake process, causing film shrinkage in the exposed areas. This results in poor pattern profile and / or poor resolution.

[0065] The present disclosure provides a photoresist material with good developer solubility, high resolution and etching resistance, but the volume shrinkage is reduced. In a plurality of embodiments of the present disclosure, a photoresist material is provided, and this photoresist material has an acid-labile group connected to a polymer backbone via an etching-resistant promoting group, and the size of this etching-resistant promoting group is greater than or equal to the size of the acid-labile group. After the cracking of the acid-labile group, the etching-resistant promoting group remains attached to the polymer backbone, thus reducing or eliminating the volume shrinkage of the photoresist layer caused by the evaporation of the acid-labile group (i.e., degassing). Therefore, a good pattern profile with reduced line edge roughness and line width roughness and high resolution and etching resistance is achieved.

[0066] Figure 1A photoresist composition 100 is illustrated that can be used to form a photoresist layer according to some embodiments of the present disclosure. For purposes of the following discussion, the photoresist composition 100 includes a negative photoresist material for forming a negative photoresist layer, wherein multiple portions of the photoresist layer exposed to radiation become insoluble in a developer, and multiple unexposed portions of the photoresist layer remain soluble in the developer. Alternatively, the present disclosure contemplates embodiments in which the photoresist composition 100 includes a positive photoresist material for forming a positive photoresist layer, wherein multiple portions of the photoresist layer exposed to radiation become soluble in a developer, and multiple unexposed portions of the photoresist layer remain insoluble in the developer. In some embodiments, the photoresist composition 100 is sensitive to radiation having a wavelength less than about 250 nanometers. For the sake of clarity, the photoresist composition 100 has been simplified. Figure 1 , in order to better understand the inventive concepts of the present disclosure. Additional features may be added to the photoresist component 100, and some of the features described below may be replaced, modified, or deleted in other embodiments of the photoresist component 100.

[0067] In some embodiments, the photoresist composition 100 includes a photosensitive polymer 104 that is resistant to integrated circuit processes used during integrated circuit fabrication. For example, the polymer 104 is etch resistant to an etching process and / or implant resistant to an implant process. The polymer 104 includes a polymer backbone 110. In some embodiments, the polymer backbone 110 is a hydrocarbon backbone, including a backbone of a poly(norbornene)-co-maleic anhydride (COMA) polymer, a poly(4-hydroxystyrene) (PHS) polymer, a phenol-formaldehyde (hakelite) polymer, a polyethylene (PE) polymer, a polypropylene (PP) polymer, a polycarbonate polymer, a polyester polymer, or an acrylate-based polymer, such as a poly(methyl methacrylate) (PMMA) polymer.

[0068] The polymer 104 has a plurality of functional groups chemically bonded to the polymer backbone 110, such as an etch resistance promoting (ERP) group 112 and an acid labile group (ALG) 114. The etch resistance promoting group 112 is suitable for increasing the etch resistance of the polymer 104 for wet etching or dry etching processes. The acid labile group 114 is chemically bonded to the etch resistance promoting group 112 and is suitable for changing the solubility of the polymer 104 in response to an acid. For example, when exposed to an acid, the acid labile group 114 is cleaved from the side chain of the polymer 104, thereby changing the solubility and / or polarity of the plurality of exposed portions of the photoresist layer. In some embodiments, the acid labile group 114 may have a one-dimensional, two-dimensional, or three-dimensional structure to control the activation energy. The activation energy is the minimum energy for initiating the deprotection reaction of the acid labile group 114.

[0069] In some embodiments, the resist component 116 may be bonded to the polymer backbone 110. The resist component 116 is configured to interact with other components of the photoresist component 100. In some embodiments, the resist component 116 may include a thermal acid generator (TAG), a quencher (base), a chromophore, a cross-linking agent, a surfactant, and / or other suitable components, depending on the requirements of the photoresist component 100. The present disclosure also contemplates embodiments in which the resist component 116 interacts with components of the photoresist component 100 but is not chemically bonded (or connected) to the polymer backbone 110, such as in Figure 1 as shown in .

[0070] In some embodiments, polymer 104 includes a monomer unit having an acid labile group bonded to the polymer backbone via an anti-etching promoting group. In some embodiments, polymer 104 includes a monomer unit having the following structure (I):

[0071]

[0072] in:

[0073] L is a direct bond, alkylene, heteroalkylene, cycloalkylene ether, arylene ether, -CO-, -C(O)O-, -CONR a -, -O-, -S-, -S(O)-, -SO2-, or -P(O)OH- linkers;

[0074] R 1 It is an anti-etching promoting group;

[0075] R 2 It is an acid-labile group;

[0076] R a is H or an alkyl group; and

[0077] n is an integer from 1 to 500.

[0078] In some embodiments, L is -(CO)O-.

[0079] In some embodiments, R 1 is an alkylene, heteroalkylene, cycloalkylene, cycloheteroalkylene, or arylene group.

[0080] In some embodiments, R 1 It is C 1-12 Alkylene.

[0081] In some embodiments, R 1 It is a ring (C3-12 In some embodiments, the ring (C 3-12 ) The alkylene group is a bicyclic alkylene group.

[0082] In some embodiments, R 1 It is a ring (C 3-12 In some embodiments, the ring (C 3-12 )Heteroalkylene is a bicyclic heteroalkylene.

[0083] In some embodiments, R 1 It is a phenylene group.

[0084] In some embodiments, R 1 Has one of the following structures:

[0085]

[0086] In some embodiments, R 2 is an alkyl, heteroalkyl, cycloalkyl, or cycloheteroalkyl group.

[0087] In some embodiments, R 2 It is C 1-12 alkyl.

[0088] In some embodiments, R 2 It is a ring (C 3-12 In some embodiments, the ring (C 3-12 ) The alkyl group is a bicyclic alkyl group.

[0089] In some embodiments, R 2 It is n-butyl, tert-butyl, methyladamantyl, methylcyclopentyl, methylcyclohexyl, ethylcyclopentyl, ethylcyclohexyl, isopropyl, cyclopentyl, isopropylcyclohexyl, tert-butoxycarbonyl, isonorbornyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, 3-methyltetrahydrofuran, 2-methyltetrahydrofuran, lactone, or 2-methyltetrahydropyran (THP).

[0090] In some embodiments, R 2 Has one of the following structures:

[0091]

[0092] In some embodiments, R a It is H or -CH3.

[0093] In some embodiments, monomer unit (I) has the following structure (Ia):

[0094]

[0095] in:

[0096] L, R 1 , R 2 , and n are as defined above; and

[0097] R 3 is H or alkyl.

[0098] In some embodiments, R 3 It is -CH3.

[0099] In some embodiments, monomer unit (Ia) has the following structure:

[0100]

[0101] Where n is 1 to 500.

[0102] In some embodiments, polymer 104 comprises, in polymerized form, a monomer having the following structure (II):

[0103]

[0104] in:

[0105] L is a direct bond, or alkylene, heteroalkylene, cycloalkylene ether, arylene ether, -CO-, -C(O)O-, -CONR a -, -O-, -S-, -S(O)-, -SO2-, or -P(O)OH- linkers;

[0106] R 1 is an alkylene, heteroalkylene, cycloalkylene, cycloheteroalkylene, or arylene group;

[0107] R 2 is an alkyl, heteroalkyl, cycloalkyl, or cycloheteroalkyl group;

[0108] R 3 is H or an alkyl group; and

[0109] R a is H or an alkyl group.

[0110] In some embodiments, L is -(CO)O-, and monomer (II) has the following structure (IIa):

[0111]

[0112] In some embodiments, the monomer has the following structure:

[0113]

[0114] The photoresist composition 100 also includes an acid generator, such as a photoacid generator (PAG) 118, which generates an acid upon absorbing radiation. Thus, when exposed to radiation, the photoacid generator 118 catalyzes the cleavage of the acid-labile groups 114 from the side chains of the polymer 104, deprotects the acid-labile groups 114 in the plurality of exposed portions of the photoresist layer, and changes the properties (e.g., polarity and / or solubility) of the plurality of exposed portions of the photoresist layer. In some embodiments, the photoacid generator 118 includes a fluorine-containing functional group, such as a perfluorosulfonate, a diphenyliodonium trifluoromethanesulfonate, a diphenyliodonium nonafluorobutanesulfonate, a triphenylsulfonium trifluoromethanesulfonate, a triphenylsulfonium nonafluorobutanesulfonate, a triphenylsulfonium bis(perfluoromethanesulfonyl)imide, a fluorine-containing functional group, or a combination thereof. In some embodiments, the photoacid generator 118 includes a benzene ring-based functional group, a heterocyclic ring-based functional group, other suitable functional groups, or a combination thereof. In various embodiments where the photoresist composition 100 includes a quencher, the quencher neutralizes the acid, such that the quencher inhibits the acid generated by the photoacid generator 118 from reacting with the acid-labile group 114. In some embodiments, the quencher is a photodecomposable base (PDB) component.

[0115] In some embodiments, the photoacid generator 118 may include a combination of cations and anions. Examples of photoacid generators according to various embodiments of the present disclosure include α-(trifluoromethylsulfonyloxy)-bicyclo[2.2.1]hept-5-ene-2,3-dicarbon-o-imide (MDT), N-hydroxy-naphthalene dicarboxylic acid imide (DDSN), benzoin toluenesulfonate, tert-butylphenyl-α-(p-toluenesulfonyloxy) acetate and tert-butyl-α-(p-toluenesulfonyloxy) acetate, triaryl germanium and diaryl iodonium hexafluoroantimonate, hexafluoroarsenate, trifluoromethanesulfonate, perfluorooctanesulfonic acid iodine, N-camphorsulfonyloxynaphthalene dicarboxylic acid imide, N-pentafluorobenzenesulfonyloxynaphthalene dicarboxylic acid imide, amines, ionic iodonium sulfonates such as diaryliodonium (alkyl or aryl) sulfonates and bis-(di-tert-butylphenyl)iodonium bornyl sulfonate, perfluoroalkane sulfonates such as perfluoropentane sulfonate, perfluorooctane sulfonate, perfluoromethane sulfonate, aryl (e.g., phenyl or benzyl) trifluoromethane sulfonates such as triphenylgermanium trifluoromethane sulfonate or bis(tert-butylphenyl)iodonium trifluoromethane sulfonate; pyrogallol derivatives (e.g., trimesylate of pyrogallol), trifluoromethane sulfonates of hydroxyimides, α,α'-bissulfonyldiazomethane, sulfonates of nitro-substituted benzyl alcohols, naphthoquinone-4-diazide, alkyl disulfones, or the like.

[0116] In some embodiments, the cation is selected from the group consisting of:

[0117]

[0118] In some embodiments, the anion is selected from the group consisting of:

[0119]

[0120]

[0121] In some embodiments, the photoresist composition 100 also includes a solvent 120. In some embodiments, the solvent 120 is an aqueous solvent. In some embodiments, the solvent 120 is an organic-based solvent, such as propylene glycol methyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 1-ethoxy-2-propanol (PGEE), γ-butyrolactone (GBL), cyclohexanone (CHN), ethyl lactate (EL), methanol, ethanol, propanol, n-butanol, acetone, dimethylformamide (DMF), isopropyl alcohol (IPA), tetrahydrofuran (THF), methyl isobutyl carbinol (MIBC), n-butyl acetate (nBA), 2-heptanone (MAK), other suitable organic-based solvents, or combinations thereof.

[0122] When forming the photoresist composition 100, the polymer 104, the photoacid generator 118, and any resist components are mixed in a solvent 120 to form a resist solution for photolithography.

[0123] Figure 2 A flow chart of a method 200 for manufacturing a semiconductor device 300 is depicted according to some embodiments of the present disclosure. The method 200 may be implemented in whole or in part via a system that employs advanced lithography processes, such as deep ultraviolet (DUV) lithography, extreme ultraviolet (EUV) lithography, electron beam lithography, x-ray lithography, and / or other lithography to improve lithography resolution. At block 210, a material layer is formed over a substrate. At block 220, a photoresist layer is formed over the material layer. At block 230, the photoresist layer is exposed to, for example, patterned radiation. At block 240, the photoresist layer is baked, for example, via a post-exposure bake process. At block 250, the photoresist layer is developed to form a patterned photoresist layer. At block 260, the material layer is etched using the patterned photoresist layer as a mask. Additional steps may be provided before, during, and after the method 200, and some of the steps described may be moved, replaced, or deleted for additional embodiments of the method 200.

[0124] FIG. 3A to FIG. 3E2 is a partial cross-sectional view of a semiconductor device 300 at various stages of fabrication of method 200 according to some embodiments of the present disclosure. Semiconductor device 300 may be an intermediate structure during fabrication of an integrated circuit or a portion thereof. An integrated circuit may include logic circuits, memory structures, passive components (e.g., resistors, capacitors, and inductors), and 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 field effect transistors (FinFETs), other three-dimensional (3D) field effect transistors, and combinations thereof. Semiconductor device 300 may include multiple semiconductor devices (e.g., multiple transistors) that may be interconnected.

[0125] refer to Figure 3A , semiconductor device 300 includes substrate 302. In some embodiments, substrate 302 may be a bulk semiconductor substrate that includes one or more semiconductor materials. In some embodiments, substrate 302 may include silicon, silicon germanium, carbon-doped silicon (Si:C), silicon germanium carbide, or other suitable semiconductor materials. In some embodiments, substrate 302 is composed entirely of silicon.

[0126] In some embodiments, substrate 302 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 introduce strain into substrate 302 to enhance performance. For example, the epitaxial layers include a semiconductor material different from the bulk semiconductor substrate, such as a layer of silicon germanium overlying bulk silicon, or a layer of silicon overlying bulk silicon germanium. In some embodiments, the epitaxial layers incorporated into substrate 302 are formed via 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.

[0127] In some embodiments, substrate 302 may be a semiconductor on insulator (SOI) substrate. In some embodiments, the semiconductor on insulator substrate includes a semiconductor layer, such as a silicon layer formed on an insulating layer. In some embodiments, the insulator layer is a buried oxide (BOX) layer including silicon oxide or silicon germanium oxide. The insulating layer is provided on a handle substrate, such as a silicon substrate. In some embodiments, the semiconductor on insulator substrate is formed using separation by implanted oxygen (SIMOX) or other suitable techniques, such as wafer bonding and grinding.

[0128] In some embodiments, substrate 302 may also include a dielectric substrate such as silicon oxide, silicon nitride, silicon oxynitride, a low-k dielectric, silicon carbide, and / or other suitable layers.

[0129] In some embodiments, substrate 302 may also include various p-type doped regions and / or n-type doped regions, implemented via processes such as ion implantation and / or diffusion. Those doped regions include n-wells, p-wells, lightly doped regions (LDDs), and various channel doping profiles, which are configured to form various integrated circuit devices, such as CMOS transistors, image sensors, and / or light emitting diodes (LEDs). Substrate 302 may also include other functional features, such as resistors and / or capacitors formed in and / or on substrate 302.

[0130] In some embodiments, substrate 302 may also include various isolation features. Isolation features separate various device regions in substrate 302. Isolation features include different structures formed using different processing techniques. For example, isolation features may include shallow trench isolation (STI) features. The formation of shallow trench isolation may include etching trenches in substrate 302 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 plus silicon nitride to fill the trenches. Chemical mechanical polishing (CMP) may be performed to grind away excess insulating material and planarize the top surface of the isolation features.

[0131] In some embodiments, the substrate 302 may also include a gate stack formed by a dielectric layer and an electrode layer. The dielectric layer may include an interfacial layer and a high-k dielectric layer deposited by a suitable technique, such as chemical vapor deposition (CVD), atomic layer deposition (ALD), physical vapor deposition (PVD), thermal oxidation, combinations thereof, and / or other suitable techniques. The interfacial layer may include silicon dioxide, and the high-k dielectric layer may include LaO, AlO, ZrO, TiO, Ta2O5, Y2O3, SrTiO3, BaTiO3, BaZrO, HfZrO, HfLaO, HfSiO, LaSiO, AlSiO, HfTaO, HfTiO, (Ba, Sr)TiO3 (BST), Al2O3, Si3N4, SiON, and / or other suitable materials. The electrode layer may include a single layer or a multilayer structure, such as 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 various combinations of a conductive layer of a metal, a metal alloy, or a metal silicide. The electrode layer may include Ti, Ag, Al, TiAlN, TaC, TaCN, TaSiN, Mn, Zr, TiN, TaN, Ru, Mo, Al, WN, Cu, W, any suitable material, and / or combinations thereof.

[0132] In some embodiments, the substrate 302 may also include multiple inter-level dielectric (ILD) layers and conductive features that are integrated to form an interconnect structure that is configured to couple various p-type and n-type doped regions and other functional features (e.g., gate electrodes) to form a functional integrated circuit. In one embodiment, the substrate 302 may include a portion of an interconnect structure, and the interconnect structure may include a multi-layer interconnect (MLI) structure and an inter-layer dielectric layer integrated with the multi-layer interconnect structure, providing electrical wiring to couple various devices in the substrate 302 to input / output power and signals. The interconnect structure includes various metal lines, contacts, and via features (or via plugs). The metal lines provide horizontal electrical wiring. Multiple contacts provide vertical connections between the silicon substrate and the metal lines, and the via features provide vertical connections between multiple metal lines in different metal layers.

[0133] A material layer 310 is deposited on the substrate 302. The material layer 310 is a layer to be processed by the method 200, such as to be patterned or implanted. In some embodiments, the material layer 310 is a hard mask layer to be patterned. In some embodiments, the material layer 310 includes a dielectric material, such as silicon oxide, silicon nitride, silicon carbide, or silicon oxynitride. In some other embodiments, the material layer 310 includes a metal oxide such as titanium oxide, or a metal nitride such as titanium nitride. In some embodiments, the material layer 310 includes a polymer such as polyimide. In some embodiments, the material layer 310 is also used as an anti-reflection coating (ARC), and the composition of the anti-reflection coating is selected to minimize the reflectivity of radiation applied during the exposure of the photoresist layer 320. For example, in some embodiments, the material layer 310 includes silicon oxide, silicon oxycarbide, or plasma enhanced chemical vapor deposited silicon oxide. The material layer 310 may be formed via any suitable process, including chemical vapor deposition, physical vapor deposition, plasma enhanced chemical vapor deposition (PECVD), atomic layer deposition, or spin coating, and may be formed to any suitable thickness.

[0134] Reference Figure 3B According to some embodiments, a photoresist layer 320 is formed over the material layer 310 .

[0135] Photoresist layer 320 is sensitive to radiation used during the photolithography exposure process, such as deep ultraviolet radiation (e.g., 248 nanometer (nm) radiation from a KrF laser or 193 nm radiation from an ArF laser), extreme ultraviolet radiation (e.g., 13.5 nm radiation), electron beam radiation, ion beam radiation, and / or other suitable radiation. In some embodiments, photoresist layer 320 is sensitive to radiation having a wavelength less than about 250 nm.

[0136] The photoresist layer 320 may be formed over the material layer 310 by any suitable process. In some embodiments, the photoresist layer 320 is formed by spin coating the photoresist composition 100 onto the surface of the material layer 310. In some embodiments, the photoresist layer 320 may be formed by chemical vapor deposition or physical vapor deposition.

[0137] In some embodiments, after spin coating the photoresist composition 100 (but before performing an exposure process), a pre-exposure bake process may be performed on the photoresist layer 320 , for example, to evaporate a solvent (eg, solvent 120 ) and densify the photoresist layer 320 .

[0138] refer to Figure 3C, an exposure process is performed on the photoresist layer 320, wherein the photoresist layer 320 is irradiated with radiation. In some embodiments, the photoresist layer 320 is exposed to radiation having a wavelength less than about 250 nanometers, such as deep ultraviolet radiation, extreme ultraviolet radiation, x-ray radiation, electron beam radiation, ion beam radiation, and / or other suitable radiation. The exposure process can be performed in air, liquid (immersion lithography), or vacuum (for example, when implementing extreme ultraviolet lithography and / or electron beam lithography). In some embodiments, a mask having an integrated circuit pattern is used to pattern the radiation so that the radiation forms an image of the integrated circuit pattern on the photoresist layer 320. The mask transmits, absorbs, and / or reflects the radiation depending on the integrated circuit pattern and the masking technology used to manufacture the mask. Various resolution enhancement techniques, such as phase shifting, off-axis illumination (OAI), and / or optical proximity correction (OPC), can be implemented by masking or exposure processes. For example, an optical proximity correction feature can be incorporated into the integrated circuit pattern. In another embodiment, the mask is a phase shift mask, such as an alternative phase shift mask, an attenuated phase shift mask, or a chrome-free phase shift mask. In yet another embodiment, the exposure process is performed in an off-axis illumination mode. In some implementations, the radiation beam is patterned by directly modulating the radiation beam according to the integrated circuit pattern without using a mask (commonly referred to as maskless lithography).

[0139] A latent pattern is formed on the photoresist layer 320 through an exposure process. The latent pattern generally refers to a pattern exposed on the photoresist layer 320, and when the photoresist layer 320 undergoes a development process, the pattern eventually becomes a physical photoresist pattern. The latent pattern includes an exposed portion 320A and an unexposed portion 320B.

[0140] When the photoresist layer 320 is exposed to radiation, the exposed portion 320A undergoes physical and / or chemical changes in response to the exposure process. For example, a photoacid generator in the exposed portion 320A of the photoresist layer 320 generates an acid upon absorbing radiation, and the acid functions as a catalyst for causing a chemical reaction that increases (or decreases) the solubility of the exposed portion 320A. For example, the acid generated by the photoacid generator catalyzes the cleavage of acid-labile groups from side chains of the polymer 104 in the exposed portion 320A of the photoresist layer 320.

[0141] After the exposure process, a post-exposure bake (PEB) process is performed on the photoresist layer 320. The post-exposure bake process increases the temperature of the photoresist layer 320 to about 80°C to about 180°C. In some embodiments, the post-exposure bake process is performed in a thermal chamber to increase the temperature of the photoresist layer 320 to about 120°C to about 150°C. During the post-exposure bake process, the acid-labile groups 114 are cleaved from the side chains of the polymer 104 in the exposed portion 320A of the photoresist layer 320, thereby chemically changing the exposed portion 320A. For example, in the illustrated embodiment, the exposure process and / or the post-exposure bake process increases the hydrophilicity of the exposed portion 320A (in other words, the polymer becomes more hydrophilic), thereby increasing the solubility of the exposed portion 320A to the developer. Alternatively, in some embodiments, the exposure process and / or the post-exposure bake process decreases the hydrophilicity of the exposed portion 320A (in other words, the polymer becomes more hydrophobic), thereby decreasing the solubility of the exposed portion 320A to the developer.

[0142] refer to Figure 3D , a development process is performed on the photoresist layer 320 to form a patterned photoresist layer 320P. In the depicted embodiment, a negative tone development (NTD) process is performed to remove the unexposed portions 320B of the photoresist layer 320. For example, a negative tone developer is applied to the photoresist layer 320, which dissolves the unexposed portions 320B, leaving a patterned photoresist layer 320P (collectively referred to as a photoresist pattern) having a plurality of openings 340 between the plurality of exposed portions 320A. In some embodiments, the negative tone developer is an organic-based developer, such as n-butylacetate (n-BA). Alternatively, a positive tone development (PTD) process is performed to remove the exposed portions 320A of the photoresist layer 320 (not shown). For example, a positive-tone developer is applied to the photoresist layer 320, dissolving the exposed portions 320A, leaving a patterned photoresist layer 320P (collectively referred to as a photoresist pattern) having a plurality of openings 340 between the plurality of unexposed portions 320B. In some embodiments, the positive-tone developer is a water-based solvent, such as tetramethylammonium hydroxide (TMAH) or tetrabutylammonium hydroxide (TBAOH).

[0143] In an embodiment of the present disclosure, by adding an anti-etching promoting group 112 between the polymer main chain 110 and the acid-labile group 114 to minimize or eliminate the shrinkage of the photoresist layer 320, the opening 340 can be formed by relatively smooth edges and / or sidewalls of the exposed portion 320A, so that the photoresist pattern of the patterned photoresist layer 320P exhibits minimal line edge roughness / line width roughness and improved resist contrast, significantly improving the lithography resolution.

[0144] In some embodiments, before developing the photoresist layer 320, a treatment is performed on the photoresist layer 320 to crosslink the photoresist layer 320, thereby reducing the solubility of portions of the photoresist layer 320 to the developer. In some embodiments, the photoresist layer 320 is treated before the exposure process. In some embodiments, the photoresist layer 320 is treated after the post-exposure bake process.

[0145] Reference Figure 3E According to some embodiments of the present disclosure, the material layer 310 is etched using the patterned photoresist layer 320P as a mask to form the patterned material layer 310P. As a result, the pattern of the patterned photoresist layer 320P is transferred to the material layer 310.

[0146] Portions of the material layer 310 not covered by the patterned photoresist layer 320P are removed via a dry etching process, a wet etching process, or a combination thereof. In some embodiments, the etching process includes a plasma etching process using an etchant having fluorine, such as CF, CF2, CF3, CF4, C2F2, C2F3, C3F4, C4F4, C4F6, C5F6, C6F6, C6F8, or a combination thereof. Thereafter, according to some embodiments of the present disclosure, the patterned photoresist layer 320P is removed. In some embodiments, the patterned photoresist layer 320P is removed via ashing.

[0147] On the one hand, a method for forming a semiconductor device is provided. The method includes forming a photoresist layer above a substrate. The photoresist layer includes a polymer and a photoacid generator (PAG). The polymer includes a polymer backbone, an anti-etching promoting group chemically bonded to the polymer backbone, and an acid-labile group (ALG) chemically bonded to the anti-etching promoting group. The method also includes exposing a portion of the photoresist layer to radiation to generate acid in the exposed portion, baking the photoresist layer, resulting in the cracking of the acid-labile group, and removing the portion of the photoresist layer to form a patterned photoresist layer.

[0148] In some embodiments, in a method of forming a semiconductor device, the cleavage of the acid-labile group forms a COOH group that is bonded to the anti-etching promoting group.

[0149] In some embodiments, in a method of forming a semiconductor device, the polymer comprises a monomer unit having the following structure (I):

[0150]

[0151] Wherein: L is a direct bond, or an alkylene, heteroalkylene, cycloalkylene ether, arylene ether, -CO-, -C(O)O-, -CONRa -, -O-, -S-, -S(O)-, -SO2-, or -P(O)OH- linker; R 1 It is an anti-etching promoting group; R 2 It is an acid-labile group; R a is H or an alkyl group; and n is an integer from 1 to 500.

[0152] In some embodiments, in a method of forming a semiconductor device, L is -(CO)O-.

[0153] In some embodiments, in a method of forming a semiconductor device, R 1 One of the following structures:

[0154]

[0155] In some embodiments, in a method of forming a semiconductor device, R 2 One of the following structures:

[0156]

[0157] In some embodiments, in a method of forming a semiconductor device, the polymer backbone is a backbone of poly(norbornene)-co-maleic anhydride (COMA), poly(4-hydroxystyrene) (PHS), phenol-formaldehyde, polyethylene (PE), polypropylene (PP), or poly(methyl methacrylate) (PMMA).

[0158] In some embodiments, in a method of forming a semiconductor device, removing a portion of the photoresist layer includes removing an unexposed portion of the photoresist layer using an organic-based developer.

[0159] In some embodiments, in a method of forming a semiconductor device, removing a portion of the photoresist layer includes removing an unexposed portion of the photoresist layer using a water-based developer.

[0160] On the other hand, a method for forming a semiconductor device is provided. The method includes depositing a material layer above a substrate and forming a photoresist layer above the material layer. The photoresist layer includes a polymer and a photoacid generator (PAG). The polymer includes a polymer backbone, an anti-etching promoting group chemically bonded to the polymer backbone, and an acid-labile group (ALG) chemically bonded to the anti-etching promoting group. The method also includes baking the photoresist layer, resulting in the cracking of the acid-labile group, removing a portion of the photoresist layer to form a patterned photoresist layer, and using the patterned photoresist layer as a mask to etch the material layer.

[0161] In some embodiments, in a method of forming a semiconductor device, the polymer comprises a monomer unit having the following structure (I):

[0162]

[0163] Wherein: L is a direct bond, or an alkylene, heteroalkylene, cycloalkylene ether, arylene ether, -CO-, -C(O)O-, -CONR a -, -O-, -S-, -S(O)-, -SO2-, or P(O)OH- linker; R 1 It is an anti-etching promoting group; R 2 It is an acid-labile group; R a is H or an alkyl group; and n is an integer from 1 to 500.

[0164] In some embodiments, in a method of forming a semiconductor device, L is -(CO)O-; R 1 is an alkylene, heteroalkylene, cycloalkylene, cycloheteroalkylene, or arylene group; and R 2 is a monoalkyl, heteroalkyl, cycloalkyl, or cycloheteroalkyl group.

[0165] In some embodiments, in a method of forming a semiconductor device, R 1 One of the following structures:

[0166]

[0167] R 2 One of the following structures:

[0168]

[0169] In some embodiments, in a method of forming a semiconductor device, the polymer has the following structure:

[0170]

[0171] In yet another aspect, a photoresist composition is provided. The photoresist composition includes a polymer, which includes a monomer having the following structure (II) in polymerized form:

[0172]

[0173] in:

[0174] L is a direct bond, or alkylene, heteroalkylene, cycloalkylene ether, arylene ether, -CO-, -C(O)O-, -CONR a-, -O-, -S-, -S(O)-, -SO2-, or -P(O)OH- linkers;

[0175] R 1 It is an anti-etching promoting group;

[0176] R 2 It is an acid-labile group;

[0177] R 3 is H or an alkyl group; and

[0178] R a is H or an alkyl group.

[0179] In some embodiments, in the photoresist composition, R 1 One of the following structures:

[0180]

[0181] In some embodiments, in the photoresist composition, R 2 One of the following structures:

[0182]

[0183] In some embodiments, in the photoresist composition, the monomer has the following structure:

[0184]

[0185] In some embodiments, the photoresist composition further comprises a photoacid generator (PAG) configured to release an acid in response to radiation.

[0186] In some embodiments, the photoresist composition further includes a solvent.

[0187] The above summarizes the features of several embodiments so that those skilled in the art can better understand the various aspects of the present disclosure. Those skilled in the art will appreciate that they may easily use the present disclosure as a basis for the design or modification of other processes and structures to achieve the same purpose as the embodiments introduced herein, and / or to achieve the same advantages. Those skilled in the art will also appreciate that such equal constructions do not depart from the spirit and scope of the present disclosure, and that they may make various changes, substitutions, and modifications without departing from the spirit and scope of the present disclosure.

Claims

1. A method for forming a semiconductor device, characterized in that: Include: Forming a photoresist layer over a substrate, the photoresist layer comprising a polymer and a photoacid generator (PAG), the polymer comprising a polymer backbone, an anti-etching promoting group chemically bonded to the polymer backbone, and an acid labile group (ALG) chemically bonded to the anti-etching promoting group; exposing a portion of the photoresist layer to radiation to generate acid in the exposed portion; baking the photoresist layer to cause cleavage of the acid-labile groups; as well as A portion of the photoresist layer is removed to form a patterned photoresist layer.

2. The method for forming a semiconductor device according to claim 1, wherein: The cleavage of the acid labile group forms a COOH group, which is bonded to the anti-etching promoting group.

3. The method for forming a semiconductor device according to claim 1, wherein: The polymer comprises a monomer unit having the following structure (I): in: L is a direct bond, or an alkylene, heteroalkylene, cycloalkylene ether, arylene ether, -CO-, -C(O)O-, -CONR a -, -O-, -S-, -S(O)-, -SO2-, or -P(O)OH- linkers; R 1 It is an anti-etching promoting group; R 2 It is an acid-labile group; R a is H or an alkyl group; and n is an integer ranging from 1 to 500.

4. The method for forming a semiconductor device according to claim 1, wherein: Removing a portion of the photoresist layer includes removing an unexposed portion of the photoresist layer using an organic-based developer.

5. A method for forming a semiconductor device, characterized in that: Include: depositing a material layer on a substrate; forming a photoresist layer over the material layer, the photoresist layer comprising a polymer and a photoacid generator (PAG), the polymer comprising a polymer backbone, an anti-etching promoting group chemically bonded to the polymer backbone, and an acid labile group (ALG) chemically bonded to the anti-etching promoting group; exposing a portion of the photoresist layer to radiation to generate acid in the exposed portion; baking the photoresist layer to cause cleavage of the acid-labile groups; removing a portion of the photoresist layer to form a patterned photoresist layer; as well as The material layer is etched using the patterned photoresist layer as a mask.

6. The method for forming a semiconductor device according to claim 5, wherein: The polymer comprises a monomer unit having the following structure (I): in: L is a direct bond, or an alkylene, heteroalkylene, cycloalkylene ether, arylene ether, -CO-, -C(O)O-, -CONR a -, -O-, -S-, -S(O)-, -SO2-, or P(O)OH- linkers; R 1 It is an anti-etching promoting group; R 2 It is an acid-labile group; R a is H or an alkyl group; and n is an integer ranging from 1 to 500.

7. The method for forming a semiconductor device according to claim 6, wherein: L is -(CO)O-; R 1 is an alkylene, heteroalkylene, cycloalkylene, cycloheteroalkylene, or arylene group; and R 2 is a monoalkyl, heteroalkyl, cycloalkyl, or cycloheteroalkyl group.

8. A photoresist composition, characterized in that: A polymer is included, the polymer comprising, in polymerized form, a monomer having the following structure (II): in: L is a direct bond, or an alkylene, heteroalkylene, cycloalkylene ether, arylene ether, -CO-, -C(O)O-, -CONR a -, -O-, -S-, -S(O)-, -SO2-, or -P(O)OH- linkers; R 1 It is an anti-etching promoting group; R 2 It is an acid-labile group; R 3 is H or an alkyl group; and R a is H or an alkyl group.

9. The photoresist composition according to claim 8, characterized in that: R 1 One of the following structures:

10. The photoresist composition according to claim 8, characterized in that: R 2 One of the following structures:

Images