Resist underlayer composition

Abstract

The present application relates to a resist underlayer composition. In particular, a resist underlayer composition for extreme ultraviolet lithography is provided. The composition includes a first polymer, a second polymer, an acid generator, and a solvent. The first polymer includes a first polymer backbone and an etch resistance enhancing unit covalently bonded to the first polymer backbone via a first linker. The etching resistance enhancing unit includes a silicon-containing unit containing a silicon-oxygen bond or a metal-containing unit containing a metal-oxygen bond. The second polymer includes a second polymer backbone and a crosslinker unit covalently bonded to the second polymer backbone via a second linker. The crosslinker unit comprises one or more crosslinkable groups.

Description

[0001] Priority Claims and Cross-References

[0002] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 591,393, filed on October 18, 2023, which is incorporated herein by reference in its entirety. Technical Field

[0003] The present invention relates to a resist underlayer composition. Background Art

[0004] Semiconductor devices are used in various electronic applications, such as personal computers, mobile phones, digital cameras and other electronic equipment. Semiconductor devices are manufactured by sequentially depositing dielectric layers, conductive layers and semiconductor layers above a semiconductor substrate and patterning various material layers using photolithography. In the photolithography process, a photoresist is deposited above the substrate and exposed to radiation such as extreme ultraviolet (EUV) rays. The radiation exposure causes a chemical reaction in the exposed area of ​​the photoresist and creates a latent image corresponding to the mask pattern in the photoresist. Next, the photoresist is developed in a developer, and the exposed portion of the photoresist is removed for a positive photoresist or the unexposed portion of the photoresist is removed for a negative photoresist. Then, the patterned photoresist is used as an etching mask in a subsequent etching process to form an integrated circuit (IC). Summary of the invention

[0005] Some embodiments of the present invention provide a resist base layer composition, which comprises: a first polymer, wherein the first polymer comprises a first polymer main chain and an etching resistance enhancing unit covalently bonded to the first polymer main chain via a first joint, wherein the etching resistance enhancing unit comprises a silicon-containing unit containing a silicon-oxygen bond or a metal-containing unit containing a metal-oxygen bond; a second polymer, wherein the second polymer comprises a second polymer main chain and a crosslinker unit covalently bonded to the second polymer main chain via a second joint, wherein the crosslinker unit comprises one or more crosslinkable groups; an acid generator; and a solvent.

[0006] Some embodiments of the present invention provide a resist bottom layer composition, the resist bottom layer composition comprising: an acid generator; a solvent; and a copolymer having the following structure (III):

[0007]

[0008] in:

[0009] L 1 and L 2is independently at each occurrence alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, cycloalkylene, heterocycloalkylene, arylene, heteroarylene, or a heteroatom linker;

[0010] E is independently an etch resistance enhancing unit at each occurrence;

[0011] C, at each occurrence, is independently a crosslinker unit comprising one or more crosslinkable groups; and

[0012] m, n and q are independently an integer of 1 or greater.

[0013] Some other embodiments of the present invention provide a method for forming a semiconductor device, the method comprising: forming a resist bottom layer above a material layer on a substrate, the resist bottom layer comprising a first polymer, a second polymer, and an acid generator, wherein: the first polymer comprises a first polymer main chain and an etching resistance enhancing unit covalently bonded to the first polymer main chain via a first joint, the etching resistance enhancing unit comprising a silicon-containing unit containing a silicon-oxygen bond or a metal-containing unit containing a metal-oxygen bond; the second polymer comprises a second polymer main chain and a crosslinker unit covalently bonded to the second polymer main chain via a second joint, wherein the crosslinker The invention relates to a method for preparing a photoresist layer comprising a metal photoresist and a photoresist unit, wherein the photoresist unit comprises one or more cross-linkable groups; performing a baking process to cause the cross-linking groups to undergo a cross-linking reaction, thereby forming a cross-linked resist bottom layer; depositing a photoresist layer comprising a metal photoresist over the cross-linked resist bottom layer; selectively exposing the photoresist layer to patterned radiation; developing the selectively exposed photoresist layer to form a patterned photoresist layer; using the patterned photoresist layer as an etching mask to etch the cross-linked resist bottom layer to form a patterned cross-linked resist bottom layer; and etching the material layer using the patterned cross-linked resist bottom layer as an etching mask. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] When read in conjunction with the accompanying drawings, various aspects of the present disclosure can be best understood from the following detailed description. It should be noted that, in accordance with standard practice in the industry, various features are not drawn to scale. In fact, for the sake of clarity of discussion, the size of the various features may be arbitrarily increased or reduced.

[0015] Figure 1 is a flow chart of a method for manufacturing a semiconductor device according to some embodiments of the present disclosure.

[0016] FIG. 2A to FIG. 2H According to some embodiments of the present disclosure, Figure 1 A cross-sectional view of a semiconductor device manufactured by the method.

[0017] Figure 3AEmbodiments of a resist underlayer composition included in a resist underlayer according to some embodiments of the present disclosure are shown.

[0018] Figure 3B Exemplary copolymers in the resist underlayer composition according to some embodiments of the present disclosure are shown.

[0019] Figure 4 Exemplary silane and silsesquioxane compounds are shown.

[0020] Figure 5 An exemplary silicon-containing etch resistance enhancing unit is shown.

[0021] Figure 6 An exemplary tin cage structure is shown.

[0022] Fig. 7A Exemplary organometallic compounds according to some embodiments are shown.

[0023] Figure 7B An exemplary reaction of an organometallic compound in the presence of water according to some embodiments is shown.

[0024] Figure 8 Exemplary reactions of organometallic compounds according to some embodiments are shown. DETAILED DESCRIPTION

[0025] The following disclosure provides many different embodiments or examples for realizing the different features of the provided subject matter. Specific examples of components, values, operations, materials, arrangements, etc. are described below to simplify the present disclosure. Of course, these are merely examples and are not intended to be limiting. Other components, values, operations, materials, arrangements, etc. can be envisioned. For example, forming a first feature above or on a second feature in the following description may include an embodiment in which the first feature and the second feature are formed as direct contacts, and may also include an embodiment in which additional features may be formed between the first feature and the second feature so that the first feature and the second feature may not be in direct contact. In addition, the present disclosure may repeat reference numerals and / or letters in various examples. This repetition is for the purpose of simplification and clarity, and does not itself specify the relationship between the various embodiments and / or configurations discussed.

[0026] Further, for ease of description, spatially relative terms such as "below," "below," "lower," "above," "upper," etc. may be used herein to describe the relationship of one element or feature to another element or features as shown in the figures. Spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. The system may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein may be interpreted accordingly.

[0027] When describing the compounds, compositions, methods and processes of the present disclosure, the following terms have the following meanings unless otherwise indicated.

[0028] As described herein, the compounds disclosed herein may be optionally substituted with one or more substituents, such as those generally described below, or as exemplified by specific classes, subclasses, and species disclosed herein. It should be understood that the phrase "optionally substituted" is used interchangeably with the phrase "substituted or unsubstituted". In general, the term "substituted", whether preceded by the term "optionally", refers to the replacement of one or more hydrogen groups in a given structure by a group of a specific substituent. Unless otherwise indicated, 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 by more than one substituent selected from a specific group, the substituents at each position may be the same or different.

[0029] As used herein, the term "polymer" generally refers to a molecule consisting of repeating structural units linked by covalent chemical bonds and characterized by a large number of repeating units (e.g., equal to or greater than 20 repeating units, and often equal to or greater than 100 repeating units and often equal to or greater than 200 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, segmented, grafted, 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 links may be generated by multivalent monomers that form crosslinking sites upon polymerization.

[0030] As used herein, the term "group" may refer to a functional group of a compound. A group of a compound of the present invention refers to an atom or collection of atoms that is part of the compound. The groups of the present disclosure may be attached to other atoms of the compound via one or more covalent bonds. The group may also be characterized by its valence state. The present disclosure includes groups characterized by univalent, divalent, trivalent, etc. valence states.

[0031] 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 Used to indicate that a given moiety (in this example, the cyclohexyl moiety) is attached to a molecule via a bond "terminated" with a wavy line.

[0032] 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., micronized particles). The linker can connect molecules via covalent bonds or other means (e.g., ionic bonds or hydrogen bond interactions). In some embodiments, the linker is a heteroatom linker (e.g., comprising 1-10 Si, N, O, P, or S atoms), a heteroalkylene (e.g., comprising 1-10 Si, N, O, P, or S atoms and an alkylene chain), or an alkylene linker (e.g., comprising 1-12 carbon atoms). In some embodiments, the linker may comprise an ether (-O-), an ester (-OC(=O)-), or a carbonate (-OC(=O)O-) bond.

[0033] "Hydroxy" or "hydroxyl" refers to an -OH group.

[0034] As used herein, "aromatic" or "aromatic group" refers to a main 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.

[0035] As used herein, "aliphatic" or "aliphatic group" means a straight or branched chain C 1-12 A hydrocarbon chain, either completely saturated or containing one or more unsaturated units, but not an aromatic monocyclic C 3-8 Hydrocarbon or bicyclic C 8-12 Hydrocarbons (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 3-7 members. For example, suitable aliphatic groups include, but are not limited to, straight or branched chain alkyl, alkenyl, alkynyl groups, and mixtures thereof, such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl, or (cycloalkyl)alkenyl.

[0036] "Alkyl" refers to a group consisting of only carbon and hydrogen atoms, containing no unsaturation, having 1 to 12 carbon atoms (C1-C 12The term "alkyl" refers to a straight or branched hydrocarbon group having 1 to 8 carbon atoms (C1-C8 alkyl) or 1 to 6 carbon atoms (C1-C6 alkyl) and attached to the rest of the molecule by 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, etc. Unless otherwise specifically stated in the specification, the alkyl group is optionally substituted.

[0037] "Alkylene" or "alkylene chain" refers to a straight or branched divalent hydrocarbon chain that connects the rest of the molecule to a group, consisting only of carbon and hydrogen, containing no unsaturation, and having 1 to 12 carbon atoms, for example, methylene, ethylene, propylene, n-butylene, etc. The alkylene chain is attached to the rest of the molecule and to the group through a single bond. The points of attachment of the alkylene chain to the rest of the molecule and to the group can be through one carbon or any two carbons within the chain. Unless otherwise specifically stated in this specification, alkylene is optionally substituted.

[0038] "Alkenylene" or "alkenylene chain" refers to a straight or branched divalent hydrocarbon chain that connects the rest of the molecule to a group, consisting only of carbon and hydrogen, containing at least one carbon-carbon double bond and having 2 to 12 carbon atoms, such as vinylene, propenylene, n-butenylene, etc. The alkenylene chain is attached to the rest of the molecule by a single bond and to the group by a double bond or a single bond. The points of attachment of the alkenylene chain to the rest of the molecule and to the group can be through one carbon or any two carbons within the chain. Unless otherwise specifically stated in this specification, alkenylene is optionally substituted.

[0039] "Alkynylidene" or "alkynylene chain" refers to a straight or branched divalent hydrocarbon chain that connects the rest of the molecule to a group, which consists only of carbon and hydrogen, contains at least one carbon-carbon triple bond and has 2 to 12 carbon atoms, such as ethynylene, propynylene, n-butynylene, etc. The alkynylene chain is attached to the rest of the molecule by a single bond and to the group by a triple bond or a single bond. The attachment points of the alkynylene chain to the rest of the molecule and to the group can be through one carbon or any two carbons within the chain. Unless otherwise specifically stated in this specification, alkynylene is optionally substituted.

[0040] "Alkoxy" refers to a group of the formula -OR a A group in which R a is an alkyl group as defined above containing 1 to 12 carbon atoms. Unless stated otherwise specifically in the specification, an alkoxy group is optionally substituted.

[0041] "Cycloalkyl" refers to a stable non-aromatic monocyclic or polycyclic carbocyclic ring, which may include a fused ring system or a bridged ring system, having 3 to 15 carbon atoms, preferably 3 to 10 carbon atoms, and which is saturated or unsaturated and attached to the rest of the molecule by a single bond. Monocyclic cycloalkyls include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Polycyclic cycloalkyls include, for example, adamantyl, norbornyl, decalinyl, 7,7-dimethyl-bicyclo-[2.2.1]heptyl, etc. Unless otherwise specifically stated in this specification, cycloalkyl groups are optionally substituted.

[0042] "Heteroalkyl" refers to an alkyl group as defined above that contains at least one heteroatom (e.g., N, O, P, or S) within or at the terminus of the alkyl group. In some embodiments, the heteroatom is within the alkyl group (i.e., the heteroalkyl group contains at least one carbon-[heteroatom] x -carbon bond, wherein x is 1, 2 or 3). In other embodiments, the heteroatom is located at the end of the alkyl group and is therefore used to join the alkyl group to the rest of the molecule (e.g., M1-HA), wherein M1 is part of the molecule, H is a heteroatom and A is an alkyl group). Unless otherwise specifically stated in this specification, heteroalkyl groups are optionally substituted. Exemplary heteroalkyl groups include ethylene oxide (e.g., polyethylene oxide), optionally including a phosphorus-oxygen bond, such as a phosphodiester bond.

[0043] "Heteroalkylene" refers to an alkylene group as defined above, which contains at least one heteroatom (e.g., N, O, P, or S) within the alkylene chain or at the end of the alkylene chain. In some embodiments, the heteroatom is within the alkylene chain (i.e., the heteroalkylene contains at least one carbon-[heteroatom]-carbon bond, where x is 1, 2, or 3). In other embodiments, the heteroatom is at the end of the alkylene and thus serves to join the alkylene to the rest of the molecule (e.g., M1-HA-M2, where M1 and M2 are part of the molecule, H is a heteroatom and A is an alkylene). Unless otherwise specifically stated in the specification, heteroalkylene groups are optionally substituted.

[0044] "Heteroalkenylene" is a heteroalkylene group as defined above containing at least one carbon-carbon double bond. Unless stated otherwise specifically in the specification, a heteroalkenylene group is optionally substituted.

[0045] "Heteroalkynylene" is a heteroalkylene group containing at least one carbon-carbon triple bond. Unless stated otherwise specifically in the specification, a heteroalkynylene group is optionally substituted.

[0046] "Heteroatom" in reference to 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, for example, a linker having the formula -P(O - )(=O)O-or-OP(O - )(=O)O- and their polymers and combinations.

[0047] "Aryl" refers to a ring system containing at least one carbocyclic aromatic ring. In some embodiments, the aryl group contains 6 to 18 carbon atoms. The aromatic ring can be a monocyclic, bicyclic, tricyclic or tetracyclic ring system, and the ring system can include a fused ring system or a bridged ring system. Aryl groups include, but are not limited to, those derived from aceanthrene, acenaphthylene, acephenanthrene, anthracene, azulene, benzene, The aryl groups of fluoranthene, fluorene, as-indacene, s-indacene, indane, indene, naphthalene, phenalene, phenanthrene, pyrene, pyrene and triphenylene. Unless otherwise specifically stated in the specification, the aryl group is optionally substituted.

[0048] "Heteroaryl" refers to a 5- to 14-membered ring system containing 1 to 13 carbon atoms, 1 to 6 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, and at least one aromatic ring. For the purposes of certain embodiments of the present disclosure, the heteroaryl group can be a monocyclic, bicyclic, tricyclic or tetracyclic ring system, which can include a fused ring system or a bridged ring system; and the nitrogen, carbon or sulfur atoms in the heteroaryl group can be optionally oxidized; the nitrogen atom can be optionally quaternized. Examples include, but are not limited to, azepinyl, acridinyl, benzimidazolyl, benzthiazolyl, benzindolyl, benzodioxolanyl, benzofuranyl, benzooxazolyl, benzothiazolyl, benzothiadiazolyl, benzo[b][1,4]dioxepanyl, 1,4-benzodioxanyl, benzonaphthofuranyl, benzoxazolyl oxazolyl), benzodioxolanyl, benzodioxinyl, benzopyranyl, benzopyrone, benzofuranyl, benzofuranone, benzothienyl / benzothiophenyl, benzotriazolyl, benzo[4,6]imidazo[1,2-a]pyridinyl, benzoxazolinone, benzimidazolesulfinyl, carbazolyl, cinnolinyl, dibenzofuranyl, dibenzothiophenyl benzothienyl, furanyl, furanonyl, isothiazolyl, imidazolyl, indazolyl, indolyl, indazolyl, isoindolyl, dihydroindolinyl, isoindolyl, isoquinolinyl, indolizinyl, isoxazolyl, naphthyridinyl, oxadiazolyl, 2-oxoazepinyl, oxazolyl, oxiranyl, 1-oxopyridinyl, 1-oxopyrimidinyl, 1-oxopyrazinyl, 1-oxopyridazinyl, 1-phenyl-1H-pyrrolyl, phenazinyl, phenothiazinyl, phenoxazinyl, phthalazinyl, pteridinyl, pteridine Keto, purinyl, pyrrolyl, pyrazolyl, pyridinyl, pyridonyl, pyrazinyl, pyrimidinyl, pyrimidonyl, pyridazinyl, pyrrolyl, pyrido [2,3-d] pyrimidonyl, quinazolinyl, quinazolinonyl, quinoxalinyl, quinoxalinonyl, 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 otherwise specifically stated in the specification, heteroaryl groups are optionally substituted.

[0049] "Heterocycle" refers to a stable 3- to 18-membered aromatic or non-aromatic ring containing 1 to 12 carbon atoms and 1 to 6 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur. Unless otherwise specifically stated in this specification, the heterocycle can be a monocyclic, bicyclic, tricyclic or tetracyclic ring system, which can include a fused ring system or a bridged ring system; and the nitrogen, carbon or sulfur atoms in the heterocycle can be optionally oxidized; the nitrogen atom can be optionally quaternized; and the heterocycle can be partially or fully saturated. Examples of aromatic heterocycles are listed 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, 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, heterocyclyl groups are optionally substituted.

[0050] The term "substituted" as used herein means any of the above groups, wherein at least one hydrogen atom (e.g., 1, 2, 3 or all 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, I; an oxygen atom in a group such as a hydroxyl group, an alkoxy group, and an ester group; a sulfur atom in a group such as a thiol group, a thioalkyl group, a sulfone group, a sulfonyl group, and a sulfoxide group; a nitrogen 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 means any of the above groups in which one or more hydrogen atoms are replaced by a higher order bond (e.g., double or triple bond) to a heteroatom, such as oxygen in oxo, carbonyl, carboxyl, and ester groups; and nitrogen in groups such as imines, oximes, hydrazones, and nitriles. 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 gC(=O)OR h 、-NR g S02R h 、-OC(=O)NR g R h 、-OR g 、-SR g 、-SOR g 、-SO2R g 、-OSO2R g 、-SO2OR g , =NSO2R g and -SO2NR g R h "Substituted" also means any of the above groups in which one or more hydrogen atoms are replaced by -C(=O)R g 、-C(=O)OR g 、-C(=O)NR g R h 、-CH2SO2R g and -CH2SO2NR g R h In the above, R g and R h The same or different, and independently hydrogen, alkyl, alkoxy, alkylamino, alkylthio, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, haloalkyl, heterocyclic radical, N-heterocyclic radical, heterocycloalkyl, heteroaryl, N-heteroaryl and / or heteroarylalkyl. "Substituted" also means any group in the above-mentioned groups, wherein one or more hydrogen atoms are replaced by a bond to an amino, cyano, hydroxyl, imino, nitro, oxo, oxo, halogen, alkyl, alkoxy, alkylamino, alkylthio, aryl, aralkyl, cycloalkyl, cycloalkylalkyl, haloalkyl, heterocyclic radical, N-heterocyclic radical, heterocycloalkyl, heteroaryl, N-heteroaryl and / or heteroarylalkyl group. In addition, each substituent in the above-mentioned substituents may also be optionally replaced by one or more of the above-mentioned substituents.

[0051] IC manufacturing uses one or more photolithography processes to transfer geometric patterns onto a film or substrate. The geometric shapes and patterns on the semiconductor form a complex structure that allows dopants, electrical properties, and wires to complete the circuit and achieve technical purposes. In the photolithography process, a photoresist is applied to the substrate as a thin film and then exposed to one or more types of radiation or light through a photomask. The photomask contains transparent and opaque features that define the pattern to be created in the photoresist layer. The areas in the photoresist that are exposed to the light transmitted through the photomask are soluble or insoluble in a specific type of solution called a developer. In the case where the exposed areas are soluble, a positive image of the photomask is produced in the photoresist, and this type of photoresist is called a positive photoresist. On the other hand, if the unexposed areas are dissolved by the developer, a negative image is produced in the photoresist, and this type of photoresist is called a negative photoresist. The developer removes the more soluble areas, leaving the patterned photoresist in place. The resist pattern is then used as an etch mask in a subsequent etching process to transfer the pattern to the underlying material layer, thereby replicating the mask pattern in the underlying material layer.

[0052] Extreme ultraviolet (EUV) lithography extends lithography downward to the range of 32 nm and below by using short exposure wavelengths in the range of 11 nm to 14 nm, typically 13.5 nm. EUV lithography uses high-performance photoresists with high sensitivity to reduce the cost of high-power exposure sources and provide good image resolution. Metal resists containing metals with high EUV light absorption have been developed to increase the sensitivity of the resist to EUV radiation, so that a lower exposure dose can be used to pattern the photoresist layer. Organic metal compounds with photo-cleavable organic ligands bonded to metals are used as precursors for EUV photoresists. These photo-cleavable ligands are cleaved to generate free radicals when exposed to radiation. The free radicals generated by the cleavage of the metal core-ligand bond initiate and trigger polymerization, during which the metal core radicals first react with the embodiment water to form a metal hydroxide, and the subsequent condensation of the metal hydroxide forms a metal-oxygen cluster.

[0053] EUV lithography uses reflective masks because no transparent materials are available to facilitate transmissive masks at EUV wavelengths. Resist underlayers with high EUV light absorption can improve resist performance such as sensitivity, imaging capability, dissolution contrast, resolution, and process window. In addition to lithography performance alone, since the resist underlayer also has a dual function as an etching mask, the resist underlayer should provide sufficient etch resistance to transfer the resist pattern into the substrate.

[0054] Embodiments of the present disclosure provide resist underlayer compositions that are designed to absorb EUV radiation used to expose photoresists, thereby minimizing substrate reflections. In addition, these compositions incorporate silicon- or metal-containing units with enhanced etch resistance to ensure efficient image transfer from photoresist to substrate while minimizing resist leakage. In the case of metals exhibiting high EUV light absorption, resist underlayer compositions also contribute to dose reduction.

[0055] Figure 1 is a flow chart of a method 100 of forming a semiconductor device according to some embodiments of the present disclosure. FIG. 2A to FIG. 2H is a cross-sectional view of a semiconductor device 200 fabricated according to one or more steps of the method 100. It should be understood that for additional implementations of the method, additional steps may be provided before, during, and after the method 100, and some of the steps described below may be replaced or eliminated. It should also be understood that for additional implementations of the semiconductor device 200, additional features may be added to the semiconductor device 200, and some of the features described below may be replaced or eliminated.

[0056] The semiconductor device 200 may be an intermediate device fabricated during processing of an integrated circuit or a portion thereof, and the intermediate device may include static random access memory (SRAM) and / or other logic circuits, passive components (e.g., resistors, capacitors, and inductors) and active components (e.g., P-channel field effect transistors (PFETs), N-channel FETs (NFETs), metal-oxide semiconductor field effect transistors (MOSFETs), complementary metal-oxide semiconductor (CMOS) transistors, bipolar transistors, high-voltage transistors, high-frequency transistors, other storage cells, and combinations thereof. The semiconductor device 200 includes a plurality of semiconductor devices (e.g., transistors) that may be interconnected.

[0057] Reference Figure 1 and Figure 2A According to some embodiments, method 100 includes operation 102 in which a material layer 210 is deposited over a substrate 202 . Figure 2Ais a cross-sectional view of the semiconductor device 200 after depositing a material layer 210 over the substrate 202 .

[0058] In some embodiments, substrate 202 is a bulk semiconductor substrate comprising one or more semiconductor materials. In some embodiments, substrate 202 comprises silicon, silicon germanium, carbon-doped silicon (Si:C), silicon germanium carbide, or other suitable semiconductor materials. In some embodiments, substrate 202 is composed entirely of silicon.

[0059] In some embodiments, substrate 202 includes one or more epitaxial layers formed on the top surface of a bulk semiconductor substrate. In some embodiments, the one or more epitaxial layers introduce strain in substrate 202 to enhance performance. For example, the epitaxial layer comprises a semiconductor material different from the bulk semiconductor substrate, such as a silicon germanium layer covering bulk silicon or a silicon layer covering bulk silicon germanium. In some embodiments, the epitaxial layer incorporated into substrate 202 is formed by selective epitaxial growth, such as metalorganic vapor phase epitaxy (MOVPE), molecular beam epitaxy (MBE), hydride vapor phase epitaxy (HVPE), liquid phase epitaxy (LPE), metal-organic molecular beam epitaxy (MOMBE), or a combination thereof.

[0060] In some embodiments, substrate 202 may be a semiconductor-on-insulator (SOI) substrate. In some embodiments, the SOI substrate includes a semiconductor layer, such as a silicon layer formed on an insulator layer. In some embodiments, the insulator layer is a buried oxide (BOX) layer comprising silicon oxide or silicon germanium oxide. The insulator layer is disposed on a processing substrate (e.g., a silicon substrate). In some embodiments, the SOI substrate is formed using separation by implanted oxygen (SIMOX) or other suitable techniques (e.g., wafer bonding and grinding).

[0061] In some embodiments, substrate 202 may also include a dielectric substrate, such as silicon oxide, silicon nitride, silicon oxynitride, a low dielectric constant (k) dielectric, silicon carbide, and / or other suitable materials.

[0062] In some embodiments, the substrate 202 may also include various p-type doped regions and / or n-type doped regions implemented by processes such as ion implantation and / or diffusion. These doped regions include n-wells, p-wells, lightly doped regions (LDDs), and various channel doping distributions configured to form various IC devices (e.g., COMOS transistors, image sensors, and / or light emitting diodes (LEDs)). The substrate 202 may further include other functional features, such as resistors and / or capacitors formed in and / or on the substrate 202.

[0063] In some embodiments, the substrate 202 may also include various isolation features. The isolation features separate the various device regions in the substrate 202. The isolation features include different structures formed by using different processing techniques. For example, the isolation features may include shallow trench isolation (STI) features. The formation of STI may include etching trenches in the substrate 202 and filling the trenches with insulator materials such as silicon oxide, silicon nitride and / or silicon oxynitride. The filled trenches may have a multilayer structure, such as a thermal oxide liner layer with silicon nitride filling the trenches. Chemical mechanical polishing (CMP) may be performed to polish away excess insulator material and flatten the top surface of the isolation features.

[0064] In some embodiments, the substrate 202 may further include a gate stack formed of a dielectric layer and an electrode layer. The dielectric layer may include an interfacial layer and a high dielectric constant 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 dielectric constant dielectric layer may include LaO, AlO, ZrO, TiO, Ta2O5, Y2O3, SrTiO3, BaTiO3, BaZrO, HfZrO, HfLaO, HfSiO, LaSiO, AlSiO, HfTaO, HfTiO, (Ba, Sr)TiO3 (BST), Al2O3, Si3N4, SiON, and / or other suitable materials. The electrode layer may include a single layer or alternatively a multilayer structure, such as a metal layer having a work function that enhances device performance (work function metal layer), a liner layer, a wetting layer, an adhesion layer, and a combination 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 a combination thereof.

[0065] In some embodiments, the substrate 202 may also include multiple interlayer dielectric (ILD) layers and conductive features, which are integrated to form an interconnect structure, which is configured to couple various p-type and n-type doped regions and other functional features (such as gate electrodes) to form a functional integrated circuit. In one example, the substrate 202 may include a portion of the interconnect structure, and the interconnect structure may include a multi-layer interconnect (MLI) structure and an ILD layer integrated with the MLI structure to provide electrical wiring to couple various devices in the substrate 202 to input / output power and signals. The interconnect structure includes various metal lines, contacts, and through-hole features (or through-hole plugs). The metal lines provide horizontal electrical wiring. The contacts provide vertical connections between the silicon substrate and the metal lines, and the through-hole features provide vertical connections between metal lines in different metal layers.

[0066] The material layer 210 is disposed on the substrate 202. The material layer 210 is configured to be patterned in a subsequent manufacturing process. The material layer 210 can be one or more material layers. In some embodiments, the material layer 210 is a semiconductor layer, a conductive layer (e.g., a metallization layer), or a dielectric layer (e.g., a passivation layer) disposed above the metallization layer. In an embodiment where the material layer 210 is a metallization layer, the material layer 210 can be formed of a conductive material using a metallization process and a metal deposition technique (including CVD, ALD, and PVD). Similarly, if the material layer 210 is a dielectric layer, the material layer 210 can be formed by a dielectric layer formation technique, including thermal oxidation, CVD, ALD, and PVD.

[0067] Reference Figure 1 and Figure 2B According to some embodiments, the method 100 proceeds to operation 104 where a resist bottom layer 220 is deposited over the material layer 210 . Figure 2B After depositing the resist bottom layer 220 on the material layer 210 Figure 2A FIG. 2 is a cross-sectional view of a semiconductor device 200 .

[0068] The resist bottom layer 220 includes a photoresist layer (eg, Figure 2D The resist bottom layer 220 is a material composition with high etching selectivity between the photoresist layer 230 in the substrate 202 and the material layer 210 below. Therefore, the resist bottom layer 220 is used as an etching mask to transfer the pattern to the material layer 210. In addition, the resist bottom layer 220 is used as a bottom anti-reflective coating (BARC) to absorb the actinic radiation passing through the photoresist layer. This prevents the actinic radiation from reflecting from the substrate 202 and exposing the unintended part of the photoresist layer. Therefore, the resist bottom layer 220 helps to improve the line width roughness and line edge roughness of the photoresist pattern formed by EUV lithography.

[0069] Figure 3A An embodiment of a resist underlayer composition 300 partially included in a resist underlayer 220 according to some embodiments of the present disclosure is shown. The resist underlayer composition 300 includes: a first polymer 310 including a functional unit capable of enhancing the etching resistance of the resist underlayer 220; a second polymer 320 including a reactive unit capable of improving the solvent resistance of the resist underlayer 220; an acid generator 330; and a solvent 340.

[0070] In some embodiments, the first polymer 310 comprises a polymer backbone 312 and a 1The etch resistance enhancing unit 314 is covalently bonded to the polymer backbone 312. In some embodiments, the etch resistance enhancing unit 314 is present in the first polymer 310 in an amount ranging from about 1 wt % to about 50 wt % of the first polymer. If the amount of the etch resistance enhancing unit is less than about 1 wt %, the resist bottom layer 220 may not have sufficient etch selectivity relative to the photoresist layer and the underlying material layer. If the amount of the etch resistance enhancing unit is greater than about 50 wt %, the first polymer 310 may lack sufficient solubility in the solvent.

[0071] In some embodiments, the first polymer 310 has the following structure (I):

[0072]

[0073] in:

[0074] L 1 is independently at each occurrence alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, cycloalkylene, heterocycloalkylene, arylene, heteroarylene, or a heteroatom linker;

[0075] E, at each occurrence, is an etch resistance enhancing unit; and

[0076] n is an integer of 1 or greater.

[0077] In some embodiments, the polymer backbone 312 has a hydrocarbon structure. In some embodiments, the first polymer 310 is a polyhydroxystyrene, polyacrylate, or polymethacrylate-based polymer. In some embodiments, the first polymer 310 includes a backbone derived from one or more monomers such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, acetoxyethyl acrylate, phenyl acrylate, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, cyclohexyl acrylate, benzyl acrylate, 2-alkyl-2-adamantyl (meth)acrylate, or dialkyl (1-adamantyl)methyl (meth)acrylate, methacrylate. Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, acetoxyethyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, 3-acetoxy-2-hydroxypropyl methacrylate, 3-chloroacetoxy-2-hydroxypropyl methacrylate, or hydroxystyrene.

[0078] The etching resistance enhancing unit 314 is a silicon- or metal-containing unit for enhancing the etching resistance of the resist bottom layer 220. In some embodiments, the silicon- or metal-containing unit is a low etching unit with a high EUV absorption coefficient. When exposed to EUV, this unit generates secondary electrons, which can react with the metal-carbon bonds in the metal photoresist to stabilize the metal photoresist intermediate. Therefore, the silicon- or metal-containing unit helps to enhance the cross-linking of the metal photoresist and achieve dose reduction. The silicon- or metal-containing unit can be an organic or inorganic cage, nanoparticle, monomer, oligomer, or polymer.

[0079] In some embodiments, the etch resistance enhancing unit 314 is a silicon-containing unit containing a silicon-oxygen bond. In some embodiments, the silicon-containing unit can be derived from silane. Examples of silanes including Q-silane, T-silane, D-silane, and M-silane are shown in Figure 4 In some embodiments, the silicon-containing unit may be derived from a silsesquioxane. The silsesquioxane may be a cage silsesquioxane, an open cage silsesquioxane, a ladder silsesquioxane, or a random silsesquioxane. Examples of silsesquioxanes are shown in Figure 4 In. Figure 4In the invention, R and R' are independently cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, or branched or unbranched C1-C12 aliphatic groups, including C1-C12 alkyl or C2-C12 alkenyl groups, at each occurrence. The C1-C12 alkyl group or C2-C12 alkenyl group may be substituted with one or more substituents selected from halogen, -SH, -PH3, -PO2, -C(=O)SH, -C(=O)OH, -OH, -NH2, -C(=O)NH2, -SO2OH, -SO2SH, -SOH, -SO2, ether, ketone, ester, epoxy, and aryl (e.g., phenyl).

[0080] The silicon-containing unit derived from silane or silsesquioxane may have a monovalent or divalent structure. A monovalent structure may be formed by losing one R group or one R' group from the corresponding silane or silsesquioxane. A divalent structure may be formed by losing two R groups, two R' groups, or one R group and one R' group from the corresponding silane or silsesquioxane. Examples of monovalent silicon-containing units are shown in Figure 5 In. Symbol Indicates to connector L 1 key.

[0081] In some embodiments, the etching resistance enhancement unit 314 is a metal-containing unit containing a metal-oxygen bond. In some embodiments, the metal has a high EUV absorption coefficient. Examples of metals include, but are not limited to, aluminum (Al), cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), hafnium (Hf), indium (In), iron (Fe), manganese (Mn), molybdenum (Mo), nickel (Ni), niobium (Nb), scandium (Sc), silver (Ag), tantalum (Ta), titanium (Ti), tin (Sn), tungsten (W), vanadium (V), zinc (Zn), zirconium (Zr), and combinations thereof. In some embodiments, the metal in the metal-containing unit is Sn, Hf, Zn, Ti, Zr, W, or Sc. In some embodiments, the metal-containing unit is derived from an organic metal compound having the following structure:

[0082] MR 1 4-x (OR 2 ) x

[0083] in:

[0084] M is metal;

[0085] R 1 and R 2 are independently C1-C12 alkyl; and

[0086] x is an integer from 0 to 4.

[0087] In some embodiments, M is Sn, Hf, Zn, Ti, Zr, W, or Sc.

[0088] In some embodiments, the organometallic compound is selected from SnR 1 3(OR 2 1. SnR 1 2(OR 2 2. SnR 1 1(OR 2 )3. and SnR 2 4. Organic tin compounds.

[0089] In some embodiments, the organometallic compound is selected from HfR 1 3(OR 2 1. HfR 1 2(OR 2 2. HfR 1 1(OR 2 )3. HfR 2 4. An organic hafnium compound.

[0090] In some embodiments, the organometallic compound is selected from ZnR 1 3(OR 2 1. ZnR 1 2(OR 2 2. ZnR 1 1(OR 2 )3. and ZnR 2 4. Organic zinc compounds.

[0091] In some embodiments, R 1 and R 2 All are -CH3.

[0092] In some embodiments, the metal-containing unit derived from such an organometallic compound may include Sn 12 Ox、Hf4O x , or Zn4O x .

[0093] In some embodiments, the metal-containing unit can be derived from an organotin dodecamer cluster, such as Figure 6 shown.

[0094] The metal-containing unit derived from the above-mentioned organometallic compound may have a monovalent or divalent structure. The monovalent structure may be formed by the above-mentioned organometallic compound by losing one of its R 1 A group or an R 2 The divalent structure can be formed by the above-mentioned organometallic compound by losing two R 1 Group, two R 2A group or an R 1 Group and an R 2 In some embodiments, the monovalent metal-containing unit has the following structure:

[0095]

[0096] in Indicates to connector L 1 key.

[0097] In some embodiments, the metal-containing unit is derived from a metal oxide having the following structure:

[0098] M y Oz

[0099] in:

[0100] M is metal;

[0101] y and z are integers of 1 or greater.

[0102] In some embodiments, M is Sn, W, Zn, Sc, Fe, Ti, or V.

[0103] In some embodiments, y and z are both integers from 1 to 6.

[0104] In some embodiments, the metal oxide includes SnO2, WO3, ZnO, ZnO2, Sc2O3, Fe2O3, FeO2, Al2O3, TiO, TiO2, or V2O5.

[0105] Connector L 1 At each occurrence, it is independently substituted and unsubstituted branched and unbranched divalent aliphatic groups, substituted and unsubstituted divalent aromatic groups, unsubstituted or halogen-substituted divalent C3-C9 carbocyclic groups, -S-, -P-, -P(O2)-, -C(=O)S-, -C(=O)O-, -O-, -N-, -C(=O)N-, -SO2O-, -SO2S-, -SO-, -SO2- or a combination thereof.

[0106] In some embodiments, L 1 Includes C1-C 12 Alkylene or a C1-C1-C6H6-O-, -C6H6-OC(=O)O-, or -C(=O)-C6H6-OC(=O)O- covalently bonded to -S-, -P-, -P(O2)-, -C(=O)S-, -C(=O)O-, -O-, -N-, -C(=O)NH-, -SO2O-, -SO2S-, -SO-, -SO2-, -C6H6-O-, -C6H6-OC(=O)O-, or -C(=O)- 12 Alkylene.

[0107] In some embodiments, L 1 is -C(=O)O-. In some embodiments, L 1 is -C(=O)O-(CH2) 1-6 -. In some embodiments, L 1 yes

[0108] In some embodiments, m is an integer from 1 to 300, such as 1 to 100, 1 to 50, 1 to 25, or 1 to 10. In certain embodiments, m is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25.

[0109] In some embodiments, the first polymer 310 has one of the following structures:

[0110]

[0111]

[0112] In some embodiments, the second polymer 320 comprises a polymer backbone 322 and a 2 A cross-linker unit 324 covalently bonded to the polymer backbone 322. In some embodiments, the cross-linker unit 324 is present in the second polymer 320 in an amount ranging from about 5 wt % to about 70 wt % of the second polymer 320. If the amount of the cross-linker unit is less than about 5 wt %, the resist bottom layer may have insufficient solvent resistance to the photoresist developer. If the amount of the cross-linker unit is greater than about 70 wt %, the second polymer may lack sufficient solubility in the solvent.

[0113] In some embodiments, the second polymer 320 has the following structure (II):

[0114]

[0115] in:

[0116] L 2 is independently at each occurrence alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, cycloalkylene, heterocycloalkylene, arylene, heteroarylene, or a heteroatom linker;

[0117] C, at each occurrence, is a crosslinker unit comprising one or more crosslinkable groups; and

[0118] n is an integer of 1 or greater.

[0119] In some embodiments, the polymer backbone 322 has a hydrocarbon structure. In some embodiments, the second polymer 320 is a polyhydroxystyrene, polyacrylate, or polymethacrylate-based polymer. In some embodiments, the second polymer 320 includes a backbone derived from one or more monomers such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, acetoxyethyl acrylate, phenyl acrylate, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, cyclohexyl acrylate, benzyl acrylate, 2-alkyl-2-adamantyl (meth)acrylate, or dialkyl (1-adamantyl)methyl (meth)acrylate, methacrylic acid. In some embodiments, the second polymer 320 may have a polymer backbone 322 that is the same as the polymer backbone 312 of the first polymer 310. In some embodiments, the second polymer 320 may have a polymer backbone 322 that is different from the polymer backbone 312 of the first polymer 310.

[0120] The crosslinking unit 324 can be any suitable crosslinking agent. The crosslinking unit 324 on one of the polymer chains can react with another crosslinking unit 324 on another polymer chain under heating. The reaction of the crosslinking unit 324 bonds the two polymer chains together to form a polymer network. Crosslinking improves the solvent resistance of the resist bottom layer 220 so that the resist bottom layer 220 will not be dissolved by the solvent used to form the photoresist layer. Crosslinking also increases the molecular weight of the polymer resin in the resist bottom layer 220, which can lead to an increase in the glass transition temperature and overall density in the resist bottom layer 220. In some embodiments, the crosslinking unit 324 is an aliphatic or aromatic group containing one or more crosslinkable groups selected from epoxy, hydroxy, azo, alkyl halide, imine, alkene, alkyne, peroxide, ketone, aldehyde, allene, silane or heterocyclic groups.

[0121] In some embodiments, the cross-linker unit 324 has one of the following structures:

[0122]

[0123]

[0124] in:

[0125] R 3 is H, alkyl, heteroalkyl, aryl or heteroaryl at each occurrence;

[0126] z is an integer from 1 to 300; and

[0127] w is an integer from 1 to 6.

[0128] In some embodiments, R 3 is a cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, or branched or unbranched C1-C 12 In some embodiments, R 3 is unsubstituted or halogen-substituted C1-C 12 In some embodiments, R 3 It is a C1-C12 alkyl or C2-C12 alkenyl group substituted by one or more substituents selected from halogen, -SH, -PH3, -PO2, -C(=O)SH, -C(=O)OH, -OH, -NH2, -C(=O)NH, -SO2OH, -SO2SH, -SOH, -SO2, ether, ketone, ester, epoxy, and aryl (e.g., phenyl).

[0129] Connector L 2 At each occurrence, it is independently substituted and unsubstituted branched and unbranched divalent aliphatic groups, substituted and unsubstituted divalent aromatic groups, unsubstituted or halogen-substituted divalent C3-C9 carbocyclic groups, -S-, -P-, -P(O2)-, -C(=O)S-, -C(=O)O-, -O-, -N-, -C(=O)NH-, -SO2O-, -SO2S-, -SO-, -SO2- or a combination thereof.

[0130] In some embodiments, L 2 Includes C1-C 12 Alkylene or a C1-C1-C6H6-O-, -C6H6-OC(=O)O-, or -C(=O)-C6H6-OC(=O)O- covalently bonded to -S-, -P-, -P(O2)-, -C(=O)S-, -C(=O)O-, -O-, -N-, -C(=O)NH-, -SO2O-, -SO2S-, -SO-, -SO2-, -C6H6-O-, -C6H6-OC(=O)O-, or -C(=O)- 12 Alkylene.

[0131] In some embodiments, L 2is -C(=O)O-. In some embodiments, L 2 is -C(=O)O-(CH2) 1-6 -. In some embodiments, L 2 yes

[0132] In some embodiments, n is an integer from 1 to 300, such as from 1 to 100, from 1 to 50, from 1 to 25, or from 1 to 10. In certain embodiments, n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25.

[0133] In some embodiments, the second polymer 320 has one of the following structures:

[0134]

[0135] In some embodiments, the etch resistance enhancing unit 314 and the cross-linker unit 324 are attached to the same polymer backbone. Figure 3B Another embodiment of a resist underlayer composition 300 partially included in the resist underlayer 220 according to some embodiments of the present disclosure is shown. Figure 3A Unlike the embodiment shown in which the polymer resin in the resist underlayer composition 300 comprises a mixture of two homopolymers (i.e., a first polymer 310 and a second polymer 320), Figure 3B The resist bottom layer composition 300 shown in FIG. 1 includes a copolymer 350. In some embodiments, the copolymer 350 includes a polymer backbone 352, a 1 The etching resistance enhancing unit 314 attached to the polymer backbone 352 and the 2 A cross-linker unit 324 is attached to the polymer backbone 352 .

[0136] In some embodiments, copolymer 350 has the following structure (III):

[0137]

[0138]

[0139] in:

[0140] L 1 and L 2 is independently at each occurrence alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, cycloalkylene, heterocycloalkylene, arylene, heteroarylene, or a heteroatom linker,

[0141] E is independently an etch resistance enhancing unit at each occurrence;

[0142] C, at each occurrence, is independently a crosslinker unit comprising one or more crosslinkable groups; and

[0143] m, n and q are independently an integer of 1 or greater.

[0144] In the polymer of structure (III), the polymer backbone, the linker L 1 and L 2 , the etching resistance enhancing unit (E), and the cross-linking agent unit (C) are as previously described with respect to the first polymer 310 and the second polymer 320 .

[0145] In some embodiments, m is an integer from 1 to 300, such as 1 to 100, 1 to 50, 1 to 25, or 1 to 10. In certain embodiments, m is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25.

[0146] In some embodiments, n is an integer from 1 to 300, such as from 1 to 100, from 1 to 50, from 1 to 25, or from 1 to 10. In certain embodiments, n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25.

[0147] In some embodiments, q is independently at each occurrence an integer from 1 to 100, such as from 1 to 50, from 1 to 25, or from 1 to 10. In certain embodiments, q is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25.

[0148] In some embodiments, copolymer 350 has one of the following structures:

[0149]

[0150] In some embodiments, the resist underlayer composition 300 further comprises an acid generator 330 for triggering a crosslinking reaction of the crosslinker unit 324. In some embodiments, the acid generator 330 comprises a thermal acid generator (TAG), a photoacid generator (PAG), or a combination thereof.

[0151] In some embodiments, the acid generator 330 comprises a thermal generator that generates acid when heated. In some embodiments, the thermal acid generator is selected from the group consisting of:

[0152] NH4 + C4H9SO3 - ; NH4 + CF3SO3 - ;

[0153] in:

[0154] R is H, alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl; and

[0155] n is an integer of 1 to 4.

[0156] In some embodiments, R is a cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, or branched or unbranched C1-C 12 In some embodiments, R is unsubstituted or halogen-substituted C1-C 12 Alkyl groups. In some embodiments, R is a C2-C12 alkenyl or C1-C12 alkyl group substituted with one or more substituents selected from halogen, -SH, -PH3, -PO2, -C(=O)SH, -C(=O)OH, -OH, -NH2, -C(=O)NH2, -SO2OH, -SO2SH, -SOH, -SO2, ether, ketone, ester, epoxy, and aryl (e.g., phenyl).

[0157] In some embodiments, the acid generator 330 includes a photoacid generator (PAG) that generates an acid when exposed to radiation (eg, EUV radiation or electron beam radiation).

[0158] In some embodiments, the photoacid generator may include a combination of cations and anions. Examples of photoacid generators according to embodiments of the present disclosure include α-(trifluoromethylsulfonyloxy)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide (MDT), N-hydroxy-naphthalene dicarboximide (DDSN), benzoin toluenesulfonate, tert-butylphenyl-α-(p-toluenesulfonyloxy) acetate and tert-butyl-α-(p-toluenesulfonyloxy) acetate, triarylsulfonium and diaryliodonium hexafluoroantimonate, hexafluoroarsenate, trifluoromethanesulfonate, iodonium perfluorooctanesulfonate, N-camphorsulfonyloxynaphthalimide, N-pentafluorophenylsulfonyloxynaphthalimide, ionic iodonium sulfonate (e.g., diaryliodonium (alkyl or aryl) sulfonates and bis-(di-tert-butylphenyl)iodonium camphenyl sulfonate), perfluoroalkane sulfonates (e.g., perfluoropentane sulfonate, perfluorooctane sulfonate, perfluoromethane sulfonate), aryl (e.g., phenyl or benzyl) trifluoromethane sulfonates (e.g., triphenylsulfonium trifluoromethane sulfonate or (bis-tert-butylphenyl)iodonium trifluoromethane sulfonate); pyrogallol derivatives (e.g., pyrogallol trimesylate), trifluoromethane sulfonates of hydroxyimides, α,α'-bissulfonyl-diazomethane, sulfonates of nitro-substituted benzyl alcohols, naphthoquinone-4-diazide, alkyl disulfones, and the like.

[0159] In some embodiments, the cation is selected from the group consisting of:

[0160]

[0161] In some embodiments, the anion is selected from the group consisting of:

[0162] C4F9SO 3- ;C6F 13 SO 3- ;

[0163] In some embodiments, the concentration of the acid generator 330 is in the range of about 0.5 wt % to about 30 wt % based on the total weight of the resist underlayer composition. When the concentration of the acid generator 330 is lower than the disclosed range, sufficient acid may not be generated to promote the cross-linking reaction of the cross-linking agent unit 324. When the concentration of the acid generator 330 is greater than the disclosed range, the efficiency of the cross-linking reaction of the cross-linking agent unit 324 may not be significantly improved.

[0164] In some embodiments, the resist bottom layer composition 300 includes a solvent 340. The solvent 340 can be any suitable solvent. In some embodiments, the solvent 340 is selected from propylene glycol methyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 1-ethoxy-2-propanol (PGEE), γ-butyrolactone (GBL), cyclohexanone (CHN), ethyl lactate (EL), methanol, ethanol, propanol, n-butanol, acetone, dimethylformamide (DMF), isopropanol (IPA), tetrahydrofuran (THF), methyl isobutyl carbinol (AMC), n-butyl acetate (nBA), and 2-heptanone (MAK) One or more.

[0165] In some embodiments, a mixture or copolymer 350 of the first polymer 310 and the second polymer 320 and an acid generator 330 are added to a solvent 340 for application, and the resist base layer 220 is formed by applying the resist base layer composition, for example, by spin coating or printing, onto the top surface of the material layer 210 (if present), or onto the substrate 202. Alternatively, the resist base layer 220 can be formed by a suitable deposition process, such as CVD, PVD, or ALD. In some embodiments, the resist base layer 220 can be formed to have a thickness ranging from about 100 to about 1000. to about A layer thickness less than the disclosed range may not be sufficient to provide adequate etch resistance and anti-reflection properties. A layer thickness greater than the disclosed range may not provide further improved etch resistance and anti-reflection properties but may result in material waste.

[0166] Reference Figure 1 and Figure 2C According to some embodiments, the method 100 proceeds to operation 106 where a first baking process is performed to form a cross-linked resist bottom layer 222 . Figure 2C is a cross-sectional view of the semiconductor device 200 after performing a first baking process according to some embodiments.

[0167] The first baking process is performed at a temperature and time period sufficient to react the crosslinking agent units 324 with each other and to bond the individual polymer chains of the second polymer 320 or the individual polymer chains of the copolymer 350 in the resist bottom layer 220 to form a polymer network. In some embodiments, the first baking process is performed at a temperature ranging from about 100° C. to about 400° C. In certain embodiments, the first baking process is performed at a temperature of about 80° C. to about 200° C. for about 20 seconds to about 3 minutes. In other embodiments, the first baking process is performed at a temperature of about 100° C. to about 250° C. for about 10 seconds to about 2 minutes. The first baking process forms a crosslinked resist bottom layer 222 having good solvent resistance to allow a photoresist layer to be applied without dissolving the crosslinked resist bottom layer 222.

[0168] Reference Figure 1 and Figure 2D According to some embodiments, the method 100 proceeds to operation 108 where a photoresist layer 230 is deposited over the cross-linked resist bottom layer 222 . Figure 2D After depositing a photoresist layer 230 over the cross-linked resist bottom layer 222 Figure 2C FIG. 2 is a cross-sectional view of a semiconductor device 200 .

[0169] Photoresist layer 230 is a photosensitive layer that can be patterned by exposure to radiation. Typically, the chemical properties of the photoresist region affected by the incident radiation vary in a manner that depends on the type of photoresist used. Photoresist layer 230 comprises a positive resist or a negative resist. A positive resist refers to a photoresist material that becomes soluble in a developer when exposed to radiation (e.g., UV light), while the unexposed (or less exposed) region of the photoresist is insoluble in the developer. On the other hand, a negative resist refers to a photoresist material that becomes insoluble in a developer when exposed to radiation, while the unexposed (or less exposed) region of the photoresist is soluble in the developer. The region of the negative resist that becomes insoluble when exposed to radiation may become insoluble due to a cross-linking reaction caused by exposure to radiation.

[0170] In some embodiments, the photoresist layer 230 comprises a high-sensitivity photoresist composition. In some embodiments, the high-sensitivity photoresist composition comprises a metal having a high absorption coefficient for EUV radiation. In some embodiments, the photoresist layer 230 may comprise an organometallic compound comprising a metal core coordinated to a plurality of organic ligands. In some embodiments and as Fig. 7A As shown, the organometallic compound has the formula:

[0171] M a L bX c ,

[0172] in:

[0173] M is at least one of tin (Sn), bismuth (Bi), antimony (Sb), indium (In), tellurium (Te), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), cobalt (Co), molybdenum (Mo), tungsten (W), aluminum (Al), arsenic (As), yttrium (Y), lanthanum (La), cerium (Ce), or lutetium (Lu);

[0174] L is independently alkyl, alkenyl, cycloalkyl, cycloheteroalkyl, arylalkyl, aryl or heteroaryl;

[0175] X is independently a hydrolyzable ligand; and

[0176] 1≤a≤2, b≥1, c≥1, and b+c≤5.

[0177] In some embodiments, M is selected from the group consisting of Sn, Bi, Sb, In, Te and combinations thereof. In some embodiments, L is a C1-C6 alkyl or a C2-C6 alkenyl. In some embodiments, L is selected from the group consisting of propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, isohexyl, sec-hexyl, tert-hexyl and combinations thereof. In some embodiments, L is fluorinated so that an alkyl or alkenyl group is substituted with one or more fluorine groups.

[0178] In some embodiments, X is any moiety that readily reacts with a second compound to generate -OH, such as a moiety selected from the group consisting of: amines, including dialkylamino and monoalkylamino; alkoxy; carboxylates, halogens, and sulfonates. In some embodiments, the sulfonate group is substituted with one or more amine groups. In some embodiments, the halogen is one or more selected from the group consisting of: F, Cl, Br, and I. In some embodiments, the sulfonate group includes a substituted or unsubstituted C1-C3 group.

[0179] In some embodiments, the second compound is at least one of an amine, a borane, a phosphine, or water. In some embodiments, the amine has the formula N p H n X m , wherein 0≤n≤3, 0≤m≤3, n+m=3 when p is 1, and n+m=4 when p is 2, and each X is independently a halogen selected from the group consisting of: F, Cl, Br, and I. In some embodiments, the borane has the formula B p H n X m, wherein 0≤n≤3, 0≤m≤3, n+m=3 when p is 1, and n+m=4 when p is 2, and each X is independently a halogen selected from the group consisting of: F, Cl, Br, and I. In some embodiments, the phosphine has the formula P p H n X m , wherein 0≤n≤3, 0≤m≤3, n+m=3 when p is 1, or n+m=4 when p is 2, and each X is independently a halogen selected from the group consisting of F, Cl, Br, and I.

[0180] Figure 7B The reaction between the organometallic compound 702 and water is shown. Figure 7B As shown, in the presence of water, the organometallic compound 702 is hydrolyzed, i.e., the hydroxyl group replaces the hydrolyzable ligand and bonds to the core M, thereby producing a hydroxyl-containing compound 704. More than one hydroxyl-containing compound 704 may undergo a condensation reaction to form an organometallic polymer 706. It should be noted that while the organometallic polymer 706 includes three organometallic compounds 702, organometallic polymers having fewer or more organometallic compounds 702 are contemplated.

[0181] In some embodiments, the organometallic compound includes secondary hexyl tris (dimethylamino) tin, tert-hexyl tris (dimethylamino) tin, isohexyl tris (dimethylamino) tin, n-hexyl tris (dimethylamino) tin, secondary amyl tris (dimethylamino) tin, tert-amyl tris (dimethylamino) tin, isopentyl tris (dimethylamino) tin, n-amyl tris (dimethylamino) tin, secondary butyl tris (dimethylamino) tin, tert-butyl tris (dimethylamino) tin, isobutyl tris (dimethylamino) tin, n-butyl tris (dimethylamino) tin, secondary butyl tris (dimethylamino) tin, isopropyl tris (dimethylamino) tin , n-propyl tri(diethylamino)tin and similar alkyl(tri)(tert-butoxy)tin compounds, including sec-hexyl tri(tert-butoxy)tin, tert-hexyl tri(tert-butoxy)tin, isohexyl tri(tert-butoxy)tin, n-hexyl tri(tert-butoxy)tin, sec-pentyl tri(tert-butoxy)tin, tert-pentyl tri(tert-butoxy)tin, isopentyl tri(tert-butoxy)tin, n-pentyl tri(tert-butoxy)tin, tert-butyl tri(tert-butoxy)tin, isobutyl tri(butoxy)tin, n-butyl tri(butoxy)tin, sec-butyl tri(butoxy)tin, or n-propyl tri(butoxy)tin. In some embodiments, the organometallic compound is fluorinated. In some embodiments, the boiling point of the organometallic compound is less than about 200°C.

[0182] In some embodiments, the organometallic compound has one of the following structures:

[0183]

[0184] In some embodiments, the photoresist layer 230 is formed by applying a photoresist composition over the crosslinked resist bottom layer 222 using, for example, spin coating. In some embodiments, the photoresist composition includes at least one type of organic metal compound and at least one type of solvent. The amount of the organic metal compound in the photoresist composition can be about 0.5 wt % to 10 wt %. In some embodiments, the photoresist composition may include about 1 wt % of the organic metal compound. In some other embodiments, the photoresist layer 230 is formed by depositing the organic metal compound using CVD, PVD or ALD.

[0185] In some embodiments, after the photoresist layer 230 is disposed over the cross-linked resist bottom layer 222, a pre-exposure bake process may be performed to remove the solvent from the photoresist layer 230. In some embodiments, the pre-exposure bake process may be performed at a temperature of about 40° C. to about 140° C. for 10 seconds to 5 minutes. In some embodiments, the photoresist layer 230 is heated at a temperature of about 60° C. to about 120° C. for 20 seconds to 3 minutes.

[0186] Reference Figure 1 and Figure 2E According to some embodiments, method 100 proceeds to operation 110 where photoresist layer 230 is exposed to radiation 240 . Figure 2E is a cross-sectional view of semiconductor device 200 after exposing photoresist layer 230 to radiation 240 , according to some embodiments.

[0187] The photoresist layer 230 is exposed to radiation 240 from a light source through a photomask 250. The photomask 250 has a predefined pattern designed for an IC based on the specifications of the IC to be manufactured. The pattern of the photomask 250 corresponds to the pattern of materials that make up the various components of the IC device to be manufactured. For example, a portion of the IC design layout includes various IC features to be formed in the substrate 202, such as active areas, gate electrodes, source and drain electrodes, metal lines or vias for interconnecting between layers, and openings for bonding pads.

[0188] In some embodiments, the photomask 250 includes a first region 252 and a second region 254. In the first region 252, the radiation 240 is blocked by the photomask 250 and cannot reach the photoresist layer 230, while in the second region 254, the radiation 240 is not blocked by the photomask 250 and can pass through the photomask 250 to reach the photoresist layer 230. Therefore, the photoresist layer 230 is selectively exposed through the photomask 250, thereby forming an exposed region 230E and an unexposed region 230U in the photoresist layer 230.

[0189] In some embodiments, radiation 240 is EUV radiation (e.g., 13.5 nm). Alternatively, in some embodiments, radiation 240 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, for EUV lithography and electron beam lithography, operation 110 is performed in a liquid (immersion lithography) or in a vacuum.

[0190] In some embodiments, the exposed regions 230E of the photoresist layer 230 irradiated by the radiation 240 undergo further condensation reactions to form metal clusters, while the unexposed regions 230U not irradiated by the radiation 240 do not undergo condensation reactions. The exposed regions 230E of the photoresist layer 230 may constitute a latent pattern. Since the metal clusters are substantially insoluble in the developer used in the subsequent development process, the exposed regions 220E of the photoresist layer 230 irradiated by the radiation 240 are substantially insoluble in the developer. The unexposed regions 230U not irradiated by the radiation 240 do not undergo condensation reactions and are soluble in the developer. The solubility difference allows the latent pattern to be developed during the development process.

[0191] Figure 8 240. The reaction of an organometallic compound due to exposure to radiation 240 is shown in some embodiments. Due to exposure to radiation 240, the ligand L is separated from the metal core M of the organometallic compound. + The organic metal compound cores are cleaved and two or more organic metal compound cores are bonded to each other to form a metal oxide cluster.

[0192] Subsequently, a post-exposure baking process may be performed on the photoresist layer 230. The post-exposure baking process may be performed at a temperature of about 80° C. to about 350° C. for a duration of about 60 seconds to about 360 seconds. The post-exposure baking process may accelerate the diffusion of the photoacid, which in turn accelerates the cross-linking reaction in the cross-linked resist bottom layer 222.

[0193] Reference Figure 1 and Figure 2F According to some embodiments, the method 100 proceeds to operation 112 in which the photoresist layer 230 is developed using a developer to form a patterned photoresist layer 230P. Figure 2F After forming the patterned photoresist layer 230P, Figure 2E A cross-sectional view of a semiconductor device.

[0194] During the development process, a developer is applied to the photoresist layer 230. The developer removes the exposed areas 230E or the unexposed areas 230U depending on the type of resist. Figure 2FAs shown, the photoresist layer 230 comprises a negative resist, so that the exposed area 230E is not dissolved by the developer and remains on the cross-linked resist bottom layer 222 after the development process. If the photoresist layer 230 comprises a positive resist, the exposed area 230E will be dissolved by the developer, so that the unexposed portion 230U remains on the cross-linked resist bottom layer 222 during the development process.

[0195] The remaining exposed areas 230E (or unexposed areas 230U) define a pattern in the patterned photoresist layer 230P. The pattern includes one or more openings that expose portions of the underlying cross-linked resist bottom layer 222. Due to the small size of the organometallic oxide hydroxide clusters, the pattern in the patterned photoresist layer 230P can define features with a pitch of about 24 nm to about 36 nm.

[0196] The developer may include alcohols, aromatic hydrocarbons, etc. Examples of alcohols include, but are not limited to, methanol, ethanol, 1-butanol, and 4-methyl-2-pentanol. Examples of aromatic hydrocarbons include, but are not limited to, xylene, toluene, and benzene. In some embodiments, the developer is selected from at least one of methanol, 4-methyl-2-pentanol, and xylene.

[0197] The developer may be applied using any suitable method. In some embodiments, the developer is applied by Figure 2E The developer is applied by dipping the structure into a developer bath. In some embodiments, the developer is sprayed into the photoresist layer 230.

[0198] Reference Figure 1 and Figure 2G According to some embodiments, the method 100 proceeds to operation 114 in which the cross-linked resist bottom layer 222 is etched using the patterned photoresist layer 230P as an etching mask. Figure 2G After etching the cross-linked resist bottom layer 222 using the patterned photoresist layer 230P as an etching mask, Figure 2F FIG. 2 is a cross-sectional view of a semiconductor device 200 .

[0199] Reference Figure 2G , the cross-linked resist bottom layer 222 is etched using the patterned photoresist layer 230P as an etching mask to form a patterned cross-linked resist bottom layer 222P. The etching can be dry etching (e.g., RIE) or wet etching. The etching of the cross-linked resist bottom layer 222 exposes portions of the underlying material layer 210. If the patterned photoresist layer 230P is not completely consumed during the etching process, after etching the cross-linked resist bottom layer 222, the patterned photoresist layer can be removed by, for example, stripping or oxygen plasma.

[0200] The presence of the etching enhancement unit 314 in the cross-linked resist bottom layer 222 increases the etching selectivity between the cross-linked resist bottom layer 222 and the patterned photoresist layer 230P. As a result, the leakage window of the photoresist can be improved by more than 3%. In addition, since the presence of the etching enhancement unit 314 also increases EUV absorption, the exposure dose (exposuredose, EOP) can be reduced by more than 3%. Therefore, the resist bottom layer composition disclosed in the present invention helps to improve the resist performance.

[0201] Reference Figure 1 and Figure 2H According to some embodiments, the method 100 proceeds to operation 116 in which the material layer 210 is etched using the patterned cross-linked resist bottom layer 222P as an etching mask. Figure 2H After etching the material layer 210 using the patterned cross-linked resist bottom layer 222P as an etching mask, Figure 2G FIG. 2 is a cross-sectional view of a semiconductor device 200 .

[0202] Reference Figure 2H The material layer 210 is etched using the patterned cross-linked resist bottom layer 222P as an etching mask to form a patterned target layer 210P. The etching of the material layer 210 exposes portions of the underlying substrate 202.

[0203] An etching process may be performed to transfer the pattern in the patterned cross-linked resist bottom layer 222P to the material layer 210. In some embodiments, the etching process is anisotropic etching, such as dry etching. In some embodiments, the dry etching is RIE or plasma etching.

[0204] One or more manufacturing processes, such as an etching process or an implantation process, may be performed on the substrate 202 using the patterned cross-linked resist bottom layer 222P and the patterned target layer 210P as masks.

[0205] One aspect of the present specification relates to a resist base layer composition. The resist base layer composition comprises a first polymer, the first polymer comprises a first polymer main chain and an etching resistance enhancing unit covalently bonded to the first polymer main chain via a first linker, wherein the etching resistance enhancing unit comprises a silicon-containing unit containing a silicon-oxygen bond or a metal-containing unit containing a metal-oxygen bond; a second polymer, the second polymer comprises a second polymer main chain and a crosslinker unit covalently bonded to the second polymer main chain via a second linker, wherein the crosslinker unit comprises one or more crosslinkable groups; an acid generator; and a solvent.

[0206] Another aspect of the present specification relates to a resist bottom layer composition. The resist bottom layer composition comprises an acid generator; a solvent; and a copolymer having the following structure (III):

[0207]

[0208] In the copolymer of structure (III), L 1 and L 2 Each occurrence is independently an alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, cycloalkylene, heterocycloalkylene, arylene, heteroarylene, or heteroatom linker. Each occurrence of E is independently an etch resistance enhancing unit. Each occurrence of C is independently a crosslinker unit comprising one or more crosslinkable groups. m, n, and q are independently an integer of 1 or greater.

[0209] Another aspect of the present specification relates to a method for forming a semiconductor device. The method includes forming a resist bottom layer above a material layer on a substrate, the resist bottom layer comprising a first polymer, a second polymer, and an acid generator. The first polymer comprises a first polymer backbone and an etching resistance enhancing unit covalently bonded to the first polymer backbone via a first joint. The etching resistance enhancing unit comprises a silicon-containing unit containing a silicon-oxygen bond or a metal-containing unit containing a metal-oxygen bond. The second polymer comprises a second polymer backbone and a crosslinker unit covalently bonded to the second polymer backbone via a second joint. The crosslinker unit comprises one or more crosslinkable groups. The method further includes: performing a baking process to cause the cross-linking groups to undergo a cross-linking reaction, thereby forming a cross-linked resist bottom layer; depositing a photoresist layer containing a metal photoresist over the cross-linked resist bottom layer; selectively exposing the photoresist layer to patterned radiation; developing the selectively exposed photoresist layer to form a patterned photoresist layer; using the patterned photoresist layer as an etching mask to etch the cross-linked resist bottom layer to form a patterned cross-linked resist bottom layer; and using the patterned cross-linked resist bottom layer as an etching mask to etch the material layer.

[0210] The present invention also includes the following exemplary embodiments:

[0211] Embodiment 1. A resist base composition, comprising:

[0212] a first polymer comprising a first polymer backbone and an etch resistance enhancing unit covalently bonded to the first polymer backbone via a first linker, wherein the etch resistance enhancing unit comprises a silicon-containing unit containing a silicon-oxygen bond or a metal-containing unit containing a metal-oxygen bond;

[0213] a second polymer comprising a second polymer backbone and a cross-linker unit covalently bonded to the second polymer backbone via a second linker, wherein the cross-linker unit comprises one or more cross-linkable groups;

[0214] Acid generators; and

[0215] Solvent.

[0216] Embodiment 2. The resist underlayer composition according to embodiment 1, wherein the silicon-containing unit is derived from silane, wherein the silane has one of the following structures:

[0217]

[0218] wherein R and R' at each occurrence are independently cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, or branched or unbranched C1-C12 aliphatic groups.

[0219] Embodiment 3. The resist underlayer composition according to embodiment 2, wherein R and R' are independently C1-C12 alkyl or C2-C12 alkenyl groups at each occurrence, wherein the C1-C12 alkyl or C2-C12 alkenyl groups are unsubstituted or substituted with one or more substituents selected from halogen, -SH, -PH3, -PO2, -C(=O)SH, -C(=O)OH, -OH, -NH2, -C(=O)NH2, -SO2OH, -SO2SH, -SOH, -SO2, ether, ketone, ester, epoxy and phenyl.

[0220] Embodiment 4. The resist underlayer composition according to embodiment 1, wherein the silicon-containing unit is derived from silsesquioxane, wherein the silsesquioxane has one of the following structures:

[0221]

[0222] wherein R at each occurrence is independently a cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, or branched or unbranched C1-C12 aliphatic group.

[0223] Embodiment 5. The resist underlayer composition according to embodiment 4, wherein R is independently a C1-C12 alkyl group or a C2-C12 alkenyl group at each occurrence, wherein the C1-C12 alkyl group or the C2-C12 alkenyl group is unsubstituted or substituted with one or more substituents selected from halogen, -SH, -PH3, -PO2, -C(=O)SH, -C(=O)OH, -OH, -NH2, -C(=O)NH2, -SO2OH, -SO2SH, -SOH, -SO2, ether, ketone, ester, epoxy and phenyl.

[0224] Embodiment 6. The resist underlayer composition according to embodiment 1, wherein the first polymer has one of the following structures:

[0225]

[0226] Embodiment 7. The resist underlayer composition according to embodiment 1, wherein the etching resistance enhancing unit is derived from an organic metal compound having the following structure:

[0227] MR 1 4-x (OR 2 ) x

[0228] in:

[0229] M is a metal, and the metal includes tin (Sn), zinc (Zn), hafnium (Hf), titanium (Ti), zirconium (Zr), tungsten (W) or scandium (Sc);

[0230] R 1 and R 2 are independently C1-C12 alkyl; and

[0231] x is an integer from 0 to 4.

[0232] Embodiment 8. According to the anti-etching base composition described in embodiment 1, the one or more crosslinkable groups in the crosslinker unit include epoxy, hydroxyl, azo, alkyl halide, imine, alkene, alkyne, peroxide, ketone, aldehyde, allene, silane or heterocyclic group.

[0233] Embodiment 9. The resist underlayer composition according to embodiment 8, wherein the crosslinking agent unit has one of the following structures:

[0234]

[0235] in:

[0236] R 3 is H, alkyl, heteroalkyl, aryl or heteroaryl at each occurrence;

[0237] z is an integer from 1 to 300; and

[0238] w is an integer from 1 to 6.

[0239] Embodiment 10. The resist underlayer composition according to embodiment 1, wherein the acid generator is a thermal acid generator, a photoacid generator, or a combination thereof.

[0240] Embodiment 11. A resist base layer composition, comprising:

[0241] Acid generators;

[0242] Solvents; and

[0243] A copolymer having the following structure (III):

[0244]

[0245] in:

[0246] L 1 and L 2 is independently at each occurrence alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, cycloalkylene, heterocycloalkylene, arylene, heteroarylene, or a heteroatom linker;

[0247] E is independently an etch resistance enhancing unit at each occurrence;

[0248] C, at each occurrence, is independently a crosslinker unit comprising one or more crosslinkable groups; and

[0249] m, n and q are independently an integer of 1 or greater.

[0250] Embodiment 12. The resist underlayer composition according to embodiment 11, wherein E is a silicon-containing unit derived from silane, wherein the silane has one of the following structures:

[0251]

[0252] wherein R and R' are independently, at each occurrence, a C1-C12 alkyl or C2-C12 alkenyl group, wherein the C1-C12 alkyl or C2-C12 alkenyl group is unsubstituted or substituted with one or more substituents selected from halogen, -SH, -PH3, -PO2, -C(=O)SH, -C(=O)OH, -OH, -NH2, -C(=O)NH2, -SO2OH, -SO2SH, -SOH, -SO2, ether, ketone, ester, epoxy and phenyl.

[0253] Embodiment 13. The resist underlayer composition according to embodiment 11, wherein the E is derived from a silsesquioxane having one of the following structures:

[0254]

[0255] wherein R at each occurrence is independently a C1-C12 alkyl or C2-C12 alkenyl group, wherein the C1-C12 alkyl or C2-C12 alkenyl group is unsubstituted or substituted with one or more substituents selected from halogen, -SH, -PH3, -PO2, -C(=O)SH, -C(=O)OH, -OH, -NH2, -C(=O)NH2, -SO2OH, -SO2SH, -SOH, -SO2, ether, ketone, ester, epoxy and phenyl.

[0256] Embodiment 14. The resist underlayer composition according to embodiment 11, wherein E is a metal-containing unit derived from an organic metal compound having the following structure:

[0257] MR 1 4-x (OR 2 ) x

[0258] in:

[0259] M is a metal, and the metal includes tin (Sn), zinc (Zn), hafnium (Hf), titanium (Ti), zirconium (Zr), tungsten (W) or scandium (Sc);

[0260] R 1 and R 2 are independently C1-C12 alkyl; and

[0261] x is an integer from 0 to 4.

[0262] Embodiment 15. The resist underlayer composition according to embodiment 12, wherein the organic metal compound is SnR 1 3(OR 2 1. SnR 1 2(OR 2 2. SnR 1 1(OR 2 3. SnR 2 4. HfR 1 3(OR 2 1. HfR 1 2(OR 2 2. HfR 1 1(OR 2 3. HfR 2 4. ZnR 1 3(OR 2 1. ZnR 1 2(OR 2 2. ZnR 1 1(OR 2 )3, or ZnR 2 4, where R1 and R 2 All are methyl.

[0263] Embodiment 16. The resist underlayer composition according to embodiment 12, wherein the copolymer of structure (III) has one of the following structures:

[0264]

[0265] Embodiment 17. A method for forming a semiconductor device, the method comprising:

[0266] A resist bottom layer is formed over the material layer on the substrate, wherein the resist bottom layer comprises a first polymer, a second polymer, and an acid generator, wherein:

[0267] The first polymer comprises a first polymer backbone and an etch resistance enhancing unit covalently bonded to the first polymer backbone via a first linker, the etch resistance enhancing unit comprising a silicon-containing unit containing a silicon-oxygen bond or a metal-containing unit containing a metal-oxygen bond;

[0268] The second polymer comprises a second polymer backbone and a cross-linker unit covalently bonded to the second polymer backbone via a second linker, wherein the cross-linker unit comprises one or more cross-linkable groups;

[0269] Performing a baking process to allow the cross-linking groups to undergo a cross-linking reaction, thereby forming a cross-linked resist bottom layer;

[0270] depositing a photoresist layer comprising a metal photoresist over the cross-linked resist bottom layer;

[0271] selectively exposing the photoresist layer to patterned radiation;

[0272] developing the selectively exposed photoresist layer to form a patterned photoresist layer;

[0273] etching the cross-linked resist bottom layer using the patterned photoresist layer as an etching mask to form a patterned cross-linked resist bottom layer; and

[0274] The material layer is etched using the patterned cross-linked resist bottom layer as an etching mask.

[0275] Embodiment 18. The method of embodiment 17, wherein the silicon-containing unit is derived from a compound having one of the following structures:

[0276]

[0277] wherein R and R' are independently, at each occurrence, a C1-C12 alkyl or C2-C12 alkenyl group, wherein the C1-C12 alkyl or C2-C12 alkenyl group is unsubstituted or substituted with one or more substituents selected from halogen, -SH, -PH3, -PO2, -C(=O)SH, -C(=O)OH, -OH, -NH2, -C(=O)NH2, -SO2OH, -SO2SH, -SOH, -SO2, ether, ketone, ester, epoxy and phenyl.

[0278] Embodiment 19. The method of embodiment 17, wherein the metal-containing unit is derived from an organometallic compound having the following structure:

[0279] MR 1 4-x (OR 2 ) x

[0280] in:

[0281] M is a metal, and the metal includes tin (Sn), zinc (Zn), hafnium (Hf), titanium (Ti), zirconium (Zr), tungsten (W) or scandium (Sc);

[0282] R 1 and R 2 are independently C1-C12 alkyl; and

[0283] x is an integer from 0 to 4.

[0284] Embodiment 20. The method of embodiment 17, wherein the crosslinker unit has one of the following structures:

[0285]

[0286] in:

[0287] R 3 is H, alkyl, heteroalkyl, aryl or heteroaryl at each occurrence;

[0288] z is an integer from 1 to 300; and

[0289] w is an integer from 1 to 6.

[0290] The foregoing summarizes the features of several embodiments so that those skilled in the art can better understand the various aspects of the present disclosure. Those skilled in the art will appreciate that they can easily use the present disclosure as a basis for designing or modifying other methods and structures to implement the same purposes and / or achieve the same advantages as the embodiments described herein. Those skilled in the art will also appreciate that such equivalent constructions do not depart from the spirit and scope of the present disclosure, and that they can make various changes, substitutions, and modifications without departing from the spirit and scope of the present disclosure.

Claims

1. A resist bottom layer composition, comprising: a first polymer comprising a first polymer backbone and an etch resistance enhancing unit covalently bonded to the first polymer backbone via a first linker, wherein the etch resistance enhancing unit comprises a silicon-containing unit containing a silicon-oxygen bond or a metal-containing unit containing a metal-oxygen bond; a second polymer comprising a second polymer backbone and a cross-linker unit covalently bonded to the second polymer backbone via a second linker, wherein the cross-linker unit comprises one or more cross-linkable groups; Acid generators; and Solvent.

2. The resist underlayer composition according to claim 1, wherein the silicon-containing unit is derived from silane, wherein the silane has one of the following structures: wherein R and R' at each occurrence are independently cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, or branched or unbranched C1-C12 aliphatic groups.

3. The resist underlayer composition according to claim 1, wherein the silicon-containing unit is derived from silsesquioxane, wherein the silsesquioxane has one of the following structures: wherein R at each occurrence is independently a cyclic or acyclic, saturated or unsaturated, substituted or unsubstituted, or branched or unbranched C1-C12 aliphatic group.

4. The resist underlayer composition according to claim 1, wherein the first polymer has one of the following structures:

5. The resist underlayer composition according to claim 1, wherein the etching resistance enhancing unit is derived from an organic metal compound having the following structure: MR 1 4-x (OR 2 ) x in: M is a metal, and the metal includes tin (Sn), zinc (Zn), hafnium (Hf), titanium (Ti), zirconium (Zr), tungsten (W) or scandium (Sc); R 1 and R 2 are independently C1-C12 alkyl; and x is an integer from 0 to 4.

6. The resist underlayer composition according to claim 1, wherein the one or more crosslinkable groups in the crosslinker unit include epoxy, hydroxyl, azo, alkyl halide, imine, alkene, alkyne, peroxide, ketone, aldehyde, allene, silane or heterocyclic groups.

7. The resist underlayer composition according to claim 6, wherein the crosslinking agent unit has one of the following structures: in: R 3 is H, alkyl, heteroalkyl, aryl or heteroaryl at each occurrence; z is an integer from 1 to 300; and w is an integer from 1 to 6. 8 . The resist underlayer composition according to claim 1 , wherein the acid generator is a thermal acid generator, a photoacid generator, or a combination thereof.

9. A resist base layer composition, comprising: Acid generators; Solvents; and A copolymer having the following structure (III): in: L 1 and L 2 is independently at each occurrence alkylene, alkenylene, alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, cycloalkylene, heterocycloalkylene, arylene, heteroarylene, or a heteroatom linker; E is independently an etch resistance enhancing unit at each occurrence; C, at each occurrence, is independently a crosslinker unit comprising one or more crosslinkable groups; and m, n and q are independently an integer of 1 or greater.

10. A method for forming a semiconductor device, the method comprising: A resist bottom layer is formed over the material layer on the substrate, wherein the resist bottom layer comprises a first polymer, a second polymer, and an acid generator, wherein: The first polymer comprises a first polymer backbone and an etch resistance enhancing unit covalently bonded to the first polymer backbone via a first linker, the etch resistance enhancing unit comprising a silicon-containing unit containing a silicon-oxygen bond or a metal-containing unit containing a metal-oxygen bond; The second polymer comprises a second polymer backbone and a cross-linker unit covalently bonded to the second polymer backbone via a second linker, wherein the cross-linker unit comprises one or more cross-linkable groups; Performing a baking process to allow the cross-linking groups to undergo a cross-linking reaction, thereby forming a cross-linked resist bottom layer; depositing a photoresist layer comprising a metal photoresist over the cross-linked resist bottom layer; selectively exposing the photoresist layer to patterned radiation; developing the selectively exposed photoresist layer to form a patterned photoresist layer; etching the cross-linked resist bottom layer using the patterned photoresist layer as an etching mask to form a patterned cross-linked resist bottom layer; and The material layer is etched using the patterned cross-linked resist bottom layer as an etching mask.

Images