Photoresist underlayer composition

Abstract

To provide a photoresist underlayer composition.SOLUTION: The photoresist underlayer composition contains a first polymer containing: 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 and further containing a crosslinkable group. The photoresist underlayer composition further contains: a second polymer containing the second structural unit, or a combination thereof; a thermal acid generator; and a solvent.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates generally to the field of manufacturing electronic devices, and more specifically to the field of materials for use in semiconductor manufacturing. [Background technology]

[0002] Photoresist underlayer compositions are used in the semiconductor industry as etch masks for lithography in the latest technology nodes for integrated circuit fabrication. These compositions are often used in integrated triple and quadruple photoresist schemes in which an organic or silicon-containing antireflective coating and a layer of patternable photoresist film are disposed above an underlayer.

[0003] An ideal photoresist underlayer material must have certain specific characteristics: it must be castable onto a substrate by a spin-coating process, it must be thermally cured with low outgassing and sublimation when heated, it must be soluble in common solvents for good compatibility with spin bowls, it must have suitable n&k values ​​to work with anti-reflective coating layers to impart the low reflectivity required for photoresist imaging, and it must have high thermal stability to avoid damage during subsequent processing steps. In addition to these requirements, an ideal photoresist underlayer material must impart a planar film with topography and sufficient dry etch selectivity to silicon-containing layers located above and below the photoresist underlayer film after spin-coating and thermal curing on a substrate to transfer the photopattern to the final substrate in a precise manner.

[0004] Thus, there remains a need for new underlayer materials, such as photoresist underlayer materials that have improved adhesion to the underlying substrate, solvent resistance after curing, and increased thermal stability (e.g., reduced sublimation during curing). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] U.S. Pat. No. 3,474,054 [Patent Document 2] U.S. Pat. No. 4,200,729 [Patent Document 3] U.S. Pat. No. 4,251,665 [Patent Document 4] U.S. Pat. No. 5,187,019 [Non-patent literature]

[0006] [Non-Patent Document 1] Pappas et al. “Organic Coatings ,Science and Technology,” pp246-257 (John Wiley&Sons, 1999, 2ed.) [Non-Patent Document 2] Houben-Weyl, “Methoden der Organischen Chemie, Band E20, Makromolekulare Soffe, Polyester,” pp1405-1429. (Georg Thieme Verlag, Stuttgart 1987) [Non-Patent Document 3] McCutcheon's Emulsifiers and Detergents, North American Edition for the Year 2000 Summary of the Invention [Means for solving the problem]

[0007] Provided is a photoresist underlayer composition comprising: a first polymer comprising first structural units derived from N-(alkoxymethyl)(meth)acrylamide monomers; second structural units comprising aromatic groups, heterocyclic groups, ester groups, and amide groups, or combinations thereof, the second structural units further comprising a crosslinkable group; a thermal acid generator; and a solvent, wherein the first polymer comprises the second structural units, the photoresist underlayer composition further comprises a second polymer comprising the second structural units, or a combination thereof.

[0008] Also provided is a coated substrate comprising a layer of a photoresist underlayer composition disposed on a substrate and a second layer disposed over the layer of photoresist underlayer composition.

[0009] Yet another aspect discloses a method of forming a pattern that includes applying a layer of a photoresist underlayer composition onto a substrate; curing the applied photoresist underlayer composition to form a photoresist underlayer; and forming a photoresist layer over the photoresist underlayer. [Brief description of the drawings]

[0010] [Figure 1A-1D] 1A-1D are microscopy images of patterns coated with the underlayer compositions of Example 1, Comparative Example 1, Example 6, and Comparative Example 3, respectively, provided herein. [Figure 2A] 1 is a scanning electron microscope (SEM) result of patterns obtained using the underlayer compositions of Example 1 and Comparative Example 1 described herein. [Figure 2B] 1 shows SEM results of patterns obtained using the underlayer compositions of Example 6 and Comparative Example 3 described herein. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Reference will now be made in detail to exemplary embodiments, examples of which are illustrated in the present description. In this regard, the exemplary embodiments may have different forms and should not be construed as being limited to the description set forth herein. Accordingly, exemplary embodiments are described below by referring to the figures to illustrate aspects of the present description only. As used herein, the term "and / or" encompasses all combinations of one or more of the associated listed items. A phrase such as "at least one of," when preceding a list of elements, modifies the entire list of elements and does not modify each individual element of the list.

[0012] As used herein, the terms "a," "an," and "the" do not denote limitations of quantity and should be construed to include both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. "Or" means "and / or," unless otherwise stated. All ranges disclosed herein are inclusive of the endpoints, which are independent and combinable with each other. The suffix "(s)" is intended to include both the singular and the plural of the term it modifies, thereby including at least one of that term. "Optional" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances when the event occurs and instances when the event does not occur. The terms "first," "second," and the like, are used herein not to denote order, quantity, or importance, but rather to distinguish one element from another. When an element is said to be "on" another element, it may be in direct contact with the other element, or intervening elements may be present between them. In contrast, when an element is said to be "directly on" another element, there are no intervening elements present. It should be understood that the described components, elements, limitations, and / or features of the embodiments may be combined in any suitable manner in the various embodiments.

[0013] Unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as commonly understood by those skilled in the art to which this invention belongs. Terms, such as those defined in commonly used dictionaries, should be interpreted to have a meaning consistent with their meaning in the context of the relevant technical field and this disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

[0014] As used herein, "actinic rays" or "radiation" refers to, for example, the emission spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, particle rays such as electron beams and ion beams, etc. Furthermore, in the present invention, "light" refers to actinic rays or radiation. Krypton fluoride lasers (KrF lasers) are a specific type of excimer laser, and are sometimes called exciplex lasers. "Excimer" stands for "excimer dimer", while "exciplex" stands for "exciplex". Excimer lasers use a mixture of rare gases (argon, krypton, or xenon) and halogen gases (fluorine or chlorine) to emit coherent induced radiation (laser light) in the ultraviolet range under appropriate conditions of electrical stimulation and high pressure. Furthermore, unless otherwise specified, "exposure" in this specification includes not only exposure to far ultraviolet light such as that provided by a mercury lamp or an excimer laser, X-rays, extreme ultraviolet light (EUV light), and the like, but also writing using particle beams such as electron beams and ion beams.

[0015] As used herein, the term "hydrocarbon" refers to an organic compound having at least one carbon atom and at least one hydrogen atom; "alkyl" refers to a straight or branched chain saturated hydrocarbon group having the specified number of carbon atoms and having a valence of one; "alkylene" refers to an alkyl group having a valence of two; "hydroxyalkyl" refers to an alkyl group substituted with at least one hydroxyl group (-OH); "alkoxy" refers to "alkyl-O-"; "carboxyl" and "carboxyl" are examples of alkyl groups. "Cycloalkyl" refers to a monovalent group having one or more saturated rings in which all ring members are carbon; "cycloalkylene" refers to a cycloalkyl group having a valence of two; "alkenyl" refers to a linear or branched monovalent hydrocarbon group having at least one carbon-carbon double bond; "alkenoxy" refers to "alkenyl-O-"; "alkenylene" refers to an alkenyl group having a valence of two; "cycloalkenyl" refers to an alkyl group having at least one carbon- "alkynyl" refers to a monovalent hydrocarbon group having at least three carbon atoms and a carbon-carbon double bond; the term "aromatic group" refers to a monocyclic or polycyclic aromatic ring system that satisfies the Huckel rule (4n+2π electrons) and contains carbon atoms in the ring; the term "heteroaromatic group" refers to an aromatic group that contains one or more heteroatoms (e.g., 1 to 4 heteroatoms) selected from N, O, and S in place of carbon atoms in the ring; "aryl" refers to a monovalent hydrocarbon group having at least one carbon atom and a carbon atom in the ring; " refers to a monovalent mono- or polycyclic aromatic ring system in which all ring members are carbon and which may include groups having an aromatic ring fused to at least one cycloalkyl or heterocycloalkyl ring; "arylene" refers to an aryl group having a valence of two; "alkylaryl" refers to an aryl group substituted with an alkyl group; "arylalkyl" refers to an alkyl group substituted with an aryl group; "aryloxy" refers to "aryl-O-"; and "arylthio" refers to "aryl-S-".

[0016] The prefix "hetero" means that the compound or group contains at least one member that is a heteroatom (e.g., 1, 2, 3, or more heteroatoms) in place of a carbon atom, where the heteroatoms are each independently N, O, S, Si, or P; a "heteroatom-containing group" refers to a substituent that contains at least one heteroatom; the term "heterocycloalkyl" refers to a cycloalkyl group having at least one heteroatom in place of carbon as a ring member; the term "heterocycloalkylene" refers to a heterocycloalkyl group having a valence of 2. The term "heteroaryl" refers to a 4-8 membered monocyclic, 8-12 membered bicyclic, or 11-14 membered tricyclic aromatic ring system having 1-4 heteroatoms (for monocyclic), 1-6 heteroatoms (for bicyclic), or 1-9 heteroatoms (for tricyclic).

[0017] The prefix "halo" refers to a group that contains one or more of fluoro, chloro, bromo, or iodo substituents in place of a hydrogen atom. The term "halogen" refers to a monovalent substituent that is fluorine (fluoro), chlorine (chloro), bromine (bromo), or iodine (iodo). Combinations of halogen groups (e.g., bromo and fluoro) or only fluoro groups may be present. The term "substituted C1-8 haloalkyl" refers to a C1-8 alkyl group that is substituted with at least one halogen, which is further substituted with one or more other substituents that are not halogens.

[0018] Unless expressly stated otherwise, each of the above substituents may be optionally substituted. The term "optionally substituted" refers to substituted or unsubstituted. "Substituted" means that at least one hydrogen atom of a chemical structure or group is replaced with another terminal substituent, which is typically monovalent, provided that the valence does not exceed the normal valence of the designated atom. When the substituent is oxo (i.e., =O), two geminal hydrogen atoms on the carbon atom are replaced with the terminal oxo group. It is further noted that the oxo group is bonded to the carbon through a double bond to form a carbonyl (C=O), and the carbonyl group is represented herein as -C(O)-. Combinations of substituents or variables are permitted. Exemplary substituents that may be present at the "substituted" position include nitro (-NO2), cyano (-CN), hydroxyl (-OH), oxo (O), amino (-NH2), mono- or di-(C 1~6 ) Alkylamino, alkanoyl (acyl, etc.) 2~6 alkanoyl group, etc.), formyl (-C(O)H), carboxylic acid or its alkali metal salt or ammonium salt;C 2~6 Alkyl esters (-C(O)O-alkyl or -OC(O)-alkyl), C 7~13 Esters, such as aryl esters (-C(O)O-aryl or -OC(O)-aryl), including acrylates, methacrylates, and lactones; amides (-C(O)NR, where R is hydrogen or C 1~6 alkyl), carboxamide (-CHC(O)NR, where R is hydrogen or C 1~6 alkyl), halogen, thiol (-SH), C 1~6 Alkylthio (-S-alkyl), thiocyano (-SCN), C 1~6 Alkyl, C 2~6 Alkenyl, C 2~6 Alkynyl, C 1~6 Haloalkyl, C 1~9 Alkoxy, C 1~6 Haloalkoxy, C 3~12 Cycloalkyl, C 5~18 Cycloalkenyl, C 2~18Heterocycloalkenyl, C having at least one aromatic ring (e.g., phenyl, biphenyl, naphthyl, etc., each ring being substituted or unsubstituted aromatic). 6~12 Aryl, C having 1-3 separate or fused rings and 6-18 ring carbon atoms 7~19 Arylalkyl, arylalkoxy having 1-3 separate or fused rings and 6-18 ring carbon atoms, C 7~12 Alkylaryl, C 3~12 Heterocycloalkyl, C 3~12 Heteroaryl, C 1~6 Alkylsulfonyl (-S(O)2-alkyl), C 6~12 Examples include, but are not limited to, arylsulfonyl, (-S(O)2-aryl), or tosyl (CH3C6H4SO2-).

[0019] In this specification, unless otherwise defined, a "divalent linking group" is any of -O-, -S-, -Te-, -Se-, -C(O)-, -C(O)O-, -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 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 each R ’ are independently hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted 1~20 Heteroalkyl, substituted or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 Typically, the divalent linking group is -O-, -S-, -C(O)-, -C(O)O-, -N(R')-, C(O)N(R ’ )-, -S(O)-, -S(O)2-, substituted or unsubstituted C 1~30Alkylene, substituted or unsubstituted C 3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 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 C 3~30 It is heteroaryl.

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

[0021] Organic underlayer films can be used to protect the underlying substrate during various pattern transfer and etching processes. Often these films are cast and cured directly onto an inorganic substrate (i.e., TiN). In these cases, it is desirable for the underlayer film to adhere well to the substrate during all subsequent processing steps to protect the substrate from conditions that would otherwise be damaging. A typical wet etch process involves immersing the substrate in a caustic solvent bath. Underlayer films that are not well adhered to the substrate can delaminate while they are immersed, exposing the underlying inorganic substrate and causing damage.

[0022] Incorporating structural units derived from N-(alkoxymethyl)(meth)acrylamides into the polymeric units of photoresist underlayer materials can significantly improve the solvent resistance and thermal stability after curing, and in some cases improve the collapse margin, without significantly compromising the etch resistance and reflectance parameters. When used in photoresist underlayer compositions, structural units derived from N-(alkoxymethyl)(meth)acrylamides can form crosslinks and / or can be crosslinkable, and preferably the polymer is crosslinkable without irradiation. The photoresist underlayer compositions of the present invention further comprise a thermal acid generator (TAG), and preferably do not comprise a photoacid generator (PAG). Crosslinking can be via a crosslinking agent or by self-crosslinking.

[0023] According to one aspect of the invention, a photoresist underlayer composition includes a first polymer including a first structural unit derived from an N-(alkoxymethyl)(meth)acrylamide monomer, a second structural unit including an aromatic group, a heterocyclic group, an ester group, an amide group, or a combination thereof, the second structural unit further including a crosslinkable group, a thermal acid generator, and a solvent. In the photoresist underlayer composition, the first polymer can include the second structural unit, or the photoresist underlayer composition can further include a second polymer including the second structural unit, or both the first polymer and the second polymer can each include the second structural unit.

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

[0025] As used herein, a "crosslinkable group" refers to a hydroxyl (-OH), carboxyl (-C(O)OH), amine (-NH2), thiol (-SH), vinyl (e.g., C 2~30Crosslinkable groups refer to nucleophilic groups containing oxygen, nitrogen, or sulfur, such as aryl, aryloxy ...

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

[0027] In yet another embodiment, the first polymer can include a first structural unit derived from an N-(alkoxymethyl)(meth)acrylamide monomer and a second structural unit comprising a first aromatic group, a first heterocyclic group, a first ester group, a first amide group, or a combination thereof, where the second structural unit further comprises a first crosslinkable group, and the photoresist underlayer composition can further include a second polymer including a third structural unit, where 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, where the third structural unit further comprises a second crosslinkable group. It should be understood that the first aromatic group and the second aromatic group can be the same or different, the first heterocyclic group and the second heterocyclic group can be the same or different, the first ester group and the second ester group can be the same or different, the first amide group and the second amide group can be the same or different, and the first crosslinkable group and the second crosslinkable group can 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, an "ester group" refers to a group of the formula -C(O)O- or -O(CO)-. As used herein, an "amide group" refers to a group of the formula -C(O)NR- or -RNC(O)-, where R is hydrogen, substituted or unsubstituted C 1~20 Alkyl group, or substituted or unsubstituted C 6~60 An "aromatic group" as used herein is a monocyclic or polycyclic C 6~60 Refers to an aromatic group. 6~60 When the aromatic group is polycyclic, the rings or ring groups may be fused (e.g., naphthyl) or directly bonded (e.g., biaryl, biphenyl). In one embodiment, the polycyclic aromatic group may contain a combination of fused and directly bonded rings or ring groups (e.g., binaphthyl). As used herein, a "heterocyclic group" refers to a monocyclic or polycyclic C 3~60 Heteroaromatic groups or monocyclic or polycyclic C 3~60 Refers to heterocycloalkyl groups. 3~60 Heteroaromatic groups and / or C 3~60 When a heterocycloalkyl is polycyclic, the rings or ring groups may be fused, directly bonded, or a combination of fused and directly bonded rings or ring groups.

[0029] In some embodiments, the first polymer comprises a first structural unit derived from an N-(alkoxymethyl)(meth)acrylamide monomer and a C 6~60 and a second structural unit comprising an aryl group and a crosslinkable group. 6~60 The aryl group may be further substituted with other substituents other than the crosslinkable group, or may be unsubstituted other than the crosslinkable group. Exemplary substituents include 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 1~30 Heterocycloalkyl, substituted or unsubstituted C 2~30Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, substituted or unsubstituted C 6~30 Aryl, substituted or unsubstituted C 7~30 Aryl alkyl, substituted or unsubstituted C 7~30 Alkylaryl, substituted or unsubstituted C 3~30 Heteroaryl, substituted or unsubstituted C 4~30 Alkylheteroaryl, or substituted or unsubstituted C 4~30 The bridging group may be one or more of the following: C 6~60 The bridging group may be attached directly to a carbon atom of the aryl group or may be 6~60 Attachment can be via a divalent linking group of an aryl group (ie, as a pendant group to the polymer backbone).

[0030] In some embodiments, the first polymer can include a first structural unit derived from an N-(alkoxymethyl)(meth)acrylamide monomer, and the photoresist underlayer composition can further include a second polymer including a second structural unit. For example, the second polymer can be 3~60 It may include a second structural unit that includes a heterocycloalkyl group and a crosslinkable group. 3~60 The heterocycloalkyl group may be further substituted with another substituent other than the crosslinkable group, or may be unsubstituted except for the crosslinkable group. Exemplary additional substituents include 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 1~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, substituted or unsubstituted C 6~30 Aryl, substituted or unsubstituted C 7~30 Aryl alkyl, substituted or unsubstituted C 7~30 Alkylaryl, substituted or unsubstituted C 3~30 Heteroaryl, substituted or unsubstituted C 4~30Alkylheteroaryl, or substituted or unsubstituted C 4~30 The bridging group may be one or more of the following: C 3~60 The bridging group may be attached directly to an atom of the heterocycloalkyl group (i.e., via a single bond) or may be attached via a divalent linking group, CC 3~60 It may also be attached to a heterocycloalkyl group (ie, as a pendant group to a polymer backbone).

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

[0032] In formula (1), R a is hydrogen, fluorine, cyano, or substituted or unsubstituted C 1~10 Preferably, R a is hydrogen, fluorine, cyano, or substituted or unsubstituted C 1~5 It is an alkyl group, typically methyl.

[0033] In formula (1), R 1 is hydrogen, or substituted or unsubstituted C 1~10 Typically, R 1 is hydrogen or methyl. In some embodiments, R 1 is not hydrogen.

[0034] In formula (1), R 2 and R 3 are each independently 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 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 6~30Aryl, substituted or unsubstituted C 7~30 Aryl alkyl, 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 alkylheteroaryl. Preferably, R 2 and R 3 are each independently hydrogen or a substituted or unsubstituted C 1~10 alkyl, typically methyl. In some embodiments, R 2 and R 3 At least one of R is hydrogen, e.g. 2 and R 3 Both R and R may be hydrogen. 2 and R 3 may optionally form a ring via a single bond or a divalent linking group, said ring being substituted or unsubstituted.

[0035] R 2 and R 3 Each of R optionally further includes a divalent linking group as part of their structure. For example, each R 2 ~R 3 may optionally include, as part of its structure, -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R ’ )-, or -C(O)N(R')-, R ’ is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 3~20 It may be a heterocycloalkyl.

[0036] R 4 is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, substituted or unsubstituted C 2~20 Heterocycloalkyl, substituted or unsubstituted C6~24 Aryl, substituted or unsubstituted C 7~25 Aryl alkyl, 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 It is an alkylheteroaryl.

[0037] R 2 or R 3 one of which is connected to R via a single bond or a divalent linking group 4 may optionally form a heterocycle, which may be substituted or unsubstituted.

[0038] Exemplary N-(alkoxymethyl)(meth)acrylamide monomers may include one or more of the following: [ka] (In the formula, R a is as defined in equation (1).

[0039] The first structural units derived from N-(alkoxymethyl)(meth)acrylamide monomers are typically present in the first polymer in an amount of from 5 to 100 mole percent (mol %), more typically from 5 to 75 mol %, and even more typically from 5 to 50 mol %, based on the total repeat units in the first polymer.

[0040] The second structural unit can include an aromatic group and can be derived from a monomer of formula (2): [ka] (In the formula, each R b is hydrogen, fluorine, cyano, cyano, or substituted or unsubstituted C 1~10 Preferably, R bis hydrogen, fluorine, or substituted or unsubstituted C 1~5 It may be alkyl, typically methyl.

[0041] In formula (2), n is 0 or 1. When n is 0, L 1 is to be understood to be attached directly to a carbon atom of the alkenyl group in formula (2).

[0042] In formula (2), L 1 represents a single bond or a divalent linking group. For example, L 1 is optionally -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -NR 102 - or -C(O)N(R 102 Optionally substituted aliphatic (C 1~6 Alkylene or C 3~20 R may be a divalent linking group selected from alkyl, aryl, cycloalkylene, and aromatic hydrocarbons, and combinations thereof; 102 is hydrogen and optionally substituted C 1~10 is selected from alkyl.

[0043] n is 0 and L 1 is a single bond, the group Ar 1 should be understood to be attached directly to a carbon atom of the alkenyl group in formula (2).

[0044] In formula (2), Ar 1 is a substituted or unsubstituted C 6~60 Aryl groups, typically substituted or unsubstituted C 6~14 It is an aryl group.

[0045] In formula (2), each L 2 L is independently a single bond or a divalent linking group. 2 Exemplary divalent linking groups include substituted or unsubstituted 1~30 Alkylene, substituted or unsubstituted C 1~30 Heteroalkylene, substituted or unsubstituted C3~30 Cycloalkylene, substituted or unsubstituted C 3~30 Heterocycloalkylene, substituted or unsubstituted C 6~30 Arylene, substituted or unsubstituted C 3~30 Heteroarylene, -O-, -C(O)-, -C(O)O-, -S-, -S(O)2-, -N(R 103 )- or -C(O)N(R 104 )-, and R103 and R104 are each independently hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, or substituted or unsubstituted C 3~20 It may be a heterocycloalkyl.

[0046] In formula (2), each Z is independently a crosslinkable group. Preferably, each Z is independently a hydroxyl, carboxyl, thiol, amino, amide, epoxy, or lactone, typically a hydroxyl, thiol, or epoxy, more typically a hydroxyl.

[0047] In formula (2), y is an integer of 1 to 3, preferably y is an integer of 1 to 2, and typically y is 1.

[0048] Non-limiting examples of monomers of formula (2) include: [ka] (In the formula, R b is as defined in equation (2).

[0049] A polymer comprising the second structural unit may comprise repeat units derived from a monomer of formula 2 in an amount of 2 to 100 mol %, typically 10 to 100 mol %, more typically 50 to 100 mol %, based on the total number of repeats in the polymer. When the first polymer comprises 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 number of structural units in the first polymer.

[0050] Non-limiting exemplary first polymers of the present invention include one or more of the following: [ka] where a, b, c, and d represent the mole fraction of each repeat unit of the first polymer.

[0051] In some embodiments, the second structural unit may include a heterocyclic group and may be a crosslinkable polyester polymer that includes a crosslinkable group. For example, the second polymer may include an isocyanurate repeat unit and a crosslinkable group. In some aspects, the crosslinkable group may be selected from hydroxyl, carboxyl, thiol, amino, epoxy, alkoxy, amide, vinyl, or a combination thereof.

[0052] The second polymer, if used, is preferably a polymer comprising one or more isocyanurate repeat units derived from a monomer of formula (3): [ka]

[0053] In formula (3), K, L, and M are each independently a linear or branched C alkyl group, each of which is optionally substituted with a carboxylic acid group. 1~10 Hydrocarbon group, C 1~10 Alkoxycarbonyl group, C 1~10 Alkanoyloxy group, or C1~5 Alkoxycarbonyl group or C 1~5 Linear or branched C optionally substituted with substituted alkoxy groups 1~10 It is a hydroxyalkyl group.

[0054] In formula (3), for K, L, and M, 1~10 Hydrocarbon group, C 1~10 Alkoxycarbonyl group, C 1~10 Alkanoyloxy group, and C 1~10 Each of the hydroxyalkyl groups is a halogen, an amino group, a thiol group, an epoxy group, an amide group, and a C 1~5 Alkyl group, C 3~8 Cycloalkyl groups, C 3~20 Heterocycloalkyl groups, C 2~5 Alkenyl group, C 1~5 Alkoxy group, C 2~5 Alkenoxy group, C 6~12 Aryl group, C 6~12 Aryloxy group, C 7~13 Alkylaryl group, or C 7~13 C may be optionally substituted with at least one alkylaryloxy group. 3~8 Cycloalkyl groups and C 3~20 The heterocycloalkyl group may be optionally substituted on at least one ring carbon atom with an oxo group (=O). At least one hydrogen atom of the first polymer derived from a monomer of formula (2) is substituted with a functional group independently selected from hydroxyl, carboxyl, thiol, amino, epoxy, alkoxy, amide, vinyl, or combinations thereof. Of these, hydroxyl, carboxyl, or alkoxy are preferred.

[0055] In some embodiments, the second structural unit can include a heterocyclic group that includes a substituted cyanurate structural unit derived from a compound represented by formula (4), formula (5), or a combination thereof: [ka]

[0056] In formulas (4) and (5), R 5 and R 6 are each independently hydrogen, substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C 3~30 Cycloalkyl, substituted or unsubstituted C 3~30 Heterocycloalkyl, substituted or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 It is heteroaryl.

[0057] In formulas (4) and (5), R 7 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 Alkynyl, substituted or unsubstituted C 2~30 Alkanoyl, 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 Alkylsulfonyl, substituted or unsubstituted C2-C 30 Alkoxycarbonyl, substituted or unsubstituted C 3~20 Cycloalkenyl, substituted or unsubstituted C 3~20 Heterocycloalkenyl, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C7-C 30 Alkylaryl, substituted or unsubstituted C7-C 30 Aryl alkyl, substituted or unsubstituted C 3~30 Heteroaryl, substituted or unsubstituted C 4~30 Alkylheteroaryl, or substituted or unsubstituted C 4~30 It is heteroarylalkyl.

[0058] In formulas (4) and (5), each of X and X′ is independently hydrogen or a substituted or unsubstituted C 1~10 Preferably, each of X and X' is hydrogen.

[0059] In formulas (4) and (5), n1, n2, m1, m2, and m3 are each independently an integer of 1 to 10. Preferably, n1, n2, m1, m2, and m3 are each independently an integer of 1 to 4, and typically 1 or 2.

[0060] The second polymer comprising the second structural unit comprising the substituted cyanurate structural unit can be formed by conventional polycondensation techniques such as those described in, for example, (Non-Patent Document 1) and references therein, and / or (Non-Patent Document 2) and references therein. In one embodiment, the diol or polyol and the dicarboxylic acid or polycarboxylic acid are placed in a conventional polymerization vessel and reacted at about 100-280°C for several hours. Optionally, an esterification catalyst can be used to reduce the reaction time. It is also understood that esterifiable derivatives of polycarboxylic acids, such as dimethyl esters or anhydrides of polycarboxylic acids, can be used to prepare the polyester. Exemplary polyols and polycarboxylic acids include isocyanurate polyols and isocyanurate polycarboxylic acids. The polyester polymer can be linear or branched.

[0061] Suitable di- or polycarboxylic acids, or their corresponding alkyl esters, that may 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, suberic acid, dodecanedioic acid, phthalic acid, phthalic anhydride, 5-tert-butylisophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, azelaic acid, sebacic acid, tetrachlorophthalic anhydride, chlorendic acid, isophthalic acid, trimellitic anhydride, terephthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, dimer fatty acids, or the anhydrides of any of these acids, or combinations thereof.

[0062] Suitable diols and polyols include ethylene glycol, diethylene glycol, triethylene glycol and higher polyethylene glycols, propylene glycol, dipropylene glycol, tripropylene glycol and higher polypropylene glycols, 1,3-propanediol, 1,4-butanediol and other butanediols, 1,5-pentanediol and other pentanediols, hexanediol, decanediol, and dodecanediol, glycerol, trimethylolpropane, trimethylolethane, neopentyl glycol, pentaerythritol, cyclohexyl ether ... Examples of suitable cyclohexane dimethanol include, but are not limited to, san dimethanol, dipentaerythritol, 1,2-methyl-1,3-propanediol, 1,4-benzyl dimethanol, 2,4-dimethyl-2-ethylhexane-1,3-diol, isopropylidenebis(p-phenylene-oxypropanol-2), 4,4'-dihydroxy-2,2'-diphenylpropane, 1,3-cyclohexane dimethanol, 1,4-cyclohexane dimethanol (or a mixture of 1,3- and 1,4-cyclohexane dimethanol, which may be cis or trans), sorbitol, and the like, or combinations thereof.

[0063] When the second polymer contains a second structural unit containing 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 contain a heterocyclic group containing 5 to 50 mol % or 5 to 30 mol % of a substituted cyanurate structural unit derived from a compound represented by formula (4), formula (5), or a combination thereof.

[0064] It should be understood that the polymers described herein, including the first polymer and the second polymer, may each independently optionally include one or more additional repeat units different from the repeat units described above. The additional repeat units may include one or more additional units for the purpose of adjusting the properties of the photoresist underlayer composition, such as, for example, etch rate and solubility. Exemplary additional units may include one or more of (meth)acrylate, vinyl ether, vinyl ketone, and vinyl ester. When present in the polymer, the one or more additional repeat units are typically used in an amount of up to 99 mol %, typically 3 to 80 mol %, based on the total of the repeat units of the respective polymer.

[0065] The polymers of the present invention have a weight average molecular weight (M) of from 1,000 to 10,000,000 grams per mole (g / mol), more typically from 2,000 to 10,000 g / mol. w ), and number average molecular weight (M n ) can have a molecular weight (M w Or M n ) is suitably determined by gel permeation chromatography (GPC) using polystyrene standards.

[0066] Suitable polymers of the present invention can be easily prepared based on and by analogy with the procedures described in the examples of the present application, which are easily understood by those skilled in the art. For example, one or more monomers corresponding to the repeating units described herein can be combined or separately fed using a suitable solvent and initiator and polymerized in a reactor. The monomer composition can further include additives such as solvents, polymerization initiators, curing catalysts (i.e., acid catalysts), etc. For example, the polymer can be obtained by polymerization of the respective monomers under any suitable conditions, such as heating at an effective temperature, irradiation with activating radiation at an effective wavelength, or a combination thereof.

[0067] The photoresist underlayer composition may further comprise one or more polymers in addition to those described above ("additional polymers"). For example, the photoresist underlayer composition may further comprise an additional polymer as described above, but of a different composition. Additionally or alternatively, the one or more additional polymers may include one or more polymers selected from those known in the art, such as polyacrylates, polyvinyl ethers, polyesters, polynorbornenes, polyacetals, polyethylene glycols, polyamides, polyacrylamides, polyphenols, novolacs, styrenic polymers, polyvinyl alcohols, or combinations thereof.

[0068] The photoresist underlayer composition further comprises a thermal acid generator (TAG) compound that aids in hardening of the photoresist underlayer composition, for example, after the photoresist underlayer composition has been applied to a surface. The photoresist underlayer compositions of the present invention can include any suitable TAG that causes hardening of the photoresist underlayer composition on the surface of a substrate.

[0069] Exemplary thermal acid generators include, but are not limited to, amine-blocked strong acids, e.g., amine-blocked sulfonic acids, such as amine-blocked dodecylbenzenesulfonic acid. It will also be appreciated by those skilled in the art that certain photoacid generators can liberate acid upon heating and function as thermal acid generators.

[0070] Suitable TAG compounds may include, for example, nitrobenzyl tosylates such as 2-nitrobenzyl tosylate, 2,4-dinitrobenzyl tosylate, 2,6-dinitrobenzyl tosylate, 4-nitrobenzyl tosylate; benzenesulfonates such as 2-trifluoromethyl-6-nitrobenzyl 4-chlorobenzenesulfonate, 2-trifluoromethyl-6-nitrobenzyl 4-nitrobenzenesulfonate; phenolsulfonate esters such as phenyl, 4-methoxybenzenesulfonate; alkylammonium salts of organic acids such as triethylammonium salts of 10-camphorsulfonic acid, trifluoromethylbenzenesulfonic acid, perfluorobutanesulfonic acid; and certain onium salts. Various aromatic (anthracene, naphthalene, or benzene derivative) sulfonic acid amine salts can be used as TAGs, such as those disclosed in (Patent Document 1), (Patent Document 2), (Patent Document 3) and (Patent Document 4). Nos. 3,474,054, 4,200,729, 4,251.665, and 5,187,019. Examples of TAGs include those sold under the names NACURE, CDX, and K-PURE, e.g., NACURE 5225, CDX-2168E, K-PURE 2678, and KPURE 2700 by King Industries, Norwalk, Conn. USA. One or more of such TAGs can be used.

[0071] The amount of TAG compound useful in the present compositions can be, for example, from 0.01 to 15 weight percent, typically from 0.01 to 10 weight percent, based on the total solids content of the photoresist underlayer composition.

[0072] In some embodiments, the photoresist underlayer composition can further comprise a photoacid generator (PAG). Suitable PAGs include, for example, onium salts such as triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; nitrobenzyl derivatives such as 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate, and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonic acid esters such as 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonate). diazomethane derivatives such as bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, glyoxime derivatives such as bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime, and bis-O-(n-butanesulfonyl)-α-dimethylglyoxime, sulfonate derivatives of N-hydroxyimide compounds such as N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, and halogen-containing 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 such PAGs can be used.

[0073] In some aspects, the photoresist underlayer composition does not include a photoacid generator, and thus, in these embodiments, the photoresist underlayer composition may be substantially free of PAG compounds.

[0074] The photoresist underlayer composition may further comprise one or more crosslinkers, including, for example, non-epoxy crosslinkers. Any suitable crosslinker may further be used in the present coating composition, provided that such crosslinker has at least two, preferably at least three, sites capable of reacting with the functional groups in the photoresist underlayer composition. Exemplary crosslinkers include novolac resins, melamine compounds, guanamine compounds, isocyanate-containing compounds, benzocyclobutenes, benzoxazines, and the like, typically including methylol, C1-C ... 10 Alkoxymethyl and C2~ 10 Examples of suitable crosslinkers include any of the above with two or more, more typically three or more, substituents selected from acyloxymethyl. [ka]

[0075] Additional crosslinking agents are well known in the art and are commercially available from a variety of sources. If present, the amount of such additional crosslinking agent useful in the present Photoresist Underlayer composition can be, for example, from 0.01 to 30 weight percent, preferably from 0.01 to 20 weight percent, based on the total solids content of the Photoresist Underlayer composition.

[0076] The photoresist underlayer composition can include one or more optional additives including, for example, surfactants, antioxidants, and the like, or combinations thereof. When present, each optional additive can be used in the photoresist underlayer composition in small amounts, such as from 0.01 to 10 weight percent, based on the total solids content of the photoresist underlayer composition.

[0077] Typical surfactants include those that exhibit amphiphilic properties, meaning that they may be both hydrophilic and hydrophobic at the same time. Amphiphilic surfactants have a hydrophilic head group that has a strong affinity for water and a long hydrophobic tail that is organophilic and repels water. Suitable surfactants may be ionic (i.e., anionic or cationic) or nonionic. Further examples of surfactants include silicone surfactants, poly(alkylene oxide) surfactants, and fluorochemical surfactants. Suitable nonionic surfactants include, but are not limited to, octyl and nonyl phenol ethoxylates such as TRITON X-114, X-100, X-45, X-15, and branched secondary alcohol ethoxylates such as TERGITOL TMN-6 (The Dow Chemical Company, Midland, Mich. USA). Still further exemplary surfactants include alcohol (primary and secondary) ethoxylates, amine ethoxylates, glucosides, glucamines, polyethylene glycols, poly(ethylene glycol-co-propylene glycol), or other surfactants disclosed in (Non-Patent Document 3) published by Manufacturers Confectioners Publishing Co., Glen Rock, NJ. Non-ionic surfactants that are acetylenic diol derivatives may also be suitable. Such surfactants are commercially available from Air Products and Chemicals, Inc., Allentown, Pa., and are sold under the trade names SURFYNOL and DYNOL. Additional suitable surfactants include other polymeric compounds such as triblock EO-PO-EO copolymers PLURONIC 25R2, L121, L123, L31, L81, L101, and P123 (BASF, Inc.).

[0078] Suitable antioxidants include, for example, phenol-based antioxidants, antioxidants consisting of organic acid derivatives, sulfur-containing antioxidants, phosphorus-based antioxidants, amine-based antioxidants, antioxidants consisting of amine-aldehyde condensates, and antioxidants consisting of amine-ketone condensates. Examples of phenolic antioxidants include 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, butyl 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-butylanilino)2,4-bis-octyl-thio~1,3,5-triazine, n-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenyl)propionate, octylated phenol, aralkyl Substituted phenols such as alkylated p-cresols and hindered phenols; 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-bridged polyhydric alkylphenols, 4,4'-butylidene-bis-(3-methyl-6-tert-butylphenol), 1,1-bis-(4-hydroxyphenyl)-cyclohexane, 2,2'-dihydroxy-3,3'-di-(α-methylcyclohexyl)-5,5'-dimethyl.Included are bis-, tris- and poly-phenols such as diphenylmethane, 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 tetrakis-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane. Suitable antioxidants are commercially available, for example, Irganox™ antioxidants (Ciba Specialty Chemicals Corp.).

[0079] The photoresist underlayer composition includes a solvent. The solvent component may be a single solvent or may include a mixture of two or more separate solvents. Preferably, each of the solvents may be miscible with each other. Suitable solvents include, for example, one or more oxyisobutyric acid esters, particularly methyl-2-hydroxyisobutyric acid, 2-hydroxyisobutyric acid, and ethyl lactate; one or more glycol ethers, particularly 2-methoxyethyl ether (diglyme), ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; one or more solvents having both ether and hydroxyl moieties, 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 dibasic esters; and / or one or more propylene carbonates and other solvents such as gamma butyrolactone.

[0080] The desired total solids content of the photoresist underlayer composition will depend on factors such as the desired final layer thickness. Typically, the total solids content of the photoresist underlayer composition can be from 0.1 to 20 weight percent, such as from 0.1 to 10 weight percent, more typically from 0.1 to 5 weight percent, based on the total weight of the photoresist underlayer composition.

[0081] The photoresist underlayer composition can be made according to known procedures. For example, the photoresist underlayer composition can be prepared by combining the first material, the second material, the additive, the solvent, and any optional components in any order. The photoresist underlayer composition can be used as is, or can be purified or diluted before being coated onto a substrate. Purification can include, for example, one or more of centrifugation, filtration, distillation, decantation, evaporation, treatment with ion exchange beads, and the like.

[0082] The patterning method of the present invention includes applying a layer of a photoresist underlayer composition on a substrate; curing the applied photoresist underlayer composition to form a photoresist underlayer; and forming a photoresist layer on the photoresist underlayer. The method may further include patterning the photoresist layer and transferring the pattern from the patterned photoresist layer to the photoresist underlayer and to a layer below the photoresist underlayer. In some embodiments, the method may further include exposing the photoresist layer to activating radiation in a pattern; and developing the exposed photoresist layer to obtain a resist relief image. In some aspects, the method may further include forming a silicon-containing layer, an organic antireflective coating layer, or a combination thereof on the photoresist underlayer 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 layer, or a combination thereof after developing the exposed photoresist layer and before transferring the pattern to the photoresist underlayer.

[0083] A wide variety of substrates may be used in the patterning method, with electronic device substrates being typical. Suitable substrates include, for example, packaging substrates such as multichip modules, flat panel display substrates, integrated circuit substrates, substrates for light emitting diodes (LEDs) such as organic light emitting diodes (OLEDs), semiconductor wafers, polycrystalline silicon substrates, and the like. Suitable substrates may be in the form of wafers such as those used in the manufacture of integrated circuits, optical sensors, flat panel displays, optical integrated circuits, and LEDs. As used herein, the term "semiconductor wafer" is intended to encompass "electronic device substrates," "semiconductor substrates," "semiconductor devices," and various packages for various levels of interconnection, such as single chip wafers, multiple chip wafers, packages for various levels, or other assemblies requiring solder connections. Such substrates may be of any suitable size. A typical wafer substrate diameter is 200 mm to 300 mm, although wafers having smaller and larger diameters may be suitably used in accordance with the present 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. By semiconductor device is meant a semiconductor substrate upon which at least one microelectronic device has been or is being batch fabricated.

[0084] The substrate is typically composed of one or more of silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. The substrate may include one or more layers and patterned features. The layers may include, for example, aluminum, copper, molybdenum, tantalum, titanium, tungsten, alloys of such metals, nitrides or silicides, one or more conductive layers such as layers of doped amorphous silicon or doped polysilicon, 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 embodiments, the substrate comprises titanium nitride. The layers can be formed by a variety of 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.

[0085] In certain patterning methods of the present invention, it may be desirable to provide one or more lithography layers, such as a hardmask layer, for example, a spin-on-carbon (SOC), amorphous carbon, or metal hardmask layer, a CVD layer such as a silicon nitride (SiN) layer, a silicon oxide (SiO) layer, or a silicon oxynitride (SiON) layer, an organic or inorganic BARC layer, or a combination thereof, on the upper layer of the substrate before forming the photoresist underlayer of the present invention. Such layers, together with the layer of the photoresist underlayer composition of the present invention and the photoresist layer, form a lithography material stack. Typical lithography 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 hardmask layer / underlayer / photoresist layer; amorphous carbon layer / underlayer / photoresist layer; and amorphous carbon layer / SiON layer / underlayer / photoresist layer.

[0086] As used herein, a "photoresist underlayer" is understood to refer to one or more layers disposed between the substrate and the photoresist layer (i.e., "over the substrate"). Thus, a coated underlayer of the invention (i.e., a layer of a photoresist underlayer composition) can be used alone as a photoresist underlayer, or a coated underlayer of the invention (i.e., a layer of a photoresist underlayer composition) can be used in combination with other underlayers, such as those described herein.

[0087] The photoresist underlayer composition can be coated on the substrate by any suitable means, such as spin coating, slot die coating, doctor blading, curtain coating, roller coating, spray coating, dip coating, and the like. In the case of semiconductor wafers, spin coating is preferred. In a typical spin coating method, the composition is applied to a substrate spinning at a speed of 500 to 4000 revolutions per minute (rpm) for a period of 15 to 90 seconds to obtain a desired layer of condensation polymer on the substrate. It will be appreciated by those skilled in the art that the thickness of the coated layer can be adjusted by varying the spin speed as well as the solids content of the composition. An underlayer formed from a photoresist underlayer composition typically has a dry layer thickness of 1 to 500 nanometers (nm), more typically 1 to 100 nm.

[0088] The coated photoresist underlayer composition is optionally soft baked at a relatively low temperature to remove any solvent and other relatively volatile components. Typically, the substrate is baked at a temperature of 150° C. or less, preferably 60-125° C., more preferably 90-115° C. The baking time is typically 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes, more preferably 6-90 seconds. When the substrate is a wafer, such a baking step may be performed by heating the wafer on a hot plate. Such a soft baking step may be performed as part of the curing of the coating layer, or may be omitted altogether.

[0089] The photoresist underlayer composition is then cured to form a coated underlayer. The coating composition should be cured sufficiently so that the coated underlayer film does not or only minimally intermixes with other underlayer components or photoresist layers formed on the underlayer. The coating composition can be cured in an oxygen-containing atmosphere such as air or in an inert atmosphere such as nitrogen, and under conditions such as heat sufficient to obtain a cured coating layer. This curing step is preferably carried out on a hotplate type apparatus, although oven curing can be used to obtain equivalent results. Typically, curing can be carried out at temperatures of 150° C. or higher, or between 150 and 450° C. Curing temperatures of 180° C. or higher, or *1 It is more preferable that the curing temperature is 00 to 400° C. The curing time is typically 10 seconds to 10 minutes, or 30 seconds to 5 minutes, or 45 seconds to 2 minutes, or 45 to 90 seconds.

[0090] Optionally, a ramped or multi-step curing process may be used. A ramp bake typically begins at a relatively low (e.g., ambient) temperature, and the temperature is increased at a constant or varying ramp rate to a higher target temperature. A multi-step curing process involves curing in two or more temperature plateaus, typically a first step at a lower bake temperature and one or more additional steps at higher temperatures. Conditions for such ramped or multi-step curing processes are known to those skilled in the art and may allow for the omission of a preceding soft bake process.

[0091] After the applied photoresist underlayer composition is cured, a photoresist layer is formed on the applied underlayer.As mentioned above, other intervening layers can be provided between the applied photoresist underlayer and the overcoated photoresist layer.In some embodiments, the method can further include forming a silicon-containing layer, an organic antireflective coating layer, or a combination thereof on the applied photoresist underlayer before forming the photoresist layer.

[0092] A wide variety of photoresists may be suitably used in the method of the invention, typically positive tone materials. The specific photoresist used will depend on the exposure wavelength used and will usually include an acid-sensitive matrix polymer, a photoactive component such as a photoacid generator, a solvent, and optional additional components. Suitable photoresists are known to those skilled in the art and are commercially available, for example, from DuPont Electronics & Imaging in their UV™ and EPIC™ product lines of various photoresist materials. The photoresist may be applied to the substrate by known coating techniques such as those described above in connection with the underlayer composition, with spin coating being typical. Typical thicknesses for the photoresist layer are between 10 and 300 nm. The photoresist layer is typically then soft baked to minimize the solvent content in the layer, thereby forming a tack-free coating and improving adhesion of the layer to the substrate. The soft bake may be performed on a hot plate or in an oven, with a hot plate being typical. A typical photoresist soft bake is performed at a temperature of between 70 and 150° C., and for a time of between 30 and 90 seconds.

[0093] The photoresist layer is then exposed to activating radiation through a photomask to create a solubility differential between exposed and unexposed regions. Reference herein to exposing a photoresist composition to radiation activating for the composition indicates that the radiation can form a latent image in the photoresist composition. The photomask has optically transparent and optically opaque regions corresponding to areas of the resist layer that are exposed and not exposed, respectively, by activating radiation. The exposure wavelength is typically less than 400 nm, more typically less than 300 nm, such as 248 nm (KrF), 193 nm (ArF), or EUV wavelengths (e.g., 13.5 nm). In a preferred embodiment, the exposure wavelength is a 193 nm or EUV wavelength. The exposure energy is typically 10 to 100 millijoules per square centimeter (mJ / cm), depending, for example, on the exposure tool and the components of the photosensitive composition. 2 ).

[0094] Following exposure of the photoresist layer, a post-exposure bake (PEB) is typically performed. The PEB can be performed, for example, on a hot plate or in an oven. The PEB is typically performed at a temperature of 70-150° C. and for a time of 30-90 seconds. A latent image is thereby formed, defined by the boundaries between the regions where polarity has been switched and the regions where it has not been switched (corresponding to the exposed and unexposed regions, respectively). The photoresist layer is then developed to remove the exposed regions of the layer, leaving the unexposed regions forming a patterned photoresist layer. The developer is typically an aqueous alkaline developer, for example a tetraalkylammonium hydroxide solution, such as a tetramethylammonium hydroxide (TMAH) solution, typically a 0.26 normal (N) (2.38 wt %) TMAH solution. The developer can be applied by known techniques, for example, spin coating or paddle coating.

[0095] The pattern of the photoresist layer can be transferred to one or more underlayers, including the coated underlayer, and to the substrate by appropriate etching techniques, such as by plasma etching using appropriate gas species for each layer to be etched. Depending on the number of layers and materials involved, the pattern transfer can include multiple etching steps using different etching gases. The patterned photoresist layer, the coated underlayer, and other optional layers in the lithography stack can be removed after the pattern transfer to the substrate using conventional techniques. Optionally, one or more of the layers of the stack can be removed after the pattern transfer to the underlayer and before the pattern transfer to the substrate, or consumed during the pattern transfer and before the pattern transfer to the substrate. For example, the pattern transfer to one or more of a silicon-containing layer, an organic anti-reflective coating layer, etc. can be performed after the exposed photoresist layer is developed and before the pattern transfer to the coated underlayer. The substrate is then further processed according to known methods to form an electronic device.

[0096] Also provided is a coated substrate, comprising a layer of the photoresist underlayer composition of the present invention disposed on a substrate, and a second layer disposed on the layer of the photoresist underlayer composition. The second layer can be any one or more layers described herein, and in some cases can be a photoresist layer disposed on the layer of the photoresist underlayer composition. As used herein, the term "hardened layer" refers to a layer derived from the photoresist underlayer composition after the composition is disposed on a substrate and then hardened to form a coating layer or film, which is also simply called "photoresist underlayer". In other words, hardening the photoresist underlayer composition can be said to form a "hardened layer" that is a photoresist underlayer.

[0097] Yet another aspect provides a layered article comprising a coated underlayer obtained from the photoresist underlayer composition of the invention. In one embodiment, the layered article can include a substrate, a coated underlayer disposed on the substrate, and a photoresist layer disposed on the coated underlayer.

[0098] The concepts of the present invention are further illustrated by the following examples, which are intended to be non-limiting. The compounds and reagents used herein are commercially available, except where procedures are given below. EXAMPLES

[0099] Synthesis Examples Synthesis of Polymer A-1 [ka] 50.0 g of propylene glycol monomethyl ether acetate (PGMEA) was placed in a 250 mL 3-neck round bottom flask (RBF) equipped with a temperature control unit. The flask was heated to 60° C. under nitrogen. A mixed solution of N-(butoxymethyl)acrylamide (BOAM, 40.0 g) and V-65 (6.52 g) in PGMEA (43.3 g) was prepared and fed to the reactor over 180 minutes. After the feed was completed, the reactor was maintained at 60° C. for an additional 60 minutes. The reactor was then allowed to cool to room temperature with stirring. The reaction mixture was precipitated with a mixture of heptane and MTBE (4:1 by volume) (a 10-fold excess by volume was added relative to the 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% solution of the product was then prepared using tetrahydrofuran (THF) and precipitated from a mixture of heptane and MTBE (4:1 by volume). The solvent was removed by filtration and the resulting precipitate was then dried under vacuum at 50° C. for 1 day.

[0100] Synthesis of Polymer A-2 [ka] Polymer A-2 was prepared using a procedure similar 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.

[0101] Synthesis of Polymer A-3 [ka] Polymer A-3 was prepared using a procedure similar 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.

[0102] Synthesis of BOMMM: N-(butoxymethyl)-N-methylmethacrylamide (BOMMM) [ka] 9.78 g of n-butyl alcohol and 0.07 g of 4-methoxyphenol (MEHQ) were placed in a 250 mL 3-neck RBF set up with a condenser and static liquid apparatus. N-methacrylamide (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 were dissolved, aqueous sodium hydroxide (10% solution) was added to it, followed by 10.0 g of paraformaldehyde, added in small portions over 20 minutes. The resulting mixture was heated at 55°C for 30 minutes. The reaction solution was allowed to cool to room temperature. The pH was then adjusted to a pH of 5-6 by adding aqueous hydrochloric acid (35% solution). 0.3 g of oxalic acid and 52.45 g of n-butyl alcohol were then added to the reaction solution, and the resulting mixture was heated at 90-95°C for 6.5 hours while extracting water using a static liquid apparatus, yielding 126.57 g of reaction solution.

[0103] Synthesis of Polymer A-4 [ka] Polymer A-4 was prepared using a procedure similar 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.

[0104] Synthesis of BOEAM: N-(1-butoxyethyl)acrylamide (BOEAM) [ka] 10.0 g of n-butyl alcohol and 0.07 g of 4-methoxyphenol (MEHQ) were placed in a 250 mL 3-neck RBF set up with a condenser and 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 were dissolved, aqueous sodium hydroxide (10% solution) was added to it, followed by 15.0 g of acetaldehyde, added in small portions over 20 minutes. The resulting mixture was heated at 55°C for 30 minutes. The reaction solution was allowed to cool to room temperature. The pH was then adjusted to a pH of 5-6 by adding hydrochloric acid (35% solution). 0.3 g of oxalic acid and 78.67 g of n-butyl alcohol were then added to the reaction solution, and the resulting mixture was heated at 90-95°C for 6.5 hours while extracting water using a static liquid apparatus, yielding a reaction solution of 119.63 g.

[0105] Synthesis of Polymer A-5 [ka] Polymer A-5 was prepared using a procedure similar 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.

[0106] Synthesis of POMA: N-(phenoxymethyl)acrylamide (POMA) [ka] 61.2 g of deionized (DI) water and 0.2 g of butylated hydroxytoluene (BHT) were placed in a 250 mL 3-neck RBF set up with a condenser and static liquid device. 56.4 g of phenol, 42.6 g of acrylamide, and 36.0 g of paraformaldehyde were then added to the solution, and the resulting mixture was heated at 110° C. for 2 hours. The solution was allowed to cool to room temperature and then concentrated under vacuum. The crude product was purified by silica gel column chromatography to give 29.0 g of product as a yellow oil.

[0107] Synthesis of Polymer A-6 [ka] Polymer A-6 was prepared using a procedure similar 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.

[0108] Synthesis of Polymer A-7 [ka] 50.0 g of PGMEA was placed in a 3-neck 250 mL RBF equipped with a temperature control unit. The flask was heated to 60° C. under nitrogen. A mixed solution 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 180 minutes. After the feeds were completed, the reactor was maintained at 60° C. for an additional 60 minutes. The reactor was then allowed to cool to room temperature with stirring. The reaction mixture was precipitated with a mixture of heptane and MTBE (4:1 by volume) (a 10-fold excess was added by volume relative to the volume of the reaction mixture). The solvent was removed by filtration, after which the precipitate was dried under vacuum at 50° C. for 1 day. A 30% solution of the product was then prepared using THF, which was precipitated from a mixture of heptane and MTBE (4:1 by volume). The solvent was removed by filtration and the resulting precipitate was then dried under vacuum at 50° C. for 1 day.

[0109] Synthesis of Polymer B-1 [ka] A 250 mL RBF was charged with 46.09 g of tris(2-hydroxyethyl)isocyanurate, 21.6 g of tris(2-carboxyethyl)isocyanurate, 1.35 g of para-toluenesulfonic acid monohydrate, 31.15 g of dimethyl terephthalate, and 52 g of anisole. The mixture was then heated to 140-150°C and the contents were vigorously stirred. Methanol was slowly removed from the reaction along with the anisole 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. M w The molecular weight was 3000 g / mol and the PDI was 1.4 (GPC).

[0110] Synthesis of Polymer B-2 [ka] A 250 mL RBF was charged with 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 dibutylnaphthalene dicarboxylate, 67 g of anisole, and 100 g of 1-butanol. The mixture was then heated to 140-160 °C and the contents were vigorously stirred. Anisole and butanol 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. M w The molecular weight was 3000 g / mol and the PDI was 1.30 (GPC).

[0111] Synthesis of Polymer B-3 [ka] A 250 mL 3-neck RBF equipped with a temperature control unit was charged with 60.0 g of ethyl lactate. 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 then this prepared mixed solution was fed into the reactor over 180 minutes. After the feeding was completed, the reactor was maintained at 90° C. for an additional 60 minutes. The reactor was then allowed to cool to room temperature with stirring. The reaction mixture was precipitated using a mixture of MTBE and heptane (4:6 by volume) (a 10-fold excess by volume was used). The solvent was removed by decantation, and the precipitate was then air-dried. The resulting white solid was dissolved in THF (120 g) and precipitated from a combination of MTBE and heptane (4:6 by volume).

[0112] lower layer composition Table 1 shows the underlayer compositions of Examples 1-11 and Comparative Examples 1-6, which were prepared by mixing the components in the amounts shown. Each composition further contained 5 mg of 2,4,6-trimethylpyridinium p-toluenesulfonate, 4.8 g of methyl-2-hydroxyisobutyrate, and 4.8 g of PGMEA. Prior to use, the solutions were filtered through a polytetrafluoroethylene (PTFE) filter with a pore size of 0.45 μm.

[0113] [Table 1]

[0114] The following abbreviations were used in Table 1: C-1 is tetramethoxymethylglycoluril; C-2 is hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine.

[0115] Solvent resistance evaluation Each composition in Table 1 was spin-coated at 1500 rpm onto each of the 200 mm bare silicon wafers and then cured at 205° C. for 60 seconds to form a cured coating layer as a film. The initial thickness of the film on the silicon wafer was measured by ellipsometry (M2000 ellipsometer, JA Woolam), and then 30 mL of PGMEA was contacted with the surface of the wafer and left for 1 minute to fix it to the surface of the wafer. The wafer was then spin-dried at 4,000 rpm for 1 minute, and the remaining film thickness was measured by ellipsometry. The thickness difference (i.e., film loss) was then calculated based on the film thickness before and after contact with PGME / spin drying. The results are shown in Table 2 as film loss (Angstroms, Å).

[0116] Sublimation resistance evaluation To determine the amount of material that sublimes from the film during the curing process, a test procedure was employed that measures the amount of material that condenses onto a quartz crystal placed approximately 1 cm above the polymer film during the process of curing the film on a bare silicon wafer using a hot plate. Each composition in Table 1 was spin coated onto each of the 200 mm bare silicon wafers at 1500 rpm without a post-bake heating step. Sublimation from the film was measured with a Quartz Crystal Microbalance (QCM) while heating at 205°C for 60 seconds to form a cured film. The thickness of the cured film was 100 nm. The results are shown in Table 2 as the sublimed mass (μg) absorbed from the cured film.

[0117] Glass transition temperature of the cured film Each composition in Table 1 was spin-coated at 1500 rpm onto a respective 200 mm bare silicon wafer and then cured at 215° C. for 60 seconds to form a cured coating layer as a 900 nm thick film. The coated wafers were cut into 2 cm×2 cm pieces and placed into the heating cell of an ellipsometer (M2000 ellipsometer, JA Woollam). Differential scanning calorimetry (DSC) was used to measure the glass transition temperature (T ) using 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 (T g ) was calculated from the initial cooling profile using Universal Analysis software. The results were compared with T g The temperatures are shown in Table 2 as (°C).

[0118] [Table 2]

[0119] As can be seen from Table 2, the samples of Examples 1-11 achieved greater solvent resistance as evidenced by less film loss (0.2-0.8 Å film loss) compared to Comparative Examples 1-6 (1.1-1.5 Å film loss). Examples 1-11 were less susceptible to sublimation as the amount of sublimation obtained ranged from 0 to 6 μg. In contrast, heating Comparative Examples 1-6 resulted in amounts of sublimated film ranging from 33 to 48 μg. Additionally, each of Examples 1-11 did not achieve a T of the film above 250° C. g However, in all of Comparative Examples 1 to 6, the T g Therefore, the underlayer compositions of the present invention in Examples 1 to 11 exhibited higher film density.

[0120] Pattern Coating Evaluation The underlayer compositions of Example 1, Comparative Example 1, Example 6, and Comparative Example 3 were spin-coated on a SiO2 substrate having a CD of 1 μm and a trench of 107.7 nm depth, followed by heating at 205 ° C for 1 min. Then, the coating stability and filling of the underlayer composition on the pattern were observed using an optical microscope. Figures 1A-1D show microscopic images of the patterns coated with the underlayer compositions of Example 1, Comparative Example 1, Example 6, and Comparative Example 3, respectively. It was found that the coating films of the compositions of Example 1 and Example 6 were well coated corresponding to the pattern. However, a pullback phenomenon was observed in the coating films of Comparative Example 1 and Comparative Example 3, and the pattern was torn during heat treatment.

[0121] Lithography Performance The underlayer compositions of Example 1 and Comparative Example 1 were spin-coated onto silicon wafers and then baked at 205°C using a TEL Mark 8 wafer coating track machine to produce a bottom antireflective coating. DuPont EPIC™ 2150 photoresist was then spin-coated onto the antireflective coating and baked at 110°C for 60 seconds to yield 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 0.93 NA (0.82 / 0.53 annular settings). The photoresist film was then post-exposure baked at 115°C for 60 seconds and then developed using Shipley MF CD-26 developer (2.38% TMAH) in a standard 60 second single paddle process. The quality of the resist patterns was examined using a scanning electron microscope (SEM) at 60,000x magnification.

[0122] The SEM results in FIG. 2A show a CD of 65 nm for a 160 nm pitch line and space pattern using the antireflective compositions of Example 1 and Comparative Example 1. When Example 1 was used as the bottom antireflective coating, a better collapse margin was observed than when Comparative Example 1 was used. This is due to the higher film T g This is believed to be due to the higher film density of Example 1 as evidenced by . The same trend was observed when Example 6 and Comparative Example 3 were used as the bottom antireflective coating, as shown in FIG. 2B.

[0123] While the disclosure has been described in conjunction with what are presently considered to be practical exemplary embodiments, it is to 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. The present invention may also include the following aspects 1 to 10. [Aspect 1] a first polymer comprising first structural units derived from N-(alkoxymethyl)(meth)acrylamide monomers; a second structural unit comprising an aromatic group, a heterocyclic group, an ester group, an amide group, or a combination thereof, the second structural unit further comprising a crosslinkable group; a thermal acid generator; With solvent; 1. A photoresist underlayer composition comprising: A photoresist underlayer composition, wherein the first polymer comprises the second structural unit, or the photoresist underlayer composition further comprises a second polymer comprising the second structural unit, or a combination thereof. [Aspect 2] the first polymer comprises the first structural unit and the second structural unit; The second structural unit is C6 ~60 The photoresist underlayer composition of embodiment 1 comprising an aryl group and the crosslinkable group. [Aspect 3] 3. The photoresist underlayer composition of any one of the preceding claims, further comprising a second polymer, the second polymer comprising the second structural unit and the crosslinkable group, the second polymer further comprising a third structural unit comprising a substituted cyanurate. [Aspect 4] The photoresist underlayer composition of any one of embodiments 1-3, wherein the N-(alkoxymethyl)(meth)acrylamide monomer is of formula (1): [ka] (In formula (1), R a is hydrogen, fluorine, cyano, or substituted or unsubstituted C 1~10 is alkyl; R 1 is hydrogen or substituted or unsubstituted C 1~10 is alkyl; R 2 and R 3 are each independently hydrogen, substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C 1~30 Heteroalkyl, substituted or unsubstituted C 3~30Cycloalkyl, substituted or unsubstituted C 2~30 Heterocycloalkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 6~30 Aryl, substituted or unsubstituted C 7~30 Aryl alkyl, substituted or unsubstituted C 7~30 Alkylaryl, substituted or unsubstituted C 7~30 Heteroaryl, substituted or unsubstituted C 4~30 Heteroarylalkyl, or substituted or unsubstituted C 4~30 is alkylheteroaryl; R 2 and R 3 each optionally further comprises a divalent linking group as part of their structure; R 2 and R 3 may optionally form a ring via a single bond or a divalent linking group, said ring being substituted or unsubstituted; R 4 is hydrogen, substituted or unsubstituted C 1~20 Alkyl, substituted or unsubstituted C 3~20 Cycloalkyl, substituted or unsubstituted C 2~20 Heterocycloalkyl, substituted or unsubstituted C 6~24 Aryl, substituted or unsubstituted C 7~25 Aryl alkyl, 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 is alkylheteroaryl; R 2 or R 3 one of which is connected to R via a single bond or a divalent linking group 4 and optionally together form a heterocycle, said heterocycle being substituted or unsubstituted. [Aspect 5] R a is hydrogen or unsubstituted C 1~3 is alkyl; R 1is hydrogen or methyl; R 2 and R 3 are each independently hydrogen or a substituted or unsubstituted C 1~10 is alkyl; R 4 is a substituted or unsubstituted C 1~10 Alkyl, substituted or unsubstituted C 3~10 Cycloalkyl, substituted or unsubstituted C 2~10 Heterocycloalkyl, substituted or unsubstituted C 6~14 Aryl, or substituted or unsubstituted C 3~20 The photoresist underlayer composition of embodiment 4, wherein the compound is heteroaryl. [Aspect 6] The photoresist underlayer composition of any one of aspects 2-5, wherein the second structural unit comprises a heterocyclic group that includes a substituted cyanurate structural unit derived from a compound represented by formula (4), formula (5), or a combination thereof: [ka] (In formulas (4) and (5), R 5 and R 6 are each independently hydrogen, substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C 3~30 Cycloalkyl, substituted or unsubstituted C 3~30 Heterocycloalkyl, substituted or unsubstituted C 6~30 Aryl, or substituted or unsubstituted C 3~30 is heteroaryl; R 7 is hydrogen, -COOH, substituted or unsubstituted C 1~30 Alkyl, substituted or unsubstituted C 2~30 Alkenyl, substituted or unsubstituted C 2~30 Alkynyl, substituted or unsubstituted C 2~30 Alkanoyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C1-C 30 Alkylthio, substituted or unsubstituted C1-C30 Alkyl sulfinyl, substituted or unsubstituted C1-C 30 Alkylsulfonyl, substituted or unsubstituted C2-C 30 Alkoxycarbonyl, substituted or unsubstituted C 3~20 Cycloalkenyl, substituted or unsubstituted C 3~20 Heterocycloalkenyl, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C7-C 30 Alkylaryl, substituted or unsubstituted C7-C 30 Aryl alkyl, substituted or unsubstituted C 3~30 Heteroaryl, substituted or unsubstituted C 4~30 Alkylheteroaryl, or substituted or unsubstituted C 4~30 Heteroarylalkyl; Each of X and X′ is independently hydrogen or a substituted or unsubstituted C 1~10 is alkyl; n1, n2, m1, m2, and m3 each independently represent an integer of 1 to 10. [Aspect 7] A layer of the photoresist underlayer composition of any one of embodiments 1-6 disposed on a substrate; and a second layer disposed over the layer of photoresist underlayer composition; and A coated substrate comprising: [Aspect 8] applying a layer of a photoresist underlayer composition of any one of embodiments 1-6 onto a substrate; curing the applied photoresist underlayer composition to form a photoresist underlayer; and forming a photoresist layer over the photoresist underlayer; A pattern forming method comprising the steps of: [Aspect 9] 9. The method of embodiment 8, further comprising forming a silicon-containing layer, an organic antireflective coating layer, or a combination thereof over the photoresist underlayer prior to forming the photoresist layer. [Aspect 10] 10. The method of any one of embodiments 8-9, further comprising patterning the photoresist layer and transferring a pattern from the patterned photoresist layer to the photoresist underlayer and to a layer below the photoresist underlayer.

Claims

1. (i) a first polymer comprising first structural units derived from N-(alkoxymethyl)(meth)acrylamide monomers; (ii) a second structural unit comprising an aromatic group, a heterocyclic group, an ester group, an amide group, or a combination thereof, the second structural unit further comprising a crosslinkable group; (iii) a thermal acid generator; (iv) a solvent; 1. A photoresist underlayer composition comprising: (a) the first polymer comprises the second structural unit, (b) the photoresist underlayer composition further comprises a second polymer comprising the second structural unit, or (c) a combination thereof; The second structural unit is represented by formula (2): 【Chemistry 1】 (In formula (2), R ｂ is hydrogen, fluorine, cyano, or substituted or unsubstituted C １～１０ alkyl, n is 0 or 1, L １ represents a single bond or a divalent linking group; Ar １ is a substituted or unsubstituted C ６～６０ is an aryl group, ２ are independently a single bond or a divalent linking group, each Z is independently a crosslinkable group, and y is an integer from 1 to 3. or The second structural unit is represented by formula (4), formula (5), or a combination thereof: 【Chemistry 2】 (In formulas (4) and (5), R ５ and R ６ are each independently hydrogen, substituted or unsubstituted C １～３０ Alkyl, substituted or unsubstituted C ３～３０ Cycloalkyl, substituted or unsubstituted C ３～３０ Heterocycloalkyl, substituted or unsubstituted C ６～３０ Aryl, or substituted or unsubstituted C ３～３０ is heteroaryl; R ７ is hydrogen, -COOH, substituted or unsubstituted C １～３０ Alkyl, substituted or unsubstituted C 2～３０ Alkenyl, substituted or unsubstituted C ２～３０ Alkynyl, substituted or unsubstituted C ２～３０ Alkanoyl, substituted or unsubstituted C １ ~C ３０ Alkoxy, substituted or unsubstituted C １ ~C ３０ Alkylthio, substituted or unsubstituted C １ ~C ３０ Alkyl sulfinyl, substituted or unsubstituted C １ ~C ３０ Alkylsulfonyl, substituted or unsubstituted C ２ ~C ３０ Alkoxycarbonyl, substituted or unsubstituted C ３～２０ Cycloalkenyl, substituted or unsubstituted C ３～２０ Heterocycloalkenyl, substituted or unsubstituted C ６ ~C ３０ Aryl, substituted or unsubstituted C ７ ~C ３０ Alkylaryl, substituted or unsubstituted C ７ ~C ３０ Aryl alkyl, substituted or unsubstituted C ３～３０ Heteroaryl, substituted or unsubstituted C ４～３０ Alkylheteroaryl, or substituted or unsubstituted C ４～３０ heteroarylalkyl; Each of X and X′ is independently hydrogen or a substituted or unsubstituted C １～１０ is alkyl; n1, n2, m1, m2 and m3 each independently represent an integer from 1 to 10.

1. A photoresist underlayer composition comprising a heterocyclic group containing a substituted cyanurate structural unit derived from a compound represented by:

2. 2. The photoresist underlayer composition of claim 1, wherein the N-(alkoxymethyl)(meth)acrylamide monomer is of formula (1): 【Chemistry 3】 (In formula (1), R ａ is hydrogen, fluorine, cyano, or substituted or unsubstituted C 1～１０ is alkyl; R １ is hydrogen or substituted or unsubstituted C 1～１０ is alkyl; R ２ and R ３ are each independently 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 Heterocycloalkyl, substituted or unsubstituted C ２～30 Alkenyl, substituted or unsubstituted C ６～３０ Aryl, substituted or unsubstituted C ７～３０ Aryl alkyl, 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 alkylheteroaryl; R ２ and R ３ each optionally further comprises a divalent linking group as part of their structure; R ２ and R ３ may optionally form a ring via a single bond or a divalent linking group, said ring being substituted or unsubstituted; R ４ is hydrogen, substituted or unsubstituted C １～２０ Alkyl, substituted or unsubstituted C ３～２０ Cycloalkyl, substituted or unsubstituted C ２～２０ Heterocycloalkyl, substituted or unsubstituted C ６～２４ Aryl, substituted or unsubstituted C ７～２５ Aryl alkyl, 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 alkylheteroaryl; R ２ Or R ３ one of which is connected via a single bond or a divalent linking group to R ４ and optionally together form a heterocycle, said heterocycle being substituted or unsubstituted.

3. applying a layer of the photoresist underlayer composition of claim 1 or 2 onto a substrate; curing the applied photoresist underlayer composition to form a photoresist underlayer; and forming a photoresist layer over the photoresist underlayer; A pattern forming method comprising the steps of:

4. 4. The method of claim 3, further comprising patterning the photoresist layer and transferring a pattern from the patterned photoresist layer to the photoresist underlayer and to a layer below the photoresist underlayer.

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