Photoresist primer composition

Abstract

A photoresist primer composition comprising a first polymer, the first polymer comprising a first structural unit derived from an N-(alkoxymethyl)(meth)acrylamide monomer; a second structural unit comprising an aromatic group, a heterocyclic group, an ester group, an amide group, or a combination thereof, wherein the second structural unit further comprises a crosslinkable group; wherein the first polymer comprises the second structural unit, the photoresist primer composition further comprising a second polymer comprising the second structural unit, or a combination thereof, a thermal acid generator; and a solvent.

Description

Technical Field

[0001] This invention relates generally to the field of manufacturing electronic devices, and more specifically to the field of materials used in semiconductor manufacturing. Background Technology

[0002] Photoresist underlayer compositions are used in the semiconductor industry as etch masks for photolithography in advanced technology nodes of integrated circuit manufacturing. These compositions are typically used in three-layer and four-layer photoresist integration schemes, in which an organic or silicon-containing antireflective coating and a patternable photoresist film are arranged on the underlayer.

[0003] An ideal photoresist underlayer should possess certain specific characteristics: it should be cast onto a substrate via spin coating, should be thermosetting upon heating, exhibit low degassing and sublimation, should be soluble in common solvents to ensure good spin bowl compatibility, should have appropriate n and k values ​​to work with antireflective coatings to impart the low reflectivity required for photoresist imaging, and should possess high thermal stability to prevent damage during subsequent processing steps. In addition to these requirements, an ideal photoresist underlayer must provide a planar film upon spin coating and thermosetting on the substrate, with a morphology and sufficient dry etching selectivity for the silicon-containing layers above and below the photoresist underlayer to precisely transfer the light pattern into the final substrate.

[0004] Therefore, new underlayer materials are still needed, such as photoresist underlayer materials, which have improved adhesion to the underlying substrate, solvent resistance after curing, and high thermal stability (e.g., reduced sublimation during curing). Summary of the Invention

[0005] A photoresist underlayer composition is provided, comprising a first polymer comprising a first structural unit derived from an N-(alkoxymethyl)(meth)acrylamide monomer; a second structural unit comprising an aromatic group, a heterocyclic group, an ester group, an amide group, or a combination thereof, wherein the second structural unit further comprises a crosslinkable group; wherein the first polymer comprises the second structural unit, and the photoresist underlayer composition further comprises a second polymer containing the second structural unit, or a combination thereof, a thermal acid generator; and a solvent.

[0006] A coated substrate is also provided, comprising: a layer of photoresist underlay composition disposed on the substrate; and a second layer disposed on the layer of photoresist underlay composition.

[0007] Another aspect provides a method for forming a pattern, the method comprising: applying a layer of a photoresist underlay composition onto a substrate; curing the applied photoresist underlay composition to form a photoresist underlay; and forming a photoresist layer on the photoresist underlay. Attached Figure Description

[0008] Figures 1A to 1D Microscopic images of patterns coated with the underlayer compositions of Example 1, Comparative Example 1, Example 6 and Comparative Example 3, respectively, as provided herein, are shown.

[0009] Figure 2A Scanning electron microscopy (SEM) results of patterns obtained using the underlying compositions of Example 1 and Comparative Example 1 as described herein are shown.

[0010] Figure 2B SEM results of patterns obtained using the underlying compositions of Example 6 and Comparative Example 3 as described herein are shown. Detailed Implementation

[0011] Reference will now be made in detail to exemplary embodiments, examples of which are shown in this specification. In this respect, these exemplary embodiments may take different forms and should not be construed as limited to the description shown herein. Therefore, exemplary embodiments are described below only with reference to the accompanying drawings to explain various aspects of this specification. As used herein, the term “and / or” includes all combinations of one or more of the related listed items. When a statement such as “at least one of…” precedes the list of elements, it modifies the entire list of elements and does not modify any individual element in the list.

[0012] As used herein, the terms “a / an” and “the” do not indicate a limitation of quantity and are to be construed as including both the singular and plural unless otherwise indicated herein or clearly contradicted by the context. Unless otherwise explicitly stated, “or” means “and / or”. The full scope disclosed herein includes endpoints, and these endpoints may be independently combined with each other. The suffix “(s)” is intended to include both the singular and plural of the term it modifies, thereby including at least one of the stated terms. “Optional” or “optionally” means that an event or situation subsequently described may or may not occur, and the description includes instances where the event occurs as well as instances where it does not occur. The terms “first,” “second,” and similar terms herein do not indicate order, quantity, or importance, but are used to distinguish one element from another. When an element is referred to as being “on” another element, it may be in direct contact with that other element or an intervening element may be present therein. In contrast, when an element is referred to as being “directly on” another element, no intervening element is present. It should be understood that the components, elements, limitations and / or features of the described aspects can be combined in any suitable manner in all aspects.

[0013] Unless otherwise defined, all terms used herein (including technical and scientific terms) shall have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. It will be further understood that terms (such as those defined in common dictionaries) shall be interpreted as having the same meaning as they have in the relevant field and in the context of this disclosure, and shall not be construed as having an idealized or overly formal meaning unless expressly defined herein.

[0014] As used herein, "photochemical rays" or "radiation" refers to, for example, the bright-line spectrum of a mercury lamp, far-ultraviolet light, extreme ultraviolet light (EUV light), X-rays, particle rays (such as electron beams and ion beams), etc., represented by excimer lasers. Additionally, in this invention, "light" refers to photochemical rays or radiation. Krypton fluoride lasers (KrF lasers) are a special type of excimer laser, sometimes called excimer complex lasers. "Excimer" is an abbreviation for "excited dimer," and "excimer complex" is an abbreviation for "excited complex." Excimer lasers use a mixture of rare gases (argon, krypton, or xenon) and halogen gases (fluorine or chlorine), which, under appropriate electrical stimulation and high voltage conditions, emit coherent stimulated emission (laser) in the ultraviolet range. Furthermore, unless otherwise stated, "exposure" in this specification includes not only exposure through a mercury lamp, far-ultraviolet light, X-rays, extreme ultraviolet light (EUV light), etc., represented by excimer lasers, but also writing with particle rays (such as electron beams and ion beams).

[0015] As used herein, the term "hydrocarbon" refers to an organic compound or group having at least one carbon atom and at least one hydrogen atom; "alkyl" refers to a straight-chain or branched saturated hydrocarbon group having a specified number of carbon atoms and a valence of 1; "alkylene" refers to an alkyl group having a valence of 2; "hydroxyalkyl" refers to an alkyl group substituted with at least one hydroxyl group (-OH); "alkoxy" refers to "alkyl-O-"; "carboxyl" and "carboxylic acid" refer to groups having the formula "-C(O)OH"; "cycloalkyl" refers to a group having all ring members being carbon. A monovalent group of one or more saturated rings; "cycloalkylene" refers to a cycloalkyl group with a valence of 2; "alkenyl" refers to a straight-chain or branched monovalent hydrocarbon group having at least one carbon-carbon double bond; "alkenoxyl" refers to "alkenyl-O-"; "alkenylene" refers to an alkenyl group with a valence of 2; "cycloalkenyl" refers to a non-aromatic cyclic divalent hydrocarbon group having at least three carbon atoms and at least one carbon-carbon double bond; "alkynyl" refers to a monovalent hydrocarbon group having at least one carbon-carbon triple bond; the term "aromatic group" refers to a group that satisfies Huckel's rule. A monocyclic or polycyclic aromatic ring system comprising (4n+2π electrons) and including a carbon atom in the ring; the term "heteroaromatic group" refers to an aromatic group comprising one or more heteroatoms (e.g., 1-4 heteroatoms) that replace one or more carbon atoms in the ring; "aryl" refers to a monovalent monocyclic or polycyclic aromatic ring system wherein each ring member is carbon and may include a group having an aromatic ring fused to at least one cycloalkyl or heterocyclic alkyl ring; "arylene" refers to an aryl group having a valence of 2; "alkylaryl" refers to an aryl group that has been substituted by an alkyl group; "arylalkyl" refers to an alkyl group that has been substituted by an aryl group; "aryloxy" refers to "aryl-O-"; and "arylthio" refers to "aryl-S-".

[0016] The prefix "hetero" indicates that the compound or group includes at least one member (e.g., 1, 2, 3, or 4 or more heteroatoms) that substitutes for a carbon atom, wherein each of the one or more heteroatoms is independently N, O, S, Si, or P; "heteroatom-containing group" refers to a substituent that includes at least one heteroatom; the term "heterocyclic alkyl" refers to a cycloalkyl group having at least one heteroatom as a ring member that substitutes for a carbon atom; and the term "heterocyclic alkylene" refers to a heterocyclic alkyl group having a valence of 2. The term "heteroaryl" refers to an aromatic ring system of 4-8 membered monocyclic, 8-12 membered bicyclic, or 11-14 membered tricyclic having 1-4 heteroatoms (if monocyclic), 1-6 heteroatoms (if bicyclic), or 1-9 heteroatoms (if tricyclic).

[0017] The prefix "halogenated" refers to a group containing one or more of the following substituents: fluorine, chlorine, bromine, or iodine, replacing a hydrogen atom. The term "halogen" refers to a monovalent substituent of fluorine (fluorinated), chlorine (chlorinated), bromine (brominated), or iodine (iodinated). Combinations of halogen groups (e.g., bromine and fluorine) or only fluorine groups may be present. The term "substituted C"... 1-8 "Halogenated alkyl" refers to a C that has been substituted with at least one halogen. 1-8 Alkyl groups, and further substituted by one or more other substituents that are not halogens.

[0018] Unless otherwise explicitly stated, each of the aforementioned substituents may be optionally substituted. The term “optionally substituted” means substituted or unsubstituted. “Substituted” means that at least one hydrogen atom of a chemical structure or group is substituted by another terminal substituent, typically monovalent, provided that the valence of the specified atom is not exceeded. When the substituent is oxo (i.e., O), the two twin hydrogen atoms on the carbon atom are replaced by a terminal oxo group. Further note that the oxo group is bonded to carbon via a double bond to form a carbonyl group (C=O), which is represented herein as -C(O)-. Combinations of substituents or variables are permitted. Exemplary substituents that may be present at the “substituted” position include, but are not limited to, nitro (-NO2), cyano (-CN), hydroxyl (-OH), oxo (O), amino (-NH2), mono- or di- (C 1-6 )alkylamino, alkanoyl (such as C 2-6 Alkyl groups (such as acyl groups), formyl groups (-C(O)H), carboxylic acids or their alkali metal or ammonium salts; esters (including acrylates, methacrylates and lactones) such as C 2-6 Alkyl esters (-C(O)O-alkyl or -OC(O)-alkyl) and C 7-13 Aryl esters (-C(O)O-aryl or -OC(O)-aryl); amide groups (-C(O)NR2, where R is hydrogen or C). 1-6 alkyl), formamido (-CH2C(O)NR2, where R is hydrogen or C 1-6 Alkyl groups, halogens, mercapto groups (-SH), C 1-6 Alkylthio (-S-alkyl), thiocyano (-SCN), C 1-6 Alkyl, C 2-6 alkenyl, C 2-6 alkynyl group, C 1-6 Haloalkyl, C 1-9 Alkoxy, C 1-6 Halogenated alkoxy groups, C 3-12 cycloalkyl, C 5-18 Cycloalkenyl, C 2-18 Heterocyclic alkenyl groups, C groups having at least one aromatic ring 6-12Aryl (e.g., phenyl, biphenyl, naphthyl, etc., each ring being substituted or unsubstituted aromatic), having 1 to 3 single or fused rings and C atoms from 6 to 18 ring carbon atoms. 7-19 arylalkyl, having 1 to 3 single or fused rings and arylalkoxy with 6 to 18 ring carbon atoms, C 7-12 alkylaryl, C 3-12 Heterocyclic alkyl, C 3-12 heteroaryl, C 1-6 alkylsulfonyl (-S(O)2-alkyl), C 6-12 Arylsulfonyl (-S(O)2-aryl) or toluenesulfonyl (CH3C6H4SO2-).

[0019] As used herein, unless otherwise defined, "divalent linker" refers to -O-, -S-, -Te-, -Se-, -C(O)-, C(O)O-, and -N(R)-. ’ )-、-C(O)N(R ’ -, -S(O)-, -S(O)2-, -C(S)-, -C(Te)-, -C(Se)-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 A divalent group of heteroaryl or a combination thereof, wherein each R ’ It is independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Heteroaryl groups. Typically, the divalent linking groups include -O-, -S-, -C(O)-, -C(O)O-, -N(R')-, and -C(O)N(R). ’ -, -S(O)-, -S(O)2-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 One or more of heteroaryl groups or combinations thereof, wherein R' is hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C3-30 Mixed aromatic compounds.

[0020] As used herein, the term "(meth)acrylic acid" includes both acrylic acid and methacrylic acid (i.e., acrylic acid and methacrylic acid monomers), and the term "(meth)acrylate" includes both acrylate and methacrylate (i.e., acrylate and methacrylate monomers).

[0021] Organic underlayer films can be used to protect the underlying substrate during various patterning and etching processes. These films are typically cast directly onto and cured on an inorganic substrate (i.e., TiN). In these cases, it is desirable for the underlayer film to have sufficient adhesion to the substrate during all subsequent processing steps to protect the substrate from further damaging conditions. Common wet etching processes involve immersing the substrate in a corrosive solvent bath. Underlayer films that are not sufficiently adhered to the substrate may delaminate during immersion, leading to exposure and damage to the underlying inorganic substrate.

[0022] Incorporating structural units derived from N-(alkoxymethyl)(meth)acrylamide into the polymer units of a photoresist underlayer material can significantly improve the solvent resistance and thermal stability after curing without significantly impairing etch resistance and reflectivity parameters, and in some cases, improve slump margin. When used in photoresist underlayer compositions, the N-(alkoxymethyl)(meth)acrylamide-derived structural units can form crosslinks and / or can be crosslinkable, preferably wherein the polymer is crosslinkable without irradiation. The photoresist underlayer composition of the present invention further comprises a thermal acid generator (TAG) and preferably does not contain a photoacid generator (PAG). Crosslinking can be carried out via a crosslinking agent or through self-crosslinking.

[0023] According to an aspect of the invention, a photoresist underlayer composition comprises a first polymer comprising a first structural unit derived from an N-(alkoxymethyl)(meth)acrylamide monomer; a second structural unit comprising an aromatic group, a heterocyclic group, an ester group, an amide group, or a combination thereof, wherein the second structural unit further comprises a crosslinkable group; a thermal acid generator; and a solvent. In this photoresist underlayer composition, the first polymer may comprise the second structural unit, or the photoresist underlayer composition may further comprise a second polymer containing the second structural unit, or both the first polymer and the second polymer may each comprise the second structural unit.

[0024] In some embodiments, the first polymer may comprise a first structural unit derived from an N-(alkoxymethyl)(meth)acrylamide monomer and a second structural unit containing an aromatic group, a heterocyclic group, an ester group, an amide group, or a combination thereof, wherein the second structural unit further comprises a crosslinkable group.

[0025] As used herein, "crosslinkable group" refers to a nucleophilic group including oxygen, nitrogen, or sulfur, such as hydroxyl (-OH), carboxyl (-C(O)OH), amine (-NH2), mercapto (-SH), vinyl (e.g., C... 2-30 Alkenyl groups (-C(O)NH2) or amide groups (-C(O)NH2). Other examples of crosslinkable groups may include those such as epoxy groups and lactones, for example, epoxy groups, β-propiolactone, γ-butyrolactone, or δ-valerolactone. Crosslinkable groups may be directly (via a single bond) or bonded to aromatic groups and / or heterocyclic groups via divalent linkers.

[0026] In some embodiments, the photoresist underlayer composition may comprise a first polymer containing a first structural unit derived from an N-(alkoxymethyl)(meth)acrylamide monomer and a second polymer, wherein the second polymer comprises a second structural unit containing an aromatic group, a heterocyclic group, or a combination thereof, wherein the second structural unit further comprises a crosslinkable group.

[0027] In other embodiments, the first polymer may comprise a first structural unit derived from an N-(alkoxymethyl)(meth)acrylamide monomer and a second structural unit containing a first aromatic group, a first heterocyclic group, a first ester group, a first amide group, or a combination thereof, wherein the second structural unit further comprises a first crosslinkable group, and the photoresist underlayer composition may further comprise a second polymer comprising a third structural unit, wherein the third structural unit comprises a second aromatic group, a second heterocyclic group, a second ester group, a second amide group, or a combination thereof, and wherein the third structural unit further comprises a second crosslinkable group. It should be understood that the first aromatic group and the second aromatic group may be the same or different, the first heterocyclic group and the second heterocyclic group may be the same or different, the first ester group and the second ester group may be the same or different, the first amide group and the second amide group may be the same or different, and the first crosslinkable group and the second crosslinkable group may be the same or different.

[0028] The second structural unit comprises an aromatic group, a heterocyclic group, an ester group, an amide group, or a combination thereof. As used herein, "ester group" refers to a group having the formula -C(O)O- or -O(CO)-. As used herein, "amide group" refers to a group having the formula -C(O)NR- or -RNC(O)-, where R is hydrogen, a substituted or unsubstituted C. 1-20 Alkyl, or substituted or unsubstituted C 6-60 Aryl group. As used herein, "aromatic group" refers to a monocyclic or polycyclic aromatic hydrocarbon group. 6-60 Aromatic groups. When C 6-60When the aromatic group is polycyclic, one or more cyclic groups can be fused (e.g., naphthyl) or directly linked (e.g., biaryl, biphenyl). In embodiments, the polycyclic aromatic group may include a combination of fused and directly linked cyclic or cyclic groups (e.g., binaphthyl). As used herein, "heterocyclic group" refers to a monocyclic or polycyclic C 3-60 heteroaromatic groups or monocyclic or polycyclic C 3-60 Heterocyclic alkyl groups. When C 3-60 heteroaromatic groups and / or C 3-60 When the heterocyclic alkyl group is polycyclic, the ring or cyclic group can be fused, directly linked, or a combination of fused and directly linked ring or cyclic groups.

[0029] In some embodiments, the first polymer may comprise a first structural unit derived from an N-(alkoxymethyl)(meth)acrylamide monomer and a C-containing unit. 6-60 The second structural unit of the aryl group and the crosslinkable group. C 6-60 The aryl group may be further substituted with other substituents besides the crosslinkable group, or may be unsubstituted except for the crosslinkable group. Exemplary substituents may include substituted or unsubstituted C groups. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 1-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne group, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 3-30 heteroaryl, substituted or unsubstituted C 4-30 alkyl heteroaryl, or substituted or unsubstituted C 4-30 One or more of the heteroarylalkyl groups. The crosslinkable group can be with C. 6-60 The carbon atoms of the aryl group are directly linked, or the crosslinkable group can be linked via C... 6-60 The aryl group is linked by a divalent linker (i.e., as a side group to the polymer backbone).

[0030] In some embodiments, the first polymer may comprise a first structural unit derived from an N-(alkoxymethyl)(meth)acrylamide monomer, and the photoresist underlayer composition may further comprise a second polymer comprising a second structural unit. For example, the second polymer may comprise C 3-60 The second structural unit of heterocyclic alkyl groups and crosslinkable groups. C 3-60The heterocyclic alkyl group may be further substituted with other substituents besides the crosslinkable group, or may be unsubstituted except for the inclusion of the crosslinkable group. Exemplary additional substituents may include substituted or unsubstituted C-groups. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 1-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne group, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 3-30 heteroaryl, substituted or unsubstituted C 4-30 alkyl heteroaryl, or substituted or unsubstituted C 4-30 One or more of the heteroarylalkyl groups. The crosslinkable group can be with C. 3-60 Heterocyclic alkyl atoms are directly linked (i.e., via a single bond), or crosslinkable groups can be linked to C via divalent linkers. 3-60 Heterocyclic alkyl groups (i.e., as side groups to the polymer backbone).

[0031] The first structural unit is derived from the N-(alkoxymethyl)(meth)acrylamide monomer, which can be represented by formula (1):

[0032]

[0033] In equation (1), R a It is a hydrogen, fluorine, cyano group, or a substituted or unsubstituted C group. 1-10 Alkyl group. Preferably, R a It is hydrogen, fluorine, cyano, or substituted or unsubstituted C. 1-5 Alkyl, typically methyl.

[0034] In equation (1), R 1 It is hydrogen, or substituted or unsubstituted C 1-10 Alkyl group. Typically, R 1 It is hydrogen or methyl. In some embodiments, R 1 It's not hydrogen.

[0035] In equation (1), R 2 and R 3 Each is independently a hydrogen, substituted or unsubstituted C. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 3-30 heteroaryl, substituted or unsubstituted C 4-30 Heteroarylalkyl, or substituted or unsubstituted C 4-30 Alkyl heteroaryl. Preferably, R 2 and R 3 Each is independently a hydrogen or substituted or unsubstituted C. 1-10 Alkyl, typically methyl. In some respects, R 2 and R 3 At least one of them is hydrogen, and for example, R 2 and R 3 Both can be hydrogen. R 2 and R 3 Optionally, a ring can be formed via a single bond or a divalent linker, wherein the ring is substituted or unsubstituted.

[0036] R 2 and R 3 Each of these optionally further comprises a divalent linker as part of its structure. For example, R 2 and R 3 Each of these may optionally further include, as part of its structure, a selection from -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R)-. ’ One or more divalent linking groups of -C(O)N(R')- or -C(O)N(R')-, wherein R ’ It can be hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 3-20 Heterocyclic alkyl groups.

[0037] R 4 It is hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 2-20 Heterocyclic alkyl, substituted or unsubstituted C 6-24 aryl, substituted or unsubstituted C 7-25 arylalkyl, substituted or unsubstituted C 7-25 alkylaryl, substituted or unsubstituted C 3-20 heteroaryl, substituted or unsubstituted C 4-20 Heteroarylalkyl, or substituted or unsubstituted C 4-20 Alkyl heteroaryl.

[0038] R 2 or R 3 One of them can be optionally associated with R 4 Together they form a heterocycle via a single bond or a divalent linker, wherein the heterocycle is substituted or unsubstituted.

[0039] Exemplary N-(alkoxymethyl)(meth)acrylamide monomers may include one or more of the following:

[0040]

[0041]

[0042] Where R a It is as defined in equation (1).

[0043] The first structural unit derived from the N-(alkoxymethyl)(meth)acrylamide monomer is typically present in the first polymer in an amount ranging from 5 to 100 mol% based on the total structural units in the first polymer, more typically from 5 to 75 mol%, and even more typically from 5 to 50 mol%.

[0044] The second structural unit may include aromatic groups and may be derived from monomers having formula (2):

[0045]

[0046] Each R b It can be hydrogen, fluorine, cyano, or substituted or unsubstituted C. 1-10 Alkyl group. Preferably, R b It can be hydrogen, fluorine, or substituted or unsubstituted C. 1-5 Alkyl, typically methyl.

[0047] In equation (2), n is either 0 or 1. It should be understood that when n is 0, then L... 1 It is directly bonded to the carbon atom of the alkenyl group in formula (2).

[0048] In equation (2), L 1 This indicates a single bond or a divalent linker. For example, L 1 It can be a divalent linker selected from the following: optionally substituted aliphatic hydrocarbons (such as C... 1-6 Alkylene or C 3-20 Cycloalkylene hydrocarbons, aromatic hydrocarbons, and combinations thereof, optionally having a group selected from -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -NR- 102 -、or-C(O)N(R) 102 One or more connecting parts of )-, where R102 Selected from hydrogen and optionally substituted C 1-10 alkyl.

[0049] In equation (2), when n is 0 and L 1 When it is a single bond, the Ar group should be understood. 1 It is directly bonded to the carbon atom of the alkenyl group.

[0050] In equation (2), Ar 1 Is it substituted or unsubstituted C? 6-60 Aryl, typically substituted or unsubstituted C 6-14 Aryl.

[0051] In equation (2), each L 2 It is independently a single bond or a divalent linker. L 2 Exemplary divalent linking groups include substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 3-30 Hybrid aryl, -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R 103 )-、or--C(O)N(R 104 One or more of )-, where R 103 and R 104 Each can be independently hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, or substituted or unsubstituted C 3-20 Heterocyclic alkyl groups.

[0052] In formula (2), each Z is independently a crosslinkable group. Preferably, each Z is independently a hydroxyl, carboxyl, mercapto, amino, amide, epoxy, or lactone, typically hydroxyl, mercapto, or epoxy, and more typically hydroxyl.

[0053] In equation (2), y is an integer from 1 to 3, preferably an integer from 1 to 2, and typically y is 1.

[0054] Non-limiting examples of monomers having formula (2) may include the following:

[0055]

[0056] Where R b It is as defined in equation (2).

[0057] The polymer containing the second structural unit may contain repeating units derived from monomers having Formula 2 in an amount of 2 to 100 mol%, typically 10 to 100 mol%, and more typically 50 to 100 mol%, based on the total repeating units in the polymer. When the first polymer contains the second structural unit, the second structural unit is typically present in the first polymer in an amount of 5 to 100 mol%, more typically 5 to 75 mol%, and even more typically 5 to 50 mol%, based on the total repeating units in the first polymer.

[0058] The non-limiting exemplary first polymer of the present invention includes one or more of the following:

[0059]

[0060]

[0061] Where a, b, c, and d represent the mole fractions of the corresponding repeating units of the first polymer.

[0062] In some embodiments, the second structural unit may comprise a heterocyclic group and may be a crosslinkable polyester polymer comprising a crosslinkable group. For example, the second polymer may comprise an isocyanurate repeating unit and a crosslinkable group. In some aspects, the crosslinkable group may be selected from hydroxyl, carboxyl, mercapto, amino, epoxy, alkoxy, amide, vinyl, or combinations thereof.

[0063] Preferably, when used, the second polymer is a polymer comprising one or more isocyanurate repeating units derived from monomers having formula (3):

[0064]

[0065] In equation (3), K, L, and M are each independently a straight chain or a branched chain of C. 1-10 hydrocarbon group, C 1-10 alkoxycarbonyl, C 1-10 Alkyloxy groups, each optionally substituted with a carboxylic acid group, or optionally with a C- group. 1-5 alkoxycarbonyl or C 1-5 Substituted alkoxy-substituted straight-chain or branched C 1-10 Hydroxyalkyl.

[0066] In equation (3), for K, L, and M, C 1-10 hydrocarbon group, C 1-10 alkoxycarbonyl, C 1-10 Alkyloxy and C 1-10 Each of the hydroxyalkyl groups may optionally be converted by a halogen, amino, mercapto, epoxy, amide, or C group. 1-5 Alkyl, C3-8 cycloalkyl, C 3-20 Heterocyclic alkyl, C 2-5 alkenyl, C 1-5 Alkoxy, C 2-5 alkenyloxy group, C 6-12 Aryl, C 6-12 aryloxy group, C 7-13 alkylaryl, or C 7-13 At least one substitution of an alkylaryl group. C 3-8 cycloalkyl and C 3-20 The heterocyclic alkyl group may optionally be substituted with an oxo group (=O) at least one carbon atom of the ring. At least one hydrogen atom of the first polymer derived from the monomer having formula (2) is substituted with a functional group independently selected from hydroxyl, carboxyl, mercapto, amino, epoxy, alkoxy, amide, vinyl, or combinations thereof. Among these, hydroxyl, carboxyl, or alkoxy are preferred.

[0067] In some embodiments, the second structural unit may comprise a heterocyclic group comprising a substituted cyanurate structural unit derived from compounds or combinations thereof represented by formulas (4) and (5):

[0068]

[0069] In equations (4) and (5), R 5 and R 6 Each is independently a hydrogen, substituted or unsubstituted C. 1-30 Alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Mixed aromatic compounds.

[0070] In equations (4) and (5), R 7 It is hydrogen, -C(O)OH, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne group, substituted or unsubstituted C 2-30 Alkyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C1-C 30 Alkylthio, substituted or unsubstituted C1-C 30 Alkyl sulfinyl, substituted or unsubstituted C1-C 30 Alkyl sulfonyl, substituted or unsubstituted C2-C 30 alkoxycarbonyl, substituted or unsubstituted C 3-20 Cycloalkenyl, substituted or unsubstituted C 3-20Heterocyclic alkenyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C7-C 30 Alkyl aryl, substituted or unsubstituted C7-C 30 arylalkyl, substituted or unsubstituted C 3-30 heteroaryl, substituted or unsubstituted C 4-30 alkyl heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl.

[0071] In equations (4) and (5), X and X' are each independently hydrogen, or substituted or unsubstituted C. 1-10 Alkyl group. Preferably, X and X' are each hydrogen.

[0072] In equations (4) and (5), n1, n2, m1, m2, and m3 are each independently an integer from 1 to 10. Preferably, each of n1, n2, m1, m2, and m3 can be an independent integer from 1 to 4, typically 1 or 2.

[0073] Second polymers comprising second structural units containing substituted cyanurate structural units can be formed by conventional polycondensation techniques, such as those described in Pappas et al., “Organic Coatings, Science and Technology,” pp. 246-257 (John Wiley & Sons, 1999, 2nd ed.) and / or Houben-Weyl, “Methoden der Organischen Chemie, Band E20, Makromolekulare Soffe, Polyester,” pp. 1405-1429 (Georg Thieme Verlag, Stuttgart, 1987) and / or Houben-Weyl, “Methodden der Organischen Chemie, Band E20, Makromolekulare Soffe, Polyester,” pp. 1405-1429 (Georg Thieme Verlag, Stuttgart, 1987) and / or Houben-Weyl. On one hand, a diol or polyol is loaded with a dicarboxylic acid or polycarboxylic acid into a conventional polymerization vessel and reacted at temperatures ranging from about 100°C to 280°C for several hours. Optionally, an esterification catalyst can be used to reduce the reaction time. It should also be understood that polyesters can be prepared using esterified derivatives of polycarboxylic acids (such as dimethyl esters or anhydrides of polycarboxylic acids). Exemplary polyols and polycarboxylic acids include isocyanurate polyols and isocyanurate polycarboxylic acids. The polyester polymer can be linear or branched.

[0074] Suitable dicarboxylic acids or polycarboxylic acids, or their corresponding alkyl esters, that can be used to form the second polymer include saturated and unsaturated dicarboxylic acids, such as isophthalic acid, maleic acid, maleic anhydride, malonic acid, fumaric acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, 2-methyl-1,6-hexanoic acid, pimelic acid, octanoic acid, dodecanoic acid, phthalic acid, phthalic anhydride, 5-tert-butylisophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, inner methylene tetrahydrophthalic anhydride, azelaic acid, sebacic acid, tetrachlorophthalic anhydride, chlorobridged acid, isophthalic acid, trimellitic anhydride, terephthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, dimer fatty acids, or anhydrides of any of these acids, or combinations thereof.

[0075] Suitable diols and polyols include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol and higher polyethylene glycols, propylene glycol, dipropylene glycol, tripropylene glycol and higher polyethylene glycols, 1,3-propanediol, 1,4-butanediol and other butanediols, 1,5-pentanediol and other pentanediols, hexanediol, decanediol, and dodecanediol, glycerol, trimethylolpropane, trimethylolethane, neopentanediol, pentaerythritol, cyclohexanediol, dipentaerythritol, 1,2 -Dimethyl-1,3-propanediol, 1,4-benzyldiethanol, 2,4-dimethyl-2-ethylhexane-1,3-diol, isopropylidene bis(p-phenyleneoxypropanol-2), 4,4'-dihydroxy-2,2'-diphenylpropane, 1,3-cyclohexanediethanol, 1,4-cyclohexanediethanol (or a mixture of 1,3-cyclohexanediethanol and 1,4-cyclohexanediethanol, which may be cis or trans), sorbitol, etc., or combinations thereof.

[0076] When the second polymer comprises a second structural unit including a heterocyclic group, the second structural unit is typically present in the second polymer in an amount of 5 to 100 mol%, more typically 5 to 50 mol%, and even more typically 5 to 30 mol%, based on the total structural units in the second polymer. For example, the second structural unit may comprise a heterocyclic group comprising substituted cyanurate structural units derived from compounds of formula (4), (5), or combinations thereof, of 5 to 50 mol% or 5 to 30 mol%.

[0077] It should be understood that the polymers described herein, including the first polymer and the second polymer, may each optionally contain one or more additional repeating units different from the repeating units described above. These additional repeating units may include one or more additional units, for example, for the purpose of adjusting the properties of the photoresist underlayer composition (such as etching rate and solubility). Exemplary additional units may include one or more of (meth)acrylates, vinyl ethers, vinyl ketones, and vinyl esters. One or more additional repeating units in the polymer (if present) are typically used in amounts up to 99 mol% based on the total repeating units of the respective polymer, and typically from 3 to 80 mol%.

[0078] The polymers of the present invention may have a weight-average molecular weight (Mg) of 1,000 to 10,000,000 g / mol, more typically 2,000 to 10,000 g / mol. w ) and number-average molecular weights (M) ranging from 500 to 1,000,000 g / mol. n The molecular weight (M) was determined by gel permeation chromatography (GPC) using appropriate polystyrene standards. w Or M n ).

[0079] Suitable polymers of the present invention can be readily prepared based on the procedures described in the examples of this application and by analogy with the procedures described in the examples of this application, as will be readily understood by those skilled in the art. For example, one or more monomers corresponding to the repeating units described herein can be fed together or separately using suitable one or more solvents and initiators and polymerized in a reactor. The monomer composition may further include additives such as solvents, polymerization initiators, curing catalysts (i.e., acid catalysts), etc. For example, the polymer can be polymerized by the respective monomers under any suitable conditions, such as by heating at an effective temperature, irradiation with activation radiation at an effective wavelength, or a combination thereof.

[0080] The photoresist underlayer composition may further comprise one or more polymers other than the polymers described above (“additional polymers”). For example, the photoresist underlayer composition may further comprise additional polymers as described above, but with different compositions. Additionally or alternatively, one or more additional polymers may include those well known in the art, such as one or more polymers selected from: polyacrylates, polyvinyl ethers, polyesters, polynorbornene, polyacetals, polyethylene glycol, polyamides, polyacrylamide, polyphenols, phenolic varnishes, styrene polymers, polyvinyl alcohol, copolymers thereof, and combinations thereof.

[0081] The photoresist underlay composition further comprises a thermoacid generator (TAG) compound to aid in the curing of the photoresist underlay composition, for example, after the photoresist underlay composition has been applied to a surface. The photoresist underlay composition of the present invention may contain any suitable TAG that causes the photoresist underlay composition to cure on the substrate surface.

[0082] Exemplary hot acid generators include, but are not limited to, amine-terminated strong acids, such as amine-terminated sulfonic acids, such as amine-terminated dodecylbenzenesulfonic acid. Those skilled in the art will also understand that some photoacid generators are capable of releasing acid upon heating and can be used as hot acid generators.

[0083] Suitable TAG compounds may include, for example, nitrobenzyl toluenesulfonate, such as 2-nitrobenzyl toluenesulfonate, 2,4-dinitrobenzyl toluenesulfonate, 2,6-dinitrobenzyl toluenesulfonate, and 4-nitrobenzyl toluenesulfonate; benzenesulfonates, such as 2-trifluoromethyl-6-nitrobenzyl 4-chlorobenzenesulfonate and 2-trifluoromethyl-6-nitrobenzyl 4-nitrobenzenesulfonate; phenolsulfonates, such as phenyl 4-methoxybenzenesulfonate; alkylammonium salts of organic acids, such as 10-camphorsulfonic acid, trifluoromethylbenzenesulfonic acid, and triethylammonium salts of perfluorobutanesulfonic acid; and specific onium salts. A variety of aromatic (anthracene, naphthalene, or benzene derivative) sulfonate amine salts may be used as TAGs, including those disclosed in U.S. Patent Nos. 3,474,054, 4,200,729, 4,251,665, and 5,187,019. Examples of such tags include those sold by King Industries, Norwalk, Conn., USA, under the names NACURE, CDX, and K-PURE, such as NACURE 5225, CDX-2168E, K-PURE 2678, and KPURE 2700. One or more of these tags may be used.

[0084] The amount of TAG compound that can be used in the compositions of the present invention can be, for example, from 0.01 to 15 wt% of the total solids based on the photoresist underlayer composition, and typically from 0.01 to 10 wt%.

[0085] In some embodiments, the photoresist underlayer composition may further comprise a photoacid generator (PAG). Suitable PAGs include, for example: onium salts, such as triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tri(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, and triphenylsulfonium p-toluenesulfonate; nitrobenzyl derivatives, such as 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate, and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonates, such as 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene; and diazomethane derivatives, such as bis(trifluoromethanesulfonyloxy)benzene. (Benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane; dioxime derivatives, such as bis-O-(p-toluenesulfonyl)-α-dimethyldioxime and bis-O-(n-butanesulfonyl)-α-dimethyldioxime; sulfonate derivatives of N-hydroxyimide compounds, such as N-hydroxysuccinimide methanesulfonate and N-hydroxysuccinimide trifluoromethanesulfonate; and halogenated triazine compounds, such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine and 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine. One or more of these PAGs may be used.

[0086] In some aspects, the photoresist underlayer composition does not contain a photoacid generator. Accordingly, in these embodiments, the photoresist underlayer composition may be substantially free of PAG compounds.

[0087] The photoresist underlayer composition may further comprise one or more crosslinking agents, such as crosslinking agents comprising non-epoxy crosslinking agents. Any suitable crosslinking agent may be further used in the coating composition of the present invention, provided that such crosslinking agent has at least two, and preferably at least three, portions capable of reacting with functional groups in the photoresist underlayer composition. Exemplary crosslinking agents may include phenolic varnish resins, melamine compounds, guanidine compounds, isocyanate-containing compounds, benzocyclobutene, benzoxazine, etc., and typically have two or more, more typically three or more, selected from hydroxymethyl, C 1-10 alkoxymethyl and C 2-10 Any of the substituents of the acyloxymethyl group. Examples of suitable crosslinking agents include those shown below:

[0088]

[0089] Additional crosslinking agents are well known in the art and are commercially available from multiple sources. When present, the amount of such additional crosslinking agent that can be used in the photoresist underlayer composition of the present invention can be, for example, from 0.01 to 30 wt% based on the total solids of the photoresist underlayer composition, and preferably from 0.01 to 20 wt%.

[0090] The photoresist underlayer composition may include one or more optional additives, including, for example, surfactants, antioxidants, or combinations thereof. When present, each optional additive may be used in the photoresist underlayer composition in a small amount, such as from 0.01 to 10 wt% of the total solids based on the photoresist underlayer composition.

[0091] Typical surfactants include those that exhibit amphiphilic properties, meaning they can be both hydrophilic and hydrophobic. Amphiphilic surfactants have one or more hydrophilic head groups (which have a strong affinity for water) and a long hydrophobic tail (which is organophilic and repels water). Suitable surfactants can be ionic (i.e., anionic or cationic) or nonionic. Other examples of surfactants include silicone surfactants, poly(oxyethylene) surfactants, and fluorinated surfactants. Suitable nonionic surfactants include, but are not limited to, octyl and nonylphenol ethoxylates, such as TRITON X-114, X-100, X-45, and X-15, and branched secondary alcohol ethoxylates, such as TERGITOL TMN-6 (Dow Chemical Company, Midland, Michigan, USA). Other exemplary surfactants include alcohol (primary and secondary alcohols) ethoxylates, amine ethoxylates, glucosides, glucosamine, polyethylene glycol, poly(ethylene glycol-co-propylene glycol), or other surfactants disclosed in McCutcheon's Emulsifiers and Detergents, North American edition, 2000, published by Manufacturers Confectioners Publishing Co., Glen Rock, NJ. Nonionic surfactants that are acetylenic diol derivatives may also be suitable. Such surfactants are commercially available from Air Products and Chemicals, Inc., Allentown, Pennsylvania, under the trade names SURFYNOL and DYNOL. Additional suitable surfactants include other polymer compounds such as triblock EO-PO-EO copolymers PLURONIC 25R2, L121, L123, L31, L81, L101 and P123 (BASF, Inc.).

[0092] Suitable antioxidants include, for example, phenol-based antioxidants, antioxidants composed of organic acid derivatives, sulfur-containing antioxidants, phosphorus-based antioxidants, amine-based antioxidants, antioxidants composed of amine-aldehyde condensates, and antioxidants composed of amine-ketone condensates. Examples of phenol-based antioxidants include substituted phenols such as 1-oxy-3-methyl-4-isopropylbenzene, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, butylated hydroxyanisole, 2-(1-methylcyclohexyl)-4,6-dimethylphenol, 2,4-dimethyl-6-tert-butylphenol, 2-methyl-4,6-dinonylphenol, 2 6-Di-tert-butyl-α-dimethylamino-p-cresol, 6-(4-hydroxy-3,5-di-tert-butylaniline)2,4-bisoctyl-thio-1,3,5-triazine, n-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenyl)propionate, octylphenol, aralkyl-substituted phenols, alkylated p-cresols and hindered phenols; bisphenols, triphenols and polyphenols, such as 4,4'-bisphenol, 4,4'-methylene-bis-(dimethyl-4,6-phenol), 2, 2'-Methylene-bis-(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis-(4-ethyl-6-tert-butylphenol), 4,4'-methylene-bis-(2,6-di-tert-butylphenol), 2,2'-methylene-bis-(6-α-methyl-benzyl-p-cresol), methylene-crosslinked polyalkylphenols, 4,4'-butylene-bis-(3-methyl-6-tert-butylphenol), 1,1-Bis-(4-hydroxyphenyl)cyclohexane, 2,2'-dihydroxy-3,3'-di-(α-methylcyclohexyl)-5,5'-dimethyldiphenylmethane, alkylated bisphenols, hindered bisphenols, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris-(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, and tetra-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane. Suitable antioxidants are commercially available, for example, Irganox. TM Antioxidant (Ciba Specialty Chemicals Corp.)

[0093] The photoresist underlayer composition contains a solvent. The solvent component can be a single solvent or a mixture comprising two or more different solvents. Suitably, each of the multiple solvents can be miscible with each other. Suitable solvents include, for example, one or more oxoisobutyrates, particularly methyl-2-hydroxyisobutyrate, 2-hydroxyisobutyric acid, and ethyl lactate; one or more glycol ethers, particularly 2-methoxyethyl ether (diethylene glycol dimethyl ether), ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; one or more solvents having both an ether and a hydroxyl moiety, particularly methoxybutanol, ethoxybutanol, methoxypropanol, and ethoxypropanol; one or more alkyl esters, particularly methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and dipropylene glycol monomethyl ether acetate, as well as other solvents such as one or more diesters; and / or other solvents, such as propylene carbonate and one or more of γ-butyrolactone.

[0094] The desired total solids of the photoresist underlayer composition will depend on a number of factors, such as the desired final layer thickness. Typically, the total solids of the photoresist underlayer composition can be from 0.1 to 20 wt% based on the total weight of the photoresist underlayer composition, for example from 0.1 to 10 wt%, more typically from 0.1 to 5 wt%.

[0095] The photoresist underlayer composition can be prepared according to known procedures. For example, the photoresist underlayer composition can be prepared by combining a first material, a second material, an additive, a solvent, and any optional components in any order. The photoresist underlayer composition can be used as is, or it can be purified or diluted before being coated onto a substrate. Purification can involve one or more of the following: centrifugation, filtration, distillation, decantation, evaporation, treatment with ion exchange beads, etc.

[0096] The patterning method of the present invention includes applying a layer of photoresist underlay composition on a substrate; curing the applied photoresist underlay composition to form a photoresist underlay; and forming a photoresist layer on the photoresist underlay. The method may further include patterning the photoresist layer and transferring the pattern from the patterned photoresist layer to the photoresist underlay and a layer below the photoresist underlay. In some embodiments, the method may further include the step of exposing the photoresist layer in a patterned manner to activation radiation; and developing the exposed photoresist layer to provide a photoresist relief image. In some aspects, the method may further include forming a silicon-containing layer, an organic antireflective coating, or a combination thereof over the photoresist underlay before forming the photoresist layer. In some aspects, the method may further include transferring the pattern to the silicon-containing layer, the organic antireflective coating, or a combination thereof after developing the exposed photoresist layer and before transferring the pattern to the photoresist underlay.

[0097] A wide variety of substrates can be used in these patterning methods, with electronic device substrates being typical. Suitable substrates include, for example, packaging substrates such as multi-chip modules; flat panel display substrates; integrated circuit substrates; substrates for light-emitting diodes (LEDs) including organic light-emitting diodes (OLEDs); semiconductor wafers; polycrystalline silicon substrates; and so on. Suitable substrates can be in the form of wafers, such as those used for manufacturing integrated circuits, optical sensors, flat panel displays, integrated optical circuits, and LEDs. As used herein, the term "semiconductor wafer" is intended to cover "electronic device substrate," "semiconductor substrate," "semiconductor device," and various packages for various interconnect levels, including single-chip wafers, multi-chip wafers, packages for various levels, or other components requiring solder connections. Such substrates can be of any suitable size. Typical wafer substrate diameters are 200 to 300 mm, but wafers with smaller and larger diameters can be suitably employed according to the invention. As used herein, the term "semiconductor substrate" includes any substrate having one or more semiconductor layers or structures that may optionally include active or operable portions of a semiconductor device. A semiconductor device refers to a semiconductor substrate on which at least one microelectronic device has been mass-produced or is being mass-produced.

[0098] The substrate is typically composed of one or more of silicon, polycrystalline silicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanide, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. The substrate may include one or more layers and patterned features. These layers may include, for example, one or more conductive layers such as aluminum, copper, molybdenum, tantalum, titanium, tungsten, alloys, nitrides, or silicides of such metals, layers doped with amorphous silicon or doped with polycrystalline silicon; one or more dielectric layers such as layers of silicon oxide, silicon nitride, silicon oxynitride, or metal oxides; semiconductor layers such as single-crystal silicon; and combinations thereof. In some aspects, the substrate includes titanium nitride. Layers may be formed using various techniques, such as chemical vapor deposition (CVD), such as plasma-enhanced CVD (PECVD), low-pressure CVD (LPCVD), or epitaxial growth, physical vapor deposition (PVD), such as sputtering or evaporation, or electroplating.

[0099] In certain patterning methods of the present invention, prior to forming the photoresist underlayer of the present invention, it may be desirable to provide one or more photolithographic layers on the upper surface of the substrate, such as hard mask layers, for example spin-coated carbon (SOC), amorphous carbon, or metal hard mask layers; CVD layers, such as silicon nitride (SiN), silicon oxide (SiO), or silicon oxynitride (SiON) layers; organic or inorganic BARC layers, or combinations thereof. These layers, together with the layers of the photoresist underlayer composition of the present invention and the photoresist layer, form a photolithographic material stack. Typical photolithographic stacks that can be used in the patterning methods of the present invention include, for example, the following: SOC layer / underlayer / photoresist layer; SOC layer / SiON layer / underlayer / photoresist layer; SOC layer / SiARC layer / underlayer / photoresist layer; SOC layer / metal hard mask layer / underlayer / photoresist layer; amorphous carbon layer / underlayer / photoresist layer; and amorphous carbon layer / SiON layer / underlayer / photoresist layer.

[0100] It should be understood that, as used herein, "photoresist underlayer" refers to one or more layers disposed between the substrate and the photoresist layer (i.e., "on the substrate"). Therefore, the coated underlayer of the present invention (i.e., a layer of the photoresist underlayer composition) can be used alone as a photoresist underlayer, or the coated underlayer of the present invention (i.e., a layer of the photoresist underlayer composition) can be used in combination with other underlayers (including those described herein).

[0101] The photoresist undercoat composition can be coated onto a substrate by any suitable means, such as spin coating, slot die coating, blade coating, curtain coating, roll coating, spray coating, dip coating, etc. In the case of semiconductor wafers, spin coating is preferred. In a typical spin coating method, the composition of the present invention is applied to a substrate rotating at a rate of 500-4000 rpm for a period of 15-90 seconds to obtain the desired condensation polymer layer on the substrate. Those skilled in the art will understand that the thickness of the coated layer can be adjusted by changing the rotation speed and the solids content of the composition. The undercoat formed from the photoresist undercoat composition typically has a dried layer thickness of 1-500 nanometers (nm), more typically 1-100 nm.

[0102] Optionally, the coated photoresist underlayer composition is soft-baked at a relatively low temperature to remove any solvents and other relatively volatile components. Typically, the substrate is baked at a temperature of less than or equal to 150°C, preferably from 60°C to 125°C, and more preferably from 90°C to 115°C. The baking time is typically from 10 seconds to 10 minutes, preferably from 30 seconds to 5 minutes, and more preferably from 6 to 90 seconds. When the substrate is a wafer, this baking step can be performed by heating the wafer on a hot plate. This soft-baking step can be performed as part of the coating curing process or can be omitted entirely.

[0103] The photoresist underlayer composition is then cured to form the coated underlayer. The coating composition should be fully cured so that the coated underlayer film does not mix with, or minimally mixes with, any other underlayer component or photoresist layer to be formed on the underlayer. The coated composition can be cured in an oxygen-containing atmosphere (such as air) or in an inert atmosphere (such as nitrogen) and under conditions sufficient to provide a cured coating (such as heating). This curing step is preferably performed on a hot plate apparatus, but oven curing can be used to obtain equivalent results. Typically, this curing can be performed at a temperature of 150°C or higher, or from 150°C to 450°C. More preferably, the curing temperature is 180°C or higher, or from 200°C to 400°C. Curing times are typically from 10 seconds to 10 minutes, or from 30 seconds to 5 minutes, or from 45 seconds to 2 minutes, or from 45 to 90 seconds.

[0104] Optionally, a ramp-up or multi-stage curing process can be used. Ramp-up baking typically begins at a relatively low (e.g., ambient) temperature, which increases at a constant or varying ramp rate to a higher target temperature. Multi-stage curing processes involve curing at two or more temperature plateaus, typically with a first stage at a lower baking temperature and one or more additional stages at higher temperatures. The conditions of such ramp-up or multi-stage curing processes are known to those skilled in the art and may allow the omission of a prior soft-baking process.

[0105] After the applied photoresist underlayer composition is cured, a photoresist layer is formed on the applied photoresist underlayer. As described above, other intermediate layers may be applied between the applied photoresist underlayer and the overcoated photoresist layer. In some aspects, the method may further include forming a silicon-containing layer, an organic antireflective coating, or a combination thereof on the applied photoresist underlayer prior to forming the photoresist layer.

[0106] A wide variety of photoresists can be suitably used in the methods of this invention, and are typically positive materials. The specific photoresist to be used will depend on the exposure wavelength used and generally comprises an acid-sensitive matrix polymer, a photoactive component such as a photoacid generator, a solvent, and optional additional components. Suitable photoresists are well known to those skilled in the art and are commercially available, for example, UV photoresists from DuPont Electronics & Industrial. TM and EPIC TMThe product family includes a variety of photoresist materials. Photoresist can be applied to a substrate using known coating techniques (such as those described above regarding the underlayer composition), with spin coating being typical. Typical thicknesses of the photoresist layer range from 10-300 nm. Next, the photoresist layer is typically soft-baked to minimize solvent content in the layer, thereby forming a non-stick coating and improving the layer's adhesion to the substrate. Soft baking can be performed on a heated plate or in an oven, with a heated plate being typical. Typical photoresist soft baking is performed at temperatures ranging from 70°C to 150°C for 30-90 seconds.

[0107] The photoresist layer is then exposed to activating radiation through a photomask to create a solubility difference between the exposed and unexposed areas. The exposure of the photoresist composition to activating radiation, as described herein, indicates that radiation can form a latent image within the photoresist composition. The photomask has optically transparent and optically opaque regions, corresponding to the areas in the resist layer to be exposed and unexposed by activating radiation, respectively. Exposure wavelengths are typically below 400 nm, and more typically below 300 nm, such as 248 nm (KrF), 193 nm (ArF), or EUV wavelengths (e.g., 13.5 nm). In a preferred aspect, the exposure wavelength is 193 nm or an EUV wavelength. Exposure energy is typically from 10 to 100 millijoules per square centimeter (mJ / cm²). 2 This depends on, for example, the components of the exposure tool and the photosensitizing composition.

[0108] After the photoresist layer is exposed, post-exposure baking (PEB) is typically performed. PEB can be performed, for example, on a heated plate or in an oven. PEB is typically performed at temperatures ranging from 70°C to 150°C for 30 to 90 seconds. This forms a latent image defined by the boundary between polarity-converted and unconverted areas (corresponding to exposed and unexposed areas, respectively). Next, the photoresist layer is developed to remove the exposed areas of the layer, leaving the unexposed areas to form a patterned photoresist layer. The developer is typically an aqueous alkaline developer, such as a tetraalkylammonium hydroxide solution, like a tetramethylammonium hydroxide (TMAH) solution, typically a 0.26 wt% (N) (2.38 wt%) TMAH solution. The developer can be applied using known techniques, such as spin coating or dip coating.

[0109] A patterned photoresist layer can be transferred to one or more underlying layers, including a coated underlayer, and then to a substrate using appropriate etching techniques, such as plasma etching of each etched layer using an appropriate type of gas. Depending on the number of layers and materials involved, pattern transfer may include multiple etching steps using different etching gases. After the pattern has been transferred to the substrate using conventional techniques, the patterned photoresist layer, the coated underlayer, and other optional layers in the photolithographic stack can be removed. Optionally, one or more layers of the stack may be removed or consumed during the process of pattern transfer to the underlying layer and before pattern transfer to the substrate. For example, pattern transfer to one or more of a silicon-containing layer, an organic antireflective coating, etc., may occur after the exposed photoresist layer has been developed and before pattern transfer to the coated underlayer. The substrate is then further processed according to known methods to form an electronic device.

[0110] A coated substrate is also provided, comprising: a layer of the photoresist underlay composition of the present invention disposed on the substrate; and a second layer disposed on the layer of the photoresist underlay composition. The second layer may be any one or more of the layers described herein, and in some cases may be a photoresist layer disposed on the layer of the photoresist underlay composition. As used herein, the term "cured layer" refers to a layer derived from the composition after the photoresist underlay composition has been disposed on the substrate and subsequently cured to form a coating or film, and is also simply referred to as a "photoresist underlay." In other words, curing the photoresist underlay composition can be said to form a "cured layer," which is a photoresist underlay.

[0111] Other aspects provide a layered article comprising a coated underlayer derived from the photoresist underlayer composition of the present invention. In embodiments, the layered article may include a substrate; a coated underlayer disposed on the substrate; and a photoresist layer disposed on the coated underlayer.

[0112] The inventive concept is further illustrated by the following examples, which are intended to be non-limiting. All compounds and reagents used herein are commercially available, except for the procedures provided below.

[0113] Example

[0114] Synthesis Example

[0115] Synthesis of Polymer A-1

[0116]

[0117] 50.0 g of propylene glycol monomethyl ether acetate (PGMEA) was loaded into a 250 mL round-bottom flask (RBF) with a three-necked neck equipped with a temperature control unit. The flask was heated to 60 °C under nitrogen. A mixture solution containing N-(butoxymethyl)acrylamide (BOAM, 40.0 g) and V-65 (6.52 g) dissolved in PGMEA (43.3 g) was prepared and fed into the reactor over a span of 180 minutes. After the feeding was complete, the reactor was maintained at 60 °C for another 60 minutes. The reactor was then cooled to room temperature with stirring. The reaction mixture was precipitated with a mixture of heptane and MTBE (4:1 volume) (10 times the excess volume was added to a given volume of the reaction mixture). The solvent was removed by filtration, and the precipitate was then dried under vacuum at 50 °C for 1 day. A 30% product solution was then prepared using tetrahydrofuran (THF) and precipitated from the mixture of heptane and MTBE (4:1 volume). The solvent was removed by filtration, and the resulting precipitate was then dried under vacuum at 50°C for 1 day.

[0118] Synthesis of Polymer A-2

[0119]

[0120] Polymer A-2 was prepared using a similar procedure to that used to prepare polymer A-1, except that N-(butoxymethyl)methacrylamide (BOMM, 40.0 g) was used instead of BOAM, and the amount of V-65 initiator was 5.80 g.

[0121] Synthesis of Polymer A-3

[0122]

[0123] Polymer A-3 was prepared using a similar procedure to that used to prepare polymer A-1, except that N-(methoxymethyl)methacrylamide (MOMM, 40.0 g) was used instead of BOAM, and the amount of V-65 initiator was 7.69 g.

[0124] Synthesis of BOMMM: N-(butoxymethyl)-N-methylmethacrylamide (BOMMM)

[0125]

[0126] 9.78 g of n-butanol and 0.07 g of 4-methoxyphenol (MEHQ) were placed in a 250 mL RBF (reactive liquid separator) with a condenser and a static liquid apparatus. N-methylacrylamide (29.2 g) was added dropwise to the contents of the RBF over 20 minutes while maintaining the solution temperature at 30°C. After the reagents dissolved, a 10% aqueous solution of sodium hydroxide was added, followed by the addition of 10.0 g of paraformaldehyde in portions over 20 minutes. The resulting mixture was heated at 55°C for 30 minutes. The reaction solution was cooled to room temperature. The pH was then adjusted to 5-6 by adding a 35% aqueous solution of hydrochloric acid. 0.3 g of oxalic acid and 52.45 g of n-butanol were then added to the reaction solution, and the resulting mixture was heated at 90-95°C for 6.5 hours while removing water using the static liquid apparatus to obtain 126.57 g of the reaction solution.

[0127] Synthesis of Polymer A-4

[0128]

[0129] Polymer A-4 was prepared using a similar procedure to that used to prepare polymer A-1, except that BOMMM (40.0 g) was used instead of BOAM, and the amount of V-65 initiator was 5.36 g.

[0130] Synthesis of BOEAM: N-(1-Butoxyethyl)acrylamide (BOEAM)

[0131]

[0132] 10.0 g of n-butanol and 0.07 g of 4-methoxyphenol (MEHQ) were loaded into a 250 mL RBF (reactive oil container) with a condenser and a static liquid apparatus. Acrylamide (21.4 g) was then added dropwise to the contents of the RBF over 20 minutes while maintaining the solution temperature at 30°C. After the reagents dissolved, a 10% aqueous solution of sodium hydroxide was added, followed by the addition of 15.0 g of acetaldehyde in portions over 20 minutes. The resulting mixture was heated at 55°C for 30 minutes. The reaction solution was then cooled to room temperature. The pH was then adjusted to 5-6 by adding hydrochloric acid (35% solution). 0.3 g of oxalic acid and 78.67 g of n-butanol were then added to the reaction solution, and the resulting mixture was heated at 90-95°C for 6.5 hours while removing water using the static liquid apparatus to obtain 119.63 g of the reaction solution.

[0133] Synthesis of Polymer A-5

[0134]

[0135] Polymer A-5 was prepared using a similar procedure to that used to prepare polymer A-1, except that BOEAM (40.0 g) was used instead of BOAM, and the amount of V-65 initiator was 5.80 g.

[0136] Synthesis of POMA: N-(phenoxymethyl)acrylamide (POMA)

[0137]

[0138] 61.2 g of deionized (DI) water and 0.2 g of butylated hydroxytoluene (BHT) were loaded into a 3-necked 250 mL RBF equipped with a condenser and a static liquid apparatus. Then, 56.4 g of phenol, 42.6 g of acrylamide, and 36.0 g of paraformaldehyde were added to the solution, and the resulting mixture was heated at 110 °C for 2 hours. The solution was cooled to room temperature and then concentrated under vacuum. The crude product was purified by silica gel column chromatography to obtain 29.0 g of a yellow oily product.

[0139] Synthesis of Polymer A-6

[0140]

[0141] Polymer A-6 was prepared using a similar procedure to that used to prepare polymer A-1, except that POMA (40.0 g) was used instead of BOAM, and the amount of V-65 initiator was 5.61 g.

[0142] Synthesis of Polymer A-7

[0143]

[0144] 50.0 g of PGMEA was loaded into a 3-necked 250 mL RBF equipped with a temperature controller unit. The flask was heated to 60 °C under nitrogen. A mixture containing 4-hydroxyphenyl methacrylate (HQMA, 29.0 g), BOAM (11.0 g), and V-65 initiator (5.78 g) dissolved in PGMEA (43.3 g) was prepared and fed into the reactor over a span of 180 minutes. After feeding, the reactor was maintained at 60 °C for another 60 minutes. The reactor was then cooled to room temperature with stirring. The reaction mixture was precipitated with a mixture of heptane and MTBE (4:1 volume) (10 times the excess volume was added to a given volume of reaction mixture). The solvent was removed by filtration, and the precipitate was then dried under vacuum at 50 °C for 1 day. A 30% product solution was then prepared using THF and precipitated from the mixture of heptane and MTBE (4:1 volume). The solvent was removed by filtration, and the precipitate was then dried under vacuum at 50°C for 1 day.

[0145] Synthesis of Polymer B-1

[0146]

[0147] 46.09 g of tris(2-hydroxyethyl) isocyanurate, 21.6 g of tris(2-carboxyethyl) isocyanurate, 1.35 g of p-toluenesulfonic acid monohydrate, 31.15 g of dimethyl terephthalate, and 52 g of anisole were added to 250 mL of RBF. The mixture was then heated to 140-150 °C with vigorous stirring. Methanol, along with anisole, was slowly removed from the reaction by distillation. The polymer solution was then diluted by adding 100 g of HBM. The mixture was precipitated from isopropanol. The polymer was collected and dried overnight under vacuum at 40-60 °C. w It is 3000 g / mol, of which PDI is 1.4 (GPC).

[0148] Synthesis of Polymer B-2

[0149]

[0150] 39.8 g of tris(2-hydroxyethyl) isocyanurate, 17.5 g of tris(2-carboxyethyl) isocyanurate, 0.73 g of p-toluenesulfonic acid monohydrate, 32.1 g of dibutyl naphthaleneate, 67 g of anisole, and 100 g of 1-butanol were added to 250 mL of RBF. The mixture was then heated to 140-160 °C with vigorous stirring. Butanol and anisole were slowly removed from the reaction by distillation. The polymer solution was then diluted by adding 100 g of THF. The mixture was precipitated from a combination of MTBE and isopropanol (1:1 by volume). The polymer was collected and dried under vacuum at 40-60 °C for 12 hours. w It is 3000 g / mol, of which PDI is 1.30 (GPC).

[0151] Synthesis of Polymer B-3

[0152]

[0153] 60.0 g of ethyl lactate was loaded into a 3-necked 250 mL RBF reactor equipped with a temperature controller unit. The reactor was heated to 90 °C. 4-hydroxyphenyl methacrylate (HQMA, 40.0 g) and V-601 initiator (10.34 g) were dissolved in cyclohexanone (60.0 g), and this prepared mixture was then fed into the reactor over 180 minutes. After feeding, the reactor was maintained at 90 °C for another 60 minutes. The reactor was then cooled to room temperature with stirring. The reaction mixture was precipitated with a mixture of MTBE and heptane (4:6 volume) (using 10 times the excess volume). The solvent was removed by decantation, and the precipitate was then dried in air. The resulting white solid was dissolved in THF (120 g) and precipitated from the combination of MTBE and heptane (4:6 volume).

[0154] Underlying composition

[0155] Table 1 shows the base compositions of Examples 1 to 11 and Comparative Examples 1 to 6 prepared by mixing the components in the indicated amounts. Each composition further comprises 5 mg of 2,4,6-trimethylpyridinium p-toluenesulfonate, 4.8 g of methyl-2-hydroxy isobutyrate, and 4.8 g of PGMEA. The solution was filtered through a polytetrafluoroethylene (PTFE) filter with a pore size of 0.45 μm prior to use.

[0156] Table 1

[0157] Polymer 1 Polymer 2 Example 1 A-1 (79mg) B-1 (316mg) Example 2 A-2 (79mg) B-1 (316mg) Example 3 A-3 (79mg) B-1 (316mg) Example 4 A-4 (79mg) B-1 (316mg) Example 5 A-5 (79mg) B-1 (316mg) Example 6 A-1 (79mg) B-2 (316mg) Example 7 A-2 (79mg) B-2 (316mg) Example 8 A-3 (79mg) B-2 (316mg) Example 9 A-4 (79mg) B-2 (316mg) Example 10 A-5 (79mg) B-2 (316mg) Example 11 A-7 (395mg) -- Comparison Example 1 C-1 (80mg) B-1 (315mg) Comparison Example 2 C-2 (80mg) B-1 (315mg) Comparison Example 3 C-1 (80mg) B-2 (316mg) Comparison Example 4 C-2 (80mg) B-2 (316mg) Comparison Example 5 C-1 (80mg) B-3 (315mg) Comparison Example 6 C-2 (80mg) B-3 (315mg)

[0158] The following abbreviations are used in Table 1: C-1 is tetramethoxymethylglycourea; and C-2 is hexa(methoxymethyl)-1,3,5-triazine-2,4,6-triamine.

[0159] Solvent resistance assessment

[0160] Each composition in Table 1 was spin-coated onto the corresponding 200-mm bare silicon wafer at 1500 rpm and then cured at 205°C for 60 seconds to form a cured coating as a film. The initial thickness of the film on the silicon wafer was measured by ellipticization (M2000 ellipticizer, JA Woolam), and then 30 mL of PGMEA was brought into contact with the wafer surface and held for one minute to be fixed to the wafer surface. Afterward, the wafer was spin-dried at 4,000 rpm for one minute, and the remaining film thickness was measured by ellipticization. The thickness difference (i.e., film loss) was then calculated based on the film thickness before and after contact with PGMEA / spin-drying. The results are shown in Table 2 as film loss (in angstroms). (as shown in the image)

[0161] Sublimation resistance assessment

[0162] To determine the amount of material sublimating from the film during the curing process, a test procedure was employed that measured the amount of material condensing on a quartz crystal placed approximately 1 cm above the polymer film during the curing process on a bare silicon wafer using a hot plate. Each composition in Table 1 was spin-coated at 1500 rpm onto the corresponding 200-mm bare silicon wafer without a post-baking heating step. Sublimation from the film was measured using a quartz crystal microbalance (QCM) while heating at 205°C for 60 seconds to form the cured film. The cured film had a thickness of 100 nm. The results are shown in Table 2 as the sublimation mass (μg) absorbed from the cured film.

[0163] Glass transition temperature of the cured film

[0164] Each composition in Table 1 was spin-coated onto a corresponding 200-mm bare silicon wafer at 1500 rpm and then cured at 215°C for 60 seconds to form a cured coating as a film with a thickness of 900 nm. The coated wafers were cut into 2 cm × 2 cm segments and placed in the hot chamber of an ellipsometer (M2000 ellipsometer, JA Woollam). The glass transition temperature (Tg) was determined using differential scanning calorimetry (DSC) with two cycles of heating to 250°C at a rate of 10°C / s and cooling to 30°C at a rate of 10°C / s. g The glass transition temperature (Tg) was calculated from the first cooling profile using general-purpose analysis software. g The results are shown in Table 2 as T. g (°C) is shown.

[0165] Table 2

[0166]

[0167] As can be seen from Table 2, the samples in Examples 1-11 achieved high solvent resistance, as compared with comparative Examples 1-6 (from 1.1 to...). Less membrane loss (from 0.2 to) compared to membrane loss (from 0.2 to This was confirmed by the membrane loss. Examples 1-11 were less prone to sublimation because the resulting sublimation amounts ranged from 0 to 6 μg. In contrast, heating Comparative Examples 1-6 produced sublimation amounts ranging from 33 to 48 μg. Furthermore, each of Examples 1-11 had a membrane temperature T greater than 250°C. g In contrast, comparative examples 1-6 did not have membrane temperatures exceeding 231°C. g Therefore, the underlying compositions of the present invention in Examples 1 to 11 exhibit high film densities.

[0168] Pattern Coating Evaluation

[0169] The underlayer compositions of Example 1, Comparative Example 1, Example 6, and Comparative Example 3 were spin-coated onto a SiO2 substrate with trenches having a depth of 1 μm CD and 107.7 nm, and then heated at 205 °C for one minute. Subsequently, the coating stability and filling characteristics of the underlayer compositions on the pattern were observed using an optical microscope. Figures 1A to 1D Optical microscopic images of patterns coated with the underlayer compositions of Example 1, Comparative Example 1, Example 6, and Comparative Example 3 are shown. It was found that the coating films of the compositions of Example 1 and Example 6 were well coated to correspond to the patterns. However, for the coating films of Comparative Example 1 and Comparative Example 3, pull-back was observed, which caused the patterns to tear during the heating process.

[0170] Photolithography performance

[0171] The underlayer compositions of Example 1 and Comparative Example 1 were spin-coated onto a silicon wafer and then baked at 205°C using a TELMark 8 wafer coating tracker to produce an underlayer antireflective coating. Next, the DuPont EPIC... TM 2150 photoresist was spin-coated on top of the antireflective coating and baked at 110°C for 60 seconds to give a photoresist film with a thickness of 170 nm. The photoresist was then exposed through a target mask using a 193 nm ArF wafer stepper with a stepper setting of 0.93 NA (0.82 / 0.53 ring settings). The photoresist film was then baked at 115°C for 60 seconds after exposure and developed using Shipley MF CD-26 developer (2.38% TMAH) in a standard 60-second single-puddle process. The quality of the photoresist pattern was examined using a scanning electron microscope (SEM) at 60,000 magnification.

[0172] Figure 2A The SEM results show that the antireflective compositions used in Example 1 and Comparative Example 1 have a 160 nm pitch linewidth and a spacing pattern with a 65 nm CD. When Example 1 is used as the bottom antireflective film, a better collapse margin is observed than when Comparative Example 1 is used, likely due to the higher film T... g The higher film density of Example 1 is confirmed. The same trend was observed when Example 6 and Comparative Example 3 were used as bottom antireflective films, as... Figure 2B As depicted in the text.

[0173] While this disclosure has been described in conjunction with exemplary embodiments now considered to be practical, it should be understood that the invention is not limited to the disclosed embodiments, but rather is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A photoresist underlayer composition comprising... A first polymer, the first polymer comprising a first structural unit derived from an N-(alkoxymethyl)(meth)acrylamide monomer; A second structural unit comprising an aromatic group, a heterocyclic group, an ester group, an amide group, or a combination thereof, wherein the second structural unit further comprises a crosslinkable group; The photoresist underlayer composition further comprises a second polymer containing the second structural unit. Hot acid generating agent; and Solvent, The second structural unit comprises a heterocyclic group, which comprises a substituted cyanurate structural unit derived from compounds or combinations thereof represented by formulas (4) and (5): in, In equations (4) and (5), R 5 and R 6 Each is independently a hydrogen, substituted or unsubstituted C. 1-30 Alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 3-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 3-30 Mixed aromatics; R 7 It is hydrogen, -C(O)OH, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne group, substituted or unsubstituted C 2-30 Alkyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C1-C 30 Alkylthio, substituted or unsubstituted C1-C 30 Alkyl sulfinyl, substituted or unsubstituted C1-C 30 Alkyl sulfonyl, substituted or unsubstituted C2-C 30 alkoxycarbonyl, substituted or unsubstituted C 3-20 Cycloalkenyl, substituted or unsubstituted C 3-20 Heterocyclic alkenyl, substituted or unsubstituted C6-C 30 aryl, substituted or unsubstituted C7-C 30 Alkyl aryl, substituted or unsubstituted C7-C 30 arylalkyl, substituted or unsubstituted C 3-30 heteroaryl, substituted or unsubstituted C 4-30 alkyl heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl; X and X' are each independently hydrogen, or substituted or unsubstituted C. 1-10 alkyl; n1, n2, m1, m2, and m3 are each an integer from 1 to 10.

2. The photoresist underlayer composition as described in claim 1, wherein, The N-(alkoxymethyl)(methyl)acrylamide monomer has the formula (1): In equation (1), R a It is a hydrogen, fluorine, cyano group, or a substituted or unsubstituted C group. 1-10 alkyl; R 1 It is hydrogen, or a substituted or unsubstituted C. 1-10 alkyl; R 2 and R 3 Each is independently a hydrogen, substituted or unsubstituted C. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 3-30 heteroaryl, substituted or unsubstituted C 4-30 Heteroarylalkyl, or substituted or unsubstituted C 4-30 Alkyl heteroaryl; R 2 and R 3 Each of them optionally further includes a divalent linker group as part of its structure; R 2 and R 3 Optionally, a ring is formed via a single bond or a divalent linker, wherein the ring is substituted or unsubstituted; R 4 It is hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 2-20 Heterocyclic alkyl, substituted or unsubstituted C 6-24 aryl, substituted or unsubstituted C 7-25 arylalkyl, substituted or unsubstituted C 7-25 alkylaryl, substituted or unsubstituted C 3-20 heteroaryl, substituted or unsubstituted C 4-20 Heteroarylalkyl, or substituted or unsubstituted C 4-20 alkyl heteroaryl; and R 2 Or R 3 One of the optional R 4 Together they form a heterocycle via a single bond or a divalent linker, wherein the heterocycle is substituted or unsubstituted.

3. The photoresist underlayer composition as described in claim 2, wherein, R a It is hydrogen or unsubstituted C 1-3 alkyl; R 1 It is hydrogen or methyl; R 2 and R 3 Each is independently hydrogen, or a substituted or unsubstituted C. 1-10 Alkyl; and R 4 Is it substituted or unsubstituted C? 1-10 Alkyl, substituted or unsubstituted C 3-10 cycloalkyl, substituted or unsubstituted C 2-10 Heterocyclic alkyl, substituted or unsubstituted C 6-14 aryl, or substituted or unsubstituted C 3-20 Mixed aromatic compounds.

4. A coated substrate comprising: A layer of the photoresist underlayer composition as described in any one of claims 1 to 3 disposed on a substrate; and A second layer disposed on the layer of the photoresist underlayer composition.

5. A method for forming a pattern, the method comprising: A layer of the photoresist underlayer composition as described in any one of claims 1 to 3 is applied to a substrate; The applied photoresist underlayer composition is cured to form a photoresist underlayer; as well as A photoresist layer is formed on the photoresist substrate.

6. The method of claim 5, further comprising forming a silicon-containing layer, an organic antireflective coating, or a combination thereof over the photoresist underlayer prior to forming the photoresist layer.

7. The method of claim 5, further comprising patterning the photoresist layer and transferring the pattern from the patterned photoresist layer to the photoresist underlayer and a layer below the photoresist underlayer.

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