Photoresist underlayer composition

Abstract

A photoresist underlayer composition is disclosed, comprising: a first material comprising two or more hydroxyl groups; a second material comprising two or more glycidyl groups; an additive comprising a compound having formula (5), a compound having formula (6), or a combination thereof; and a solvent, wherein the structures of formulas (5) and (6) are as disclosed herein.

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. [Previous Technology]

[0002] Photoresist underlayer compositions are used in the semiconductor industry as etching 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 an underlayer with a high carbon content.

[0003] Spin-on carbon (SOC) compositions are used as resist underlayers in the semiconductor industry, serving as etching 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 organic or silicon-containing antireflective coatings and patternable photoresist films are arranged on an underlayer of SOC material with high carbon content.

[0004] An ideal SOC material should possess certain specific characteristics: it should be able to be cast onto a substrate via a spin coating process; it should be heat-set upon heating, exhibiting low degassing and sublimation; it should be soluble in common solvents for good spin bowl compatibility; it should have an appropriate n / k ratio to allow the antireflective coating to function effectively, imparting the low reflectivity necessary for photoresist imaging; and it should possess high thermal stability to prevent damage during subsequent process steps. Furthermore, it is desirable for the underlayer film to adhere sufficiently to the substrate to prevent delamination during immersion, for example, during a standard cleaning process known as SC-1 using a hydrogen peroxide / ammonium hydroxide bath.

[0005] Therefore, there is still a need for novel photoresist underlayer materials that can improve adhesion to the underlying substrate and have good peel resistance and resistance to SC-1 cleaning conditions. [Summary of the Invention]

[0006] A photoresist underlayer composition is provided, comprising: a first material comprising two or more hydroxyl groups; a second material comprising two or more glycidyl groups; an additive, wherein the additive comprises a compound having formula (5), a compound having formula (6), or a combination thereof; and a solvent, (5) and (6), wherein in formulas (5) and (6) In this context, AA represents a single or double bond; X represents a single bond, -C(O)-, an unsubstituted C1 alkyl group, or a hydroxyl-substituted C1 alkyl group; Ar5, Ar6, and Ar7 are each independently C6-60 aryl or C1-60 heteroaryl; wherein Ar5, Ar6, and Ar7 are each independently substituted by at least two groups having the formula -OR2; and, if necessary, wherein Ar5, Ar6, and Ar7 are each independently further substituted; R1 and R2 are each independently hydrogen, a substituted or unsubstituted C1-30 alkyl group, a substituted or unsubstituted C3-30 cycloalkyl group, -C(O)OR5a, or a glycidyl group; Each RA is independently a substituted or unsubstituted C1-10 alkyl, a substituted or unsubstituted C1-10 heteroalkyl, a substituted or unsubstituted C3-10 cycloalkyl, a substituted or unsubstituted C2-10 heterocycloalkyl, a substituted or unsubstituted C6-12 aryl, or a substituted or unsubstituted C1-10 heteroaryl; each R5a is independently hydrogen, a substituted or unsubstituted C1-30 alkyl, a substituted or unsubstituted C1-30 heteroalkyl, a substituted or unsubstituted C3-30 cycloalkyl, a substituted or unsubstituted C2-30 heterocycloalkyl, a substituted or unsubstituted C2-30 alkenyl, a substituted or unsubstituted C6-30 aryl, or a substituted or unsubstituted C6-30 aryl. Substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C1-30 heteroaryl, substituted or unsubstituted C2-30 heteroarylalkyl, or substituted or unsubstituted C2-30 alkylheteroaryl; R3-series hydrogen, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C1-30 heterocycloalkyl, carboxylic acid group or its derivative, or -C(O)OR5b; R5b-series substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 heteroalkyl, substituted or unsubstituted C3-30 cycloalkyl The following are substituted or unsubstituted C2-30 heterocyclic alkyl groups, substituted or unsubstituted C2-30 alkenyl groups, substituted or unsubstituted C6-30 aryl groups, substituted or unsubstituted C7-30 arylalkyl groups, substituted or unsubstituted C7-30 alkylaryl groups, substituted or unsubstituted C1-30 heteroaryl groups, substituted or unsubstituted C2-30 heteroarylalkyl groups, or substituted or unsubstituted C2-30 alkyl heteroaryl groups; a-series integers from 2 to 4; m-series integers from 1 to 6; n-series 0 or 1; p-series integers from 0 to 2; and Y2-series hydrogen, substituted or unsubstituted C6-60 aryl groups, or substituted or unsubstituted C1-60 heteroaryl groups.

[0007] A coated substrate is also provided, comprising: a layer of the above-mentioned photoresist underlayer composition disposed on the substrate; and a photoresist layer disposed on the layer of the photoresist underlayer composition.

[0008] Another method for forming a pattern is provided, the optical method comprising: applying a layer of the above-mentioned photoresist underlayer composition onto a substrate to form a coated underlayer; forming a photoresist layer on the optically coated underlayer; patterning the optically patterned photoresist layer; and transferring the pattern from the optically patterned photoresist layer to the coated underlayer and to a layer below the coated underlayer.

Implementation Method

[0010] Exemplary embodiments, examples of which are shown in this specification, will now be described in detail. In this regard, these exemplary embodiments may take different forms and should not be construed as limited to the description shown herein. Therefore, the exemplary embodiments are described below only by 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.

[0011] 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 such endpoints may be independently combined with each other. The suffix "(s)" is intended to include both the singular and plural forms of the terms it modifies, thereby including at least one of the stated terms. "As needed" or "as needed" means that an event or situation subsequently described may or may not occur, and the description includes examples of the event occurring as well as examples of its non-occurrence. 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.

[0012] 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 interpreted as having an idealized or overly formal meaning unless expressly defined herein.

[0013] As used herein, the term "alkyl group" refers to an organic compound having at least one carbon atom and at least one hydrogen atom, which is substituted by one or more substituents at indicated locations as required; "alkyl" refers to a straight-chain or branched saturated hydrocarbon having a specified number of carbon atoms and a valence of one; "alkyl group" 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-"; and "carboxylic acid group" refers to a group having the formula "-C(O)-OH". "Cycloalkyl" refers to a monovalent group having one or more saturated rings in which all ring members are carbon atoms; "cycloalkyl" refers to a cycloalkyl group having a valence of two; "alkenyl" refers to a straight-chain or branched monovalent hydrocarbon group having at least one carbon-carbon double bond; "alkenyloxy" refers to "alkenyl-O-"; "alkenyl" refers to an alkenyl group having at least a valence of two; "cycloalkenyl" refers to a cycloalkyl group having 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" means, as in the literature, especially in IUPAC. The conventional concept of aromaticity as defined in 19 refers to a monocyclic or polycyclic aromatic ring system comprising carbon atoms in one or more rings, and may, where appropriate, include one or more heteroatoms independently selected from N, O, and S replacing one or more carbon atoms in one or more rings; "aryl" refers to a monovalent, monocyclic or polycyclic aromatic group containing only carbon atoms in one or more aromatic rings, and may include groups having an aromatic ring fused to at least one cycloalkyl or heterocyclic alkyl ring; "arylaryl" refers to an aryl group having a valence of at least 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-".

[0014] The prefix "hetero" means that the compound or group includes at least one member (e.g., 1, 2, 3, or 4 or more heteroatoms) as a heteroatom in place of a carbon atom, wherein each heteroatom is independently selected from N, O, S, Si, or P; "heteroatom-containing group" refers to a substituent that includes at least one heteroatom; "heteroalkyl" refers to an alkyl group having 1 to 4 heteroatoms in place of a carbon atom; "heterocyclic alkyl" refers to a cycloalkyl group having one or more N, O, or S atoms in place of a carbon atom; "extrinsic heterocyclic alkyl" refers to a heterocyclic alkyl group having at least two valences; "heteroaryl" refers to an aryl group having 1 to 3 individual or fused rings having one or more N, O, or S atoms in place of a carbon atom as ring members; and "extrinsic heteroaryl" refers to a heteroaryl group having at least two valences.

[0015] The term "halogen" refers to a monovalent substituent of fluorine (fluorinated), chlorine (chlorinated), bromine (brominated), or iodine (iodinated). The prefix "halogenated" refers to a group that includes one or more of the fluorine, chlorine, bromine, or iodine substituents that replace a hydrogen atom. Combinations of halogen groups (e.g., bromine and fluorine) or only fluorine groups may be present.

[0016] The symbol "*" represents the bonding site (i.e. attachment point) of the repeating unit.

[0017] "Substituted" means that at least one hydrogen atom on a group is replaced by another group, provided that the normal valence of the specified atom is not exceeded. When the substituent is a side oxygen group (i.e., O), then both hydrogen atoms on the carbon atom are replaced. Combinations of substituents or variables are permissible. Exemplary groups that may be present at the "substituted" position include, but are not limited to, nitro (-NO2), cyano (-CN), hydroxyl (-OH), oxy (O), amino (-NH2), mono- or di-(C1-6)alkylamino, alkylyl (such as C2-6 alkylyl such as acetyl), methylamino (-C(O)H), carboxylic acid or its alkali metal or ammonium salt, C2-6 alkyl ester (-C(O)O-alkyl or -OC(O)-alkyl), C7-13 aryl ester (-C(O)O-aryl or -OC(O)-aryl), acetamyl (-C(O)NR2, where R is hydrogen or C1-6 alkyl), methylamino (-CH2C(O)NR2, where R is hydrogen or C1-6 alkyl), halogen, mercapto (-SH), C1-6 alkylthio (-S-alkyl), cyanothio (-SCN). C1-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, C1-6 haloalkyl, C1-9 alkoxy, C1-6 haloalkoxy, C3-12 cycloalkyl, C5-18 cycloalkenyl, C6-12 aryl (e.g., phenyl, biphenyl, naphthyl, etc., each ring system substituted or unsubstituted aromatic), C7-19 arylalkyl having 1 to 3 separate or fused rings and 6 to 18 ring carbon atoms, arylalkoxy having 1 to 3 separate or fused rings and 6 to 18 ring carbon atoms, C7-12 alkylaryl, C4-12 heterocyclic alkyl, C3-12 heteroaryl, C1-6 alkylsulfonyl (-S(O)2-alkyl), C6-12 arylsulfonyl (-S(O)2-aryl), or toluenesulfonyl (CH3C6H4SO2-). When the group is substituted, the indicated number of carbon atoms is the total number of carbon atoms in the group, excluding those with any substituents. For example, the group -CH2CH2CN is a C2 alkyl group substituted with a cyano group.

[0018] As used herein, the terms "polymer" and "polymeric" refer to polymeric materials comprising one or more repeating units, wherein the repeating units may be the same or different from each other. Therefore, the polymers and polymeric materials disclosed in this invention may be referred to herein as "polymers" or "copolymers." It should be further understood that the terms "polymer" and "polymeric" further include oligomers. As used herein, each of the one or more different repeating units is present at least twice in the polymeric material. In other words, a polymeric material comprising one repeating unit comprises a first repeating unit present in two or more amounts, and, for example, a polymeric material comprising two repeating units comprises a first repeating unit present in two or more amounts, and a second repeating unit present in two or more amounts.

[0019] As used herein, unless otherwise defined, "divalent linker" means a divalent linker comprising one or more of the following: -O-, -S-, -Te-, -Se-, -C(O)-, -N(Ra)-, -S(O)-, -S(O)2-, -C(S)-, -C(Te)-, -C(Se)-, substituted or unsubstituted C1-30 alkyl groups, substituted or unsubstituted C3-30 cycloalkyl groups, substituted... Or unsubstituted C1-30 heterocyclic alkyl, substituted or unsubstituted C6-30 heteroaryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C1-30 heteroaryl, substituted or unsubstituted C3-30 heteroarylalkyl, or combinations thereof, wherein Ra is a hydrogen group, substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C1-20 heteroalkyl, substituted or unsubstituted C6-30 aryl, or substituted or unsubstituted C4-30 heteroaryl. More typically, the divalent linking group includes one or more of the following: -O-, -S-, -C(O)-, -N(R')-, -S(O)-, -S(O)2-, substituted or unsubstituted C1-30 alkylene, substituted or unsubstituted C3-30 cycloalkylene, substituted or unsubstituted C1-30 heterocycloalkylene, substituted or unsubstituted C6-30 arylene, substituted or unsubstituted C7-30 arylalkylene, substituted or unsubstituted C1-30 heteroarylene, substituted or unsubstituted C3-30 heteroarylalkylene, or combinations thereof, wherein R' is hydrogen, substituted or unsubstituted C1-20 alkylene, substituted or unsubstituted C1-20 heteroalkylene, substituted or unsubstituted C6-30 arylene, or substituted or unsubstituted C4-30 heteroarylene.

[0020] Organic underlayer films can be used to protect the underlying substrate during various pattern transfer and etching processes. These films are typically cast directly onto an inorganic substrate (i.e., TiN). In such 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. A commonly used processing step is the wet etching process known as SC-1, which involves immersing the substrate in a hydrogen peroxide / ammonium hydroxide bath. Underlayer films that do not adhere sufficiently to the substrate may delaminate during immersion, resulting in exposure and damage to the underlying inorganic substrate.

[0021] This invention provides an additive for a photoresist underlayer formulation that can be applied to a substrate to form a coating. The inventors of this invention have discovered that EUV underlayers and / or BARC formulations containing additives having multiple phenolic hydroxyl groups distributed on different aromatic groups can increase phenol density. The additive of this invention can be used in photoresist underlayer compositions to achieve improved adhesion to the substrate and increase the mechanical properties of the resulting film. The multiple phenolic hydroxyl groups of the additive of this invention increase the adhesion of the underlayer film to the substrate, particularly when the film and substrate are immersed in a hydrogen peroxide / ammonium hydroxide (SC-1) bath.

[0022] According to an aspect of the present invention, a photoresist underlayer composition is provided, comprising: a first material comprising two or more hydroxyl groups; a second material comprising two or more glycidyl groups; an additive comprising a compound having formula (5) as described below, a compound having formula (6) as described below, or a combination thereof; and a solvent.

[0023] The first material contains two or more hydroxyl groups and may be polymeric or non-polymeric. In some aspects, the first material may be a polymer containing two or more hydroxyl groups, for example, having repeating units containing one or more hydroxyl groups, or repeating units containing 1 to 4 hydroxyl groups, preferably repeating units containing 1 to 3 hydroxyl groups, and more typically polymers containing 1 or 2 repeating units. In some aspects, the polymer may have a first repeating unit containing one or more hydroxyl groups and a second repeating unit containing one or more hydroxyl groups, wherein the first repeating unit and the second repeating unit are different.

[0024] For example, the first material for a polymer containing two or more hydroxyl groups may be derived from a monomer containing a polymerizable group and one or more hydroxyl groups. In embodiments, the polymer containing two or more hydroxyl groups may comprise a repeating unit derived from a monomer having formula (1): (1) wherein Ra may be hydrogen, fluorine, cyano, substituted or unsubstituted C1-10 alkyl, or substituted or unsubstituted C1-10 fluoroalkyl. Preferably, Ra is hydrogen, fluorine, or substituted or unsubstituted C1-5 alkyl, typically methyl.

[0025] Q1 is a divalent linking group and is typically selected from one or more of the following: substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C1-30 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted divalent C7-30 arylalkyl, substituted or unsubstituted C1-30 heteroaryl, substituted or unsubstituted divalent C3-30 heteroarylalkyl, -C(O)-O- or -C(O)-NR1a, wherein R1a is a linking group. Hydrogen, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 heteroalkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C1-30 heteroaryl, substituted or unsubstituted C2-30 heteroarylalkyl, or substituted or unsubstituted C2-30 alkyl heteroaryl.

[0026] A-series C6-30 aryl groups substituted with one or more hydroxyl groups or C4-60 heteroaryl groups substituted with one or more hydroxyl groups. If desired, each of the hydroxyl-substituted C6-30 aryl and hydroxyl-substituted C4-60 heteroaryl groups may be further substituted with one or more of the following: substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 heteroalkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C1-30 heterocycloalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C2-30 alkynyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C2-30 heteroaryl The aryl group, substituted or unsubstituted C3-30 heteroarylalkyl, C3-30 alkylheteroaryl, -OR1a, or -NR1bR1c, wherein R1a to R1c are each independently a substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C1-30 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C4-30 heteroaryl, substituted or unsubstituted C5-30 heteroarylalkyl, or substituted or unsubstituted C5-30 alkylheteroaryl.

[0027] Non-limiting examples of monomers having formula (1) include:

[0028] Another exemplary monomer for forming repeating units of polymers comprising two or more hydroxyl groups comprises an N-hydroxyarylmaleimide monomer having formula (2): (2) wherein an Ar1-based hydroxy-substituted C6-60 aryl, a hydroxy-substituted C4-60 heteroaryl, or a combination thereof, is further substituted as required by one or more of the following: substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 heteroalkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C1-30 heterocycloalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C2-30 alkynyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C2-30 Heteroaryl, substituted or unsubstituted C3-30 heteroarylalkyl, C3-30 alkylheteroaryl, -OR2a or -NR2bR2c, wherein R2a to R2c are each independently a substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C1-30 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C4-30 heteroaryl, substituted or unsubstituted C5-30 heteroarylalkyl, or substituted or unsubstituted C5-30 alkylheteroaryl. For Ar1, it may be desirable to include a single hydroxyl group or multiple hydroxyl groups.

[0029] Non-limiting examples of N-hydroxyarylmaleimide monomers having formula (2) include the following:

[0030] In some aspects, the polymer may comprise repeating units containing aromatic or heteroaromatic groups incorporated into the polymer backbone. For example, the polymer may comprise repeating units having formulas (3a) and (3b), or combinations thereof: (3a) and (3b).

[0031] In formulas (3a) and (3b), Ar2 and Ar3 are each independently a substituted or unsubstituted C5-60 aromatic group (substituted with at least one hydroxyl group) or a substituted or unsubstituted C1-60 heteroaromatic group (substituted with at least one hydroxyl group). For example, an aromatic or heteroaromatic group typically contains 1 to 3 hydroxyl groups or 1 or 2 hydroxyl groups. The term "substituted with at least one hydroxyl group" in the context of unsubstituted C5-60 aromatic groups and unsubstituted C1-60 heteroaromatic groups means that the corresponding aromatic or heteroaromatic group is substituted with at least one hydroxyl group and is not further substituted by additional groups or substituents that are not hydroxyl groups.

[0032] The C5-60 aromatic group and the C1-60 heteroaromatic group may further comprise one or more heteroatoms selected from N, O, or S, as desired. It should be understood that one or more heteroatoms of the C5-60 aromatic group and the C1-60 heteroaromatic group as one or more heteroatoms of a heteroatom-containing substituent. It should be understood that one or more heteroatoms of the C1-60 heteroaromatic group in formulas (3a) and (3b) as aromatic ring members replacing carbon atoms (e.g., Ar2 and / or Ar3 may be extended aryl groups).

[0033] The C5-60 aromatic groups and C1-60 heteroaromatic groups can be monocyclic or polycyclic. When the group is polycyclic, one or more ring groups can be fused (e.g., naphthyl), directly linked (e.g., biaryl, biphenyl), bridged by heteroatoms (e.g., triphenylamino or diphenyl ether), or combinations thereof. In embodiments, the polycyclic aromatic group can include a combination of fused and directly linked rings (e.g., binaphthyl).

[0034] In addition to at least one hydroxyl group, and as described above, the substituted C5-60 aromatic groups and substituted C1-60 heteroaromatic groups of formulas (3a) and (3b) are further substituted. Exemplary substituents include, but are not limited to, substituted or unsubstituted C1-30 alkyl groups, substituted or unsubstituted C1-30 haloalkyl groups, substituted or unsubstituted C3-30 cycloalkyl groups, substituted or unsubstituted C1-30 heterocycloalkyl groups, substituted or unsubstituted C2-30 alkenyl groups, substituted or unsubstituted C2-30 alkynyl groups, substituted or unsubstituted C6-30 aryl groups, substituted or unsubstituted C7-30 arylalkyl groups, substituted or unsubstituted C7-30 alkylaryl groups, substituted or unsubstituted C3-30 heteroaryl groups, substituted or unsubstituted C4-30 heteroarylalkyl groups, halogens, -OR31, -SR32, or -NR33R34, wherein R31 is a substituted or unsubstituted C1-30 Alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C3-30 heteroaryl, or substituted or unsubstituted C4-30 heteroarylalkyl; and R32 to R34 are each independently hydrogen, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C3-30 heteroaryl, or substituted or unsubstituted C4-30 heteroarylalkyl.

[0035] In formula (3b), Ar4 is a substituted or unsubstituted C5-60 aromatic group or a substituted or unsubstituted C1-60 heteroaromatic group. The C5-60 aromatic group and the C1-60 heteroaromatic group may further contain one or more heteroatoms selected from N, O, or S, as desired. It should be understood that one or more heteroatoms of the C5-60 aromatic group and the C1-60 heteroaromatic group as one or more heteroatoms of a heteroatom-containing substituent. It should be understood that one or more heteroatoms of the C1-60 heteroaromatic group in formula (3b) as an aromatic ring member replacing a carbon atom (e.g., Ar4 may be an enantiaryl group).

[0036] In formulas (3a) and (3b), Rb, Rc, Rd, and Re are each independently hydrogen, a substituted or unsubstituted C1-30 alkyl, a substituted or unsubstituted C1-30 heteroalkyl, a substituted or unsubstituted C3-30 cycloalkyl, a substituted or unsubstituted C2-30 heterocycloalkyl, a substituted or unsubstituted C2-30 alkenyl, a substituted or unsubstituted C2-30 alkynyl, a substituted or unsubstituted C6-30 aryl, a substituted or unsubstituted C7-30 arylalkyl, a substituted or unsubstituted C7-30 alkylaryl, a substituted or unsubstituted C3-30 heteroaryl, or a substituted or unsubstituted C4-30 heteroarylalkyl. Preferably, Rb, Rc, Rd, and Re are each independently hydrogen or a substituted or unsubstituted C1-10 alkyl, wherein hydrogen is typically the dominant group.

[0037] An exemplary repeating unit having formula (3a) may include one or more of the following:

[0038] An exemplary repeating unit having formula (3b) may include one or more of the following:

[0039] A polymer containing two or more hydroxyl groups may contain repeating units containing one or more hydroxyl groups in amounts ranging from 2 to 100 mol%, typically 10 to 100 mol%, and more typically 50 to 100 mol%, based on the total repeating units of the polymer.

[0040] In other respects, the first material containing two or more hydroxyl groups may be non-polymeric. Exemplary non-polymeric materials containing two or more hydroxyl groups include, but are not limited to, tris(4-hydroxyphenyl)methane, 2,6-bis(4-hydroxy-3,5-dimethylbenzyl)-4-methylphenol, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, α,α,α',α'-tetra(4-hydroxyphenyl)-p-xylene, 2,2-bis[4,4-bis(4-hydroxybenzyl)-cyclohexyl]propane, or combinations thereof.

[0041] The first material of a coating composition may typically be present in an amount of 5 to 95 wt% of the total solids of the coating composition, more typically in an amount of 25 to 75 wt% of the total solids of the coating composition. As used herein, “total solids” of a coating composition means all materials and components of the coating composition other than the solvent carrier.

[0042] The coating composition further comprises a second material containing two or more glycidyl groups. The second material may be a non-polymer material or a polymer material. In an embodiment, the second material containing two or more glycidyl groups may be a non-polymer compound containing two or more glycidyl groups or a polymer containing two or more glycidyl groups.

[0043] A particularly suitable second material may be a polymer comprising repeating units derived from monomers having formula (4): (4) wherein Ra is hydrogen, fluorine, cyano, substituted or unsubstituted C1-10 alkyl, or substituted or unsubstituted C1-10 fluoroalkyl. Preferably, Ra is hydrogen, fluorine, or substituted or unsubstituted C1-5 alkyl, typically methyl.

[0044] In formula (4), L1 is a divalent linking group and is typically selected from substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted divalent C7-30 arylalkyl, substituted or unsubstituted C1-30 heteroaryl, substituted or unsubstituted divalent C2-30 heteroarylalkyl, -O-, -C(O)-, -N(R4a)-, -S-, or -S(O)2-. R4a can be hydrogen, a substituted or unsubstituted C1-20 alkyl, a substituted or unsubstituted C3-20 cycloalkyl, a substituted or unsubstituted C2-20 heterocycloalkyl, a substituted or unsubstituted C6-30 aryl, a substituted or unsubstituted C7-30 arylalkyl, a substituted or unsubstituted C7-30 alkylaryl, a substituted or unsubstituted C1-30 heteroaryl, or a substituted or unsubstituted C2-30 heteroarylalkyl. Y1 can be selected from substituted or unsubstituted C1-30 alkyl or substituted or unsubstituted C6-30 aryl, wherein Y1 contains at least one epoxy group. In some embodiments, L1 and Y1 can be combined to form a carbamate ring containing side chains or fused epoxy groups, if desired.

[0045] An exemplary monomer having formula (4) includes Ra, which is the same as defined in formula (4).

[0046] For example, the second material of the polymer may have one or more repeating units selected from the following: where each n is an integer independently from 1 to 6.

[0047] In some aspects, the second material comprising two or more glycidyl groups may be a non-polymeric material or compound. Exemplary non-polymeric second materials include compounds containing glycidyl groups, which may be selected from 1,1,2,2-tetra(p-hydroxyphenyl)ethane tetraglycidyl ether, glycerol triglycidyl ether, o-dibutylphenyl glycidyl ether, 1,6-bis(2,3-epoxypropoxy)naphthalene, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, triglycidyl isocyanurate, 4,4'-methylenebis(N,N-diglycidylaniline), or combinations thereof.

[0048] The second material of the photoresist underlayer composition may typically be present in an amount of 5 to 99 wt% of the total solids of the photoresist underlayer composition, more typically in an amount of 25 to 75 wt% of the total solids of the photoresist underlayer composition.

[0049] Preferably, when the first material and / or the second material is a polymer, the corresponding polymer may have a weight average molecular weight (Mw) of 1,000 to 10,000,000 g / mol, more typically 2,000 to 10,000 g / mol, and a number average molecular weight (Mn) of 500 to 1,000,000 g / mol. The molecular weight (Mw or Mn) is determined by gel permeation chromatography (GPC) using polystyrene standards as appropriate.

[0050] The photoresist underlayer composition includes an additive, which includes a compound having formula (5), a compound having formula (6), or a combination thereof: (5) (6) wherein AA-type single or double bonds.

[0051] In formula (5), X is a single bond, -C(O)-, an unsubstituted C1 alkyl group, or a hydroxy-substituted C1 alkyl group. It should be understood that "hydroxy-substituted C1 alkyl group" is not further substituted by a group other than hydroxyl. For example, X can be -C(O)- or an unsubstituted C1 alkyl group.

[0052] In formulas (5) and (6), Ar5, Ar6, and Ar7 are each independently a C6-60 aryl or C1-60 heteroaryl, wherein each of Ar5, Ar6, and Ar7 is independently substituted by at least two groups having the formula -OR2. In some respects, each of Ar5, Ar6, and Ar7 may be further independently substituted by groups other than the formula -OR2.

[0053] In formulas (5) and (6), R1 and R2 are each independently hydrogen, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, -C(O)OR5a, or glycidyl, wherein R5a is hydrogen, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 heteroalkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C1-30 heteroaryl, substituted or unsubstituted C2-30 heteroarylalkyl, or substituted or unsubstituted C2-30 alkyl heteroaryl. Typically, R1 and R2 can be hydrogen. a represents integers from 2 to 4, typically 2 or 3. m represents integers from 1 to 6, typically 1 to 3. n represents 0 or 1.

[0054] In formula (5), each RA is independently a substituted or unsubstituted C1-10 alkyl, a substituted or unsubstituted C1-10 heteroalkyl, a substituted or unsubstituted C3-10 cycloalkyl, a substituted or unsubstituted C2-10 heterocycloalkyl, a substituted or unsubstituted C6-12 aryl, or a substituted or unsubstituted C1-10 heteroaryl. Typically, each RA is an unsubstituted C1-6 alkyl. p is an integer from 0 to 2, typically 0 or 1.

[0055] In formula (6), R3 is hydrogen, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C1-30 heterocycloalkyl, carboxylic acid or its derivative, or -C(O)OR5b, wherein R5b is substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 heteroalkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C1-30 heteroaryl, substituted or unsubstituted C2-30 heteroarylalkyl, or substituted or unsubstituted C2-30 alkyl heteroaryl. Typically, R3 can be hydrogen, a carboxylic acid group or a derivative thereof, or -C(O)OR5b, preferably a carboxylic acid group or a derivative thereof. As used herein, "carboxylic acid or a derivative thereof" means carboxylic acid (-COOH) or a carboxylic acid derivative having the formula -COO-M+, wherein M+ is an organic or inorganic group of a cation, such as an alkylammonium cation.

[0056] In formula (5), Y2 is hydrogen, a substituted or unsubstituted C6-60 aryl group, or a substituted or unsubstituted C1-60 heteroaryl group. It should be understood that when n is 0, the oxygen atom is directly bonded to the group Y2 to form a partial structure represented by -O-Y2. In some aspects, n is 0 and Y2 is hydrogen. In other aspects, n is 1 and Y2 is a substituted or unsubstituted C6-60 aryl group, preferably a C6-60 aryl group substituted with two or more hydroxyl groups, such as 2, 3 or 4 hydroxyl groups, typically from 2 to 3 hydroxyl groups, wherein the C6-60 aryl group may be further substituted with one or more non-hydroxyl substituents as needed.

[0057] In some respects, the additive having formula (5) can be a compound represented by formula (5a): (5a)

[0058] In equation (5a), AA, X, R1, R2, Y2, a and n are related to equation (5). The same as defined; each RA is independently a substituted or unsubstituted C1-10 alkyl, substituted or unsubstituted C1-10 heteroalkyl, substituted or unsubstituted C3-10 cycloalkyl, substituted or unsubstituted C2-10 heterocycloalkyl, substituted or unsubstituted C6-12 aryl, or substituted or unsubstituted C1-10 heteroaryl; each RB is independently a substituted or unsubstituted C1-10 alkyl, substituted or unsubstituted C1-10 heteroalkyl, substituted or unsubstituted C3-10 cycloalkyl, substituted or unsubstituted C2-10 heterocycloalkyl, substituted or unsubstituted C6-12 aryl, or substituted or unsubstituted C1-10 heteroaryl; b refers to integers from 2 to 5, preferably from 2 to 4; p refers to integers from 0 to 2, typically 0 or 1; and q refers to integers from 0 to 3, typically 0 or 1.

[0059] For example, a compound represented by formula (5b): (5b) where AA, X, RA, RB, R1, R2, Y2, a, b and n are the same as those defined for formula (5a).

[0060] In some aspects, additives having formula (5), (5a) and / or (5b) may be represented by compounds selected from formula (5c), formula (5d) or combinations thereof: (5c) (5d) wherein R6 is hydrogen, substituted or unsubstituted C1-10 alkyl, substituted or unsubstituted C1-10 heteroalkyl, substituted or unsubstituted C3-10 cycloalkyl, substituted or unsubstituted C2-10 heterocycloalkyl, substituted or unsubstituted C6-12 aryl, or substituted or unsubstituted C1-10 heteroaryl; each Rb is independently a substituted or unsubstituted C1-10 alkyl, substituted or unsubstituted C1-10 heteroalkyl, substituted or unsubstituted C3-10 cycloalkyl, substituted or unsubstituted C2-10 heterocycloalkyl, substituted or unsubstituted C6-12 aryl, substituted or unsubstituted C1-10 heteroaryl, or a group having formula -OR1; R7 is hydrogen, taking The substituted or unsubstituted C1-10 alkyl, substituted or unsubstituted C1-10 heteroalkyl, substituted or unsubstituted C3-10 cycloalkyl, substituted or unsubstituted C2-10 heterocycloalkyl, substituted or unsubstituted C6-12 aryl, or substituted or unsubstituted C1-10 heteroaryl; each Rb is independently a substituted or unsubstituted C1-10 alkyl, substituted or unsubstituted C1-10 heteroalkyl, substituted or unsubstituted C3-10 cycloalkyl, substituted or unsubstituted C2-10 heterocycloalkyl, substituted or unsubstituted C6-12 aryl, or substituted or unsubstituted C1-10 heteroaryl, or a group having the formula -OR2; wherein R1 and R2 are the same as those defined for formula (5).

[0061] In some respects, an additive having formula (5) can be represented by a compound represented by formula (5e): (5e) where a and b are each independently an integer from 2 to 4, typically 2 or 3.

[0062] In some respects, additives having formula (5) can be represented by compounds having formula (5e), ​​formula (5f), or combinations thereof: (5e)(5f) Wherein R6 is hydrogen or a group having the formula -OR1; R7 is hydrogen or a group having the formula -OR2; and R8 is hydrogen, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, -C(O)OR5d, or glycidyl, wherein R5d is hydrogen, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 heteroalkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C1-30 heteroaryl, substituted or unsubstituted C2-30 heteroarylalkyl, or substituted or unsubstituted C2-30 alkyl heteroaryl; wherein R1 and R2 are the same as those for formula (5). The definitions are the same.

[0063] Preferably, the additive having formula (5) can be represented by a compound having formula (5g) where a, b and c are each independently an integer from 2 to 4, typically 2 or 3.

[0064] An exemplary additive having formula (5) may include one or more compounds selected from the following:

[0065] In some respects, the additive having formula (6) can be a compound represented by formula (6a): (6a)

[0066] In equation (6a), R2 and R3 are related as in equation (6) As defined; each R2 is independently the same as or different from each other R2 group; each RA is independently a substituted or unsubstituted C1-10 alkyl, substituted or unsubstituted C1-10 heteroalkyl, substituted or unsubstituted C3-10 cycloalkyl, substituted or unsubstituted C2-10 heterocycloalkyl, substituted or unsubstituted C6-12 aryl, or substituted or unsubstituted C1-10 heteroaryl; each RB is independently a substituted or unsubstituted C1-10 alkyl, substituted or unsubstituted C1-10 heteroalkyl, substituted or unsubstituted C3-10 cycloalkyl, substituted or unsubstituted C2-10 heterocycloalkyl, substituted or unsubstituted C6-12 aryl, or substituted or unsubstituted C1-10 heteroaryl; c and d are each independently an integer from 2 to 5, typically an integer from 2 to 4; p is an integer from 0 to 2, typically 0 or 1; and q is an integer from 0 to 3, typically 0 or 1.

[0067] For example, an additive having formula (6) can be a compound represented by formula (6b): (6b) where R2, R3, c and d are as defined in formula (6a).

[0068] In some aspects, additives having formula (6), (6a) and / or (6b) may be represented by compounds selected from formula (6c), formula (6d) or combinations thereof: (6c) (6d) wherein R8 is hydrogen, substituted or unsubstituted C1-10 alkyl, substituted or unsubstituted C1-10 heteroalkyl, substituted or unsubstituted C3-10 cycloalkyl, substituted or unsubstituted C2-10 heterocycloalkyl, substituted or unsubstituted C6-12 aryl, or substituted or unsubstituted C1-10 heteroaryl; each Rb is independently a substituted or unsubstituted C1-10 alkyl, substituted or unsubstituted C1-10 heteroalkyl, substituted or unsubstituted C3-10 cycloalkyl, substituted or unsubstituted C2-10 heterocycloalkyl, substituted or unsubstituted C6-12 aryl, substituted or unsubstituted C1-10 heteroaryl, or a group having formula -OR2; R9 is hydrogen, substituted Or unsubstituted C1-10 alkyl, substituted or unsubstituted C1-10 heteroalkyl, substituted or unsubstituted C3-10 cycloalkyl, substituted or unsubstituted C2-10 heterocycloalkyl, substituted or unsubstituted C6-12 aryl, or substituted or unsubstituted C1-10 heteroaryl; each Rb is independently a substituted or unsubstituted C1-10 alkyl, substituted or unsubstituted C1-10 heteroalkyl, substituted or unsubstituted C3-10 cycloalkyl, substituted or unsubstituted C2-10 heterocycloalkyl, substituted or unsubstituted C6-12 aryl, substituted or unsubstituted C1-10 heteroaryl, or a group having the formula -OR2; wherein each R2 is independently the same as that defined for formula (6).

[0069] In some respects, an additive having formula (6) can be represented by a compound having formula (6e): (6e) where R3 is the same as defined in formulas (6) and (6b), and c and d are each independently an integer from 2 to 5, typically an integer from 2 to 4.

[0070] An exemplary additive having formula (6) may include one or more compounds selected from the following:

[0071] The additive may be included in the photoresist underbody composition in an amount from 0.1 to 20 wt%, typically 1 to 20 wt%, or 5 to 20 wt%, based on the total solids of the photoresist underbody composition.

[0072] In some aspects, the photoresist underlayer composition may further comprise a polymeric or non-polymeric material containing protected amine groups as part of its structure. The protected amine groups may be derived from primary or secondary amine moieties. Various amine protecting groups are suitable for this invention, provided that such protecting groups are removable (degradable) by heat, acid, or a combination thereof. Preferably, the amine protecting groups are thermally degradable, such as at temperatures from 75°C to 350°C, more preferably from 100°C to 300°C, and even more preferably from 100°C to 250°C.

[0073] Suitable amine protecting groups may include carbamates, such as 9-carbamate, tributyl carbamate, and benzyl carbamate; acetamides, such as acetamide, trifluoroacetamide, and p-toluenesulfonamide; benzylamine; triphenylmethylamine (triphenylmethylamine); and benzylamine. Such amine protecting groups, their formation, and their removal are well known in the art. See, for example, TW Green et al., Protective Groups in Organic Synthesis, Wiley-Interscience, New York, 1999.

[0074] In some aspects, the photoresist underlayer composition may comprise a polymer containing protected amine groups as part of its structure. For example, the material may be a polymer comprising repeating units derived from monomers having formula (7), repeating units derived from monomers having formula (8), or combinations thereof: (7)(8)

[0075] In formulas (7) and (8), Ra can be hydrogen, fluorine, cyano, substituted or unsubstituted C1-10 alkyl, or substituted or unsubstituted C1-10 fluoroalkyl. Preferably, Ra is hydrogen, fluorine, or substituted or unsubstituted C1-5 alkyl, typically methyl.

[0076] In formula (7), A1 is a single bond or a substituted or unsubstituted C1-2 alkyl group, typically methylene.

[0077] In formula (7), R10 to R12 are each independently a substituted or unsubstituted C1-20 alkyl, a substituted or unsubstituted C3-20 cycloalkyl, a substituted or unsubstituted C3-20 heterocycloalkyl, a substituted or unsubstituted C2-20 alkenyl, a substituted or unsubstituted C3-20 cycloalkenyl, a substituted or unsubstituted C3-20 heterocycloalkenyl, a substituted or unsubstituted C6-20 aryl, or a substituted or unsubstituted C4-20 heteroaryl. Any two of R10 to R12 may form a ring together if desired.

[0078] In formula (7), each Rk can independently be a halogen, hydroxyl, carboxylic acid, mercapto, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 heteroalkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C1-30 heteroaryl, substituted or unsubstituted C2-30 heteroarylalkyl, or substituted or unsubstituted C2-30 alkyl heteroaryl, wherein Rk It may further include one or more of -O-, -C(O)-, -NR7a-, -S-, -S(O)-, or -S(O)2-, wherein R7a refers to a substituted or unsubstituted C1-30 alkyl, a substituted or unsubstituted C3-30 cycloalkyl, a substituted or unsubstituted C1-20 heterocycloalkyl, a substituted or unsubstituted C6-30 aryl, a substituted or unsubstituted C7-30 arylalkyl, a substituted or unsubstituted C7-30 alkylaryl, a substituted or unsubstituted C4-30 heteroaryl, a substituted or unsubstituted C5-30 heteroarylalkyl, or a substituted or unsubstituted C5-30 alkylheteraryl. n refers to an integer from 0 to 3, typically 0, 1, or 2.

[0079] In formula (8), L2 is a divalent linking group, and may be selected, for example, from one or more of the following: substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted divalent C7-30 arylalkyl, substituted or unsubstituted C1-30 heteroaryl, or substituted or unsubstituted divalent C2-30 heteroarylalkyl, -O-, -C(O -, -NR8a-, -S-, or -S(O)2-, wherein R8a is hydrogen, substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C3-20 cycloalkyl, substituted or unsubstituted C2-20 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C1-30 heteroaryl, or substituted or unsubstituted C2-30 heteroarylalkyl.

[0080] In formula (8), R13 to R15 are each independently a substituted or unsubstituted C1-20 alkyl, a substituted or unsubstituted C3-20 cycloalkyl, a substituted or unsubstituted C3-20 heterocycloalkyl, a substituted or unsubstituted C2-20 alkenyl, a substituted or unsubstituted C3-20 cycloalkenyl, a substituted or unsubstituted C3-20 heterocycloalkenyl, a substituted or unsubstituted C6-20 aryl, or a substituted or unsubstituted C4-20 heteroaryl. Any two or more of R13 to R15 may form a ring together, if desired.

[0081] In some aspects, the photoresist underlayer composition may comprise a nonpolymer material including protected amine groups. For example, a nonpolymer material having formula (9), a compound having formula (10), or a combination thereof: (9)(10)

[0082] In formulas (9) and (10), R16 to R18 and R21 to R23 may each be independently a substituted or unsubstituted C1-20 alkyl, a substituted or unsubstituted C3-20 cycloalkyl, a substituted or unsubstituted C3-20 heterocycloalkyl, a substituted or unsubstituted C2-20 alkenyl, a substituted or unsubstituted C3-20 cycloalkenyl, a substituted or unsubstituted C3-20 heterocycloalkenyl, a substituted or unsubstituted C6-20 aryl, or a substituted or unsubstituted C4-20 heteroaryl. Any two or more of R16 to R18 may form a ring together if desired. Any two or more of R21 to R23 may form a ring together if desired.

[0083] In formula (9), R19 and R20 are each independently hydrogen, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 heteroalkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C1-30 heteroaryl, substituted or unsubstituted C2-30 heteroarylalkyl, or substituted or unsubstituted C2-30 alkyl heteroaryl.

[0084] In formula (10), A2 is a single bond or a substituted or unsubstituted C1-2 alkyl group, typically methylene. Each R1 can independently be a halogen, hydroxyl, carboxylic acid, mercapto, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 heteroalkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C1-30 heteroaryl, substituted or unsubstituted C2-30 heteroarylalkyl, or substituted or unsubstituted C2-30 alkylheteroaryl, wherein R1 It may further include one or more of -O-, -C(O)-, -NR10a-, -S-, -S(O)-, or -S(O)2-, wherein R10a is a substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C1-20 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C4-30 heteroaryl, substituted or unsubstituted C5-30 heteroarylalkyl, or substituted or unsubstituted C5-30 alkylheteraryl. p can be an integer from 0 to 11. Typically, p can be 0, 1, 2, or 3.

[0085] Exemplary groups having structures represented by -C(R10)(R11)(R12) in formula (7), structures represented by -C(R13)(R14)(R15) in formula (8), structures represented by -C(R16)(R17)(R18) in formula (9), and structures represented by -C(R21)(R22)(R23) in formula (10) may include: wherein Ph-based phenyl groups.

[0086] It should be understood that the polymers described herein include polymers containing two or more hydroxyl groups (e.g., the first polymer), polymers containing two or more glycidyl groups (e.g., the second polymer), and polymers containing repeating units derived from monomers having formula (7) and / or repeating units derived from monomers having formula (8) (e.g., the third and / or fourth polymers), each independently and as needed containing 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%.

[0087] Suitable polymers of the present invention can be readily prepared based on 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 from 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.

[0088] 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, the 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, polynorcampene, polyacetals, polyethylene glycol, polyamide, polyacrylamide, polyphenols, phenolic varnishes, styrene polymers, polyvinyl alcohol, copolymers thereof, and combinations thereof.

[0089] The polymers of the present invention may have a weight average molecular weight (Mw) of 1,000 to 10,000,000 g / mol, more typically 2,000 to 10,000 g / mol, and a number average molecular weight (Mn) of 500 to 1,000,000 g / mol. The molecular weight (Mw or Mn) is determined by gel permeation chromatography (GPC) using suitable polystyrene standards.

[0090] In some aspects, the photoresist underlayer composition may further include one or more curing agents to aid in the curing of the photoresist underlayer composition, for example, after the photoresist underlayer composition has been applied to a surface. The curing agent is any component that causes the photoresist underlayer composition to cure on the substrate surface.

[0091] It may be beneficial for the photoresist underlayer composition to contain acid-generating compounds such as photoacid generators (PAG) and / or thermal acid generators (TAG). A preferred curing agent is a thermal acid generator (TAG).

[0092] Suitable PAGs are known in the field of chemically enhanced photoresists and include, for example: onium salts, such as triphenylstrontium trifluoromethanesulfonate, (p-tributoxyphenyl)diphenylstrontium trifluoromethanesulfonate, tri(p-tributoxyphenyl)strontium trifluoromethanesulfonate, triphenylstrontium 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. Benzene; diazomethane derivatives, such as bis(benzenesulfonyl)diazomethane and 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-hydroxyimines, such as N-hydroxysuccinimide methane sulfonate and N-hydroxysuccinimide trifluoromethane sulfonate; and halogenated trihalomethane compounds, such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-trihalomethane and 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-trihalomethane. One or more of these PAGs may be used.

[0093] TAG compounds are any compounds that release acid upon exposure to heat. 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.

[0094] 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.

[0095] The amount of such curing agent that can be used in the composition of the present invention can be, for example, from more than 0 to 10 wt% of the total solids of the photoresist underlayer composition, and typically from more than 0 to 3 wt%.

[0096] In some aspects, the photoresist underlayer composition does not contain a photoacid generator. Therefore, in these embodiments, the photoresist underlayer composition may be substantially free of PAG compounds and / or polymeric PAGs, for example, free of PAG compounds or polymeric PAGs.

[0097] 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 the functional groups in the photoresist underlayer composition. Exemplary crosslinking agents may include phenolic varnish resins, melamine compounds, guanidine compounds, isocyanate-containing compounds, benzocyclobutene, benzo[a]pyrene, etc., and typically have two or more, more typically three or more, substituents selected from hydroxymethyl, C1-10 alkoxymethyl, and C2-10 acetoxymethyl groups. Examples of suitable crosslinking agents include those shown below:

[0098] Additional crosslinking agents are well known in the art and are commercially available from multiple sources. The amount of such additional crosslinking agents used in the coating compositions of the present invention can, for example, be in the range of greater than 0 to 30 wt% based on the total solids of the coating composition, and more preferably from greater than 0 to 10 wt%.

[0099] The photoresist underbody 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 underbody composition in a small amount, such as from 0.01 to 10 wt% of the total solids based on the photoresist underbody composition.

[0100] 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 organic-loving and water-repellent). Suitable surfactants can be ionic (i.e., anionic, cationic) or nonionic. Other examples of surfactants include silicone surfactants, poly(oxyalkylene) 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, 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., Arlandton, 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.).

[0101] Antioxidants may be added to prevent or minimize the oxidation of organic materials in the underlying composition of the photoresist. 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-tri-butylphenol, 2,6-di-tri-butyl-4-ethylphenol, 2,6-di-tri-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-tri-butylphenol, butyl hydroxyanisole, 2-(1-methylcyclohexyl)-4,6-dimethylphenol, 2,4-dimethyl-6-tri-butylphenol, and 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-trimethylamine, n-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenyl)propionate, octylphenol, aralkyl-substituted phenol, alkylated p-cresol 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-tertiary butylphenol), 2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis-(4-ethyl-6-tertiary butylphenol), 4,4'-methylene-bis-(2,6-di-tertiary butylphenol), 2,2'-methylene-bis-(6-α-methyl-benzyl-p-cresol), methylene-crosslinked polyalkylphenols, 4,4'-extrinyl-bis-(3-methyl-6-tertiary 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-tri-butyl-4-hydroxybenzyl)benzene, tris-(2-methyl-4-hydroxy-5-tri-butylphenyl)butane, and tetra-[methylene-3-(3',5'-di-tri-butyl-4'-hydroxyphenyl)propionate]methane. Suitable antioxidants are commercially available, for example, Irganox™ antioxidants (Ciba Specialty Chemicals Corp.).

[0102] The photoresist underlayer composition contains a solvent. The solvent component may be a single solvent or may include a mixture of two or more different solvents. Suitably, each of the multiple solvents may be miscible with each other. Suitable solvents include, for example, one or more oxyisobutyrates, 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.

[0103] The desired total solids of the photoresist underlayer composition will depend on a variety 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 coating composition, for example from 0.1 to 10 wt%, more typically from 0.11 to 5 wt%.

[0104] 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 other components as desired 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.

[0105] The patterning method of the present invention includes applying a layer of photoresist underlayer composition on a substrate; curing the applied photoresist underlayer composition to form a coated underlayer; and forming a photoresist layer on the coated underlayer. The method may further include the step of exposing the photoresist layer to activation radiation in a patterned manner; and developing the exposed photoresist layer to provide a resist relief image. In some aspects, the method may further include forming a silicon-containing layer, an organic antireflective coating, or a combination thereof on the coated 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, or a combination thereof after developing the exposed photoresist layer and before transferring the pattern to the coated underlayer.

[0106] 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 monochip 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 mm to 300 mm, but wafers with smaller and larger diameters can be suitably used according to the invention. As used herein, the term "semiconductor substrate" includes any substrate having one or more semiconductor layers or structures, which may, as desired, 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.

[0107] 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 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 can 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.

[0108] In some patterning methods of the present invention, before 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) layers, silicon oxide (SiO) layers, or silicon oxynitride (SiON) layers, organic or inorganic BARC layers, or combinations thereof. Such layers, together with the layers of the photoresist underlayer composition of the present invention and the photoresist layers, 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.

[0109] 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 (i.e., the layer of the photoresist underlayer composition) of the present invention can be used alone as a photoresist underlayer, or the coated underlayer (i.e., the layer of the photoresist underlayer composition) of the present invention can be used in combination with other underlayers (including those described herein).

[0110] The photoresist underlayer 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. Spin coating is preferred in the case of semiconductor wafers. In a typical spin coating method, the composition of the present invention is applied to a substrate rotating at a rate of 500 to 4000 rpm for a period of 15 to 90 seconds to obtain a 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 underlayer formed from the photoresist underlayer composition typically has a dried layer thickness of 1 to 50 nanometers (nm), more typically 1 to 10 nm.

[0111] The coated photoresist underlayer composition is soft-baked at a relatively low temperature, as needed, to remove any solvents and other relatively volatile components. Typically, the substrate is baked at a temperature of 150°C or lower, preferably from 60°C to 125°C, and more preferably from 90°C to 115°C. 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.

[0112] 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, another underlayer composition 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 an oven curing can be used to obtain equivalent results. Typically, curing can be performed at a temperature of 150°C or higher, and preferably 150°C to 450°C. More preferably, the curing temperature is 180°C or higher, even more preferably 200°C or higher, and even more preferably from 200°C to 400°C. Curing times are typically from 10 seconds to 10 minutes, preferably from 30 seconds to 5 minutes, more preferably from 45 seconds to 2 minutes, and even more preferably from 45 to 90 seconds. Depending on the requirements, 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.

[0113] After the applied photoresist underlayer composition is cured, a photoresist layer is formed on the coated underlayer. As described above, other intermediate layers may be applied between the coated underlayer and the outer coated 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 coated underlayer prior to forming the photoresist layer.

[0114] A wide variety of photoresists can be suitably used in the methods of the present 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 additional components as needed. Suitable photoresists are well known to those skilled in the art and are commercially available, for example, a variety of photoresist materials from the UV™ and EPIC™ product families of DuPont Electronics & Imaging. The photoresist can be applied to the substrate by known coating techniques (as described above with respect to the underlayer composition), with spin coating being typical. The typical thickness of the photoresist layer is from 10 to 300 nm. Next, the photoresist layer is typically soft-baked to minimize the solvent content in the layer, thereby forming a non-stick coating and improving the adhesion of the layer to the substrate. Soft baking can be performed on a heated plate or in an oven, with a heated plate being typical. Typical soft baking is carried out at temperatures ranging from 70°C to 150°C and for times ranging from 30 to 90 seconds.

[0115] Next, the photoresist layer is exposed to activating radiation via a photomask to create a solubility difference between the exposed and unexposed areas. The exposure of the photoresist composition to radiation that activates the composition, as described herein, indicates that radiation can form a latent image within the photoresist composition. The photomask has optically transparent and optically opaque areas, corresponding to the areas in the resist layer to be exposed and unexposed by the activating radiation, respectively. The exposure wavelength is 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). Preferably, the exposure wavelength is 193 nm or an EUV wavelength. The exposure energy is typically 10 to 100 millijoules per square centimeter (mJ / cm²), depending on, for example, the exposure tool and the composition of the photosensitive component.

[0116] After exposing the photoresist layer, 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 a temperature of 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 equivalent concentration (N) (2.38 wt%) TMAH solution. The developer can be applied using known techniques, such as spin coating or dip coating.

[0117] The pattern of the photoresist layer can be transferred to one or more lower 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, the pattern transfer may include multiple etching steps using different etching gases. After the pattern is transferred to the substrate using conventional techniques, the patterned photoresist layer, the coated underlayer, and other layers as needed in the photolithographic stack can be removed. As needed, one or more layers of the stack can be removed or consumed during the process of pattern transfer to the lower layer and before pattern transfer to the substrate. For example, pattern transfer to one or more of silicon-containing layers, organic antireflective coatings, etc., can occur after the exposed photoresist layer has been developed and before the pattern is transferred to the coated underlayer. The substrate is then further processed according to known methods to form an electronic device.

[0118] A coated substrate is also provided, comprising: a layer of the photoresist underlay composition of the present invention on the substrate; and 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. In other words, curing the photoresist underlay composition forms a cured layer derived from the photoresist underlay composition.

[0119] In other aspects, a layered article is provided, 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.

[0120] The photoresist underlayer, including a coated underlayer prepared from the photoresist underlayer composition of the present invention, exhibits excellent photosensitivity and improved pattern collapse. The preferred photoresist underlayer composition of the present invention can therefore be used in various semiconductor manufacturing processes.

[0121] The inventive concept is further illustrated by the following examples, which are intended to be non-limiting. The compounds and reagents used herein are commercially available, except for the procedures provided below. Examples

[0122] The following shows the structures of the compounds and polymers used in the examples: (A-1)(A-2)(A-3)(A-4)(PHS)(CN)(GMA)(TBG-1)(TBG-2)(DGA) Underlying components

[0123] Table 1 shows the coating compositions of Examples 1 to 17 and Comparative Examples 1 to 3 prepared by mixing the components shown in the indicated amounts. The amounts in parentheses are weight percentages based on the total weight of the coating composition containing Material 1, Material 2, additive compound, thermal alkali generating agent (TBG) compound, and one or more solvents. [Table 1] Material 1 Material 2 additive TBG One or more solvents Example 1 CN (1.7) GMA (2.3) A-1 (0.4) - PGMEA (95.6) Example 2 CN (1.6) DGA (2.0) A-1 (0.4) - PGMEA (48.0) / PGME (48.0) Example 3 CN (1.7) GMA (2.3) A-1 (0.4) TBG-1 (0.4) PGMEA (95.2) Example 4 CN (1.7) GMA (2.3) A-1 (0.4) TBG-2 (0.4) PGMEA (95.2) Example 5 CN (1.7) GMA (2.3) A-2 (0.4) - PGME (95.6) Example 6 CN (1.7) GMA (2.3) A-2 (0.4) TBG-2 (0.4) PGMEA (95.2) Example 7 CN (1.7) GMA (2.3) A-3 (0.4) - PGMEA (95.6) Example 8 CN (1.7) GMA (2.3) A-4 (0.4) - PGMEA (47.8) / PGME (47.8) Example 9 CN (0.9) GMA (1.1) A-4 (2.0) - PGMEA (48.0) / PGME (48.0) Example 10 CN (1.6) DGA (2.0) A-4 (0.4) - PGMEA (48.0) / PGME (48.0) Example 11 CN (1.7) GMA (2.3) A-4 (0.4) TBG-2 (0.4) PGMEA (47.6) / PGME (47.6) Example 12 PHS (2.0) GMA (2.0) A-1 (0.4) - PGMEA (47.8) / PGME (47.8) Example 13 PHS (1.6) DGA (2.0) A-1 (0.4) - PGMEA (48.0) / PGME (48.0) Example 14 PHS (2.0) GMA (2.0) A-2 (0.4) - PGMEA (47.8) / PGME (47.8) Example 15 PHS (2.0) GMA (2.0) A-3 (0.4) - PGMEA (47.8) / PGME (47.8) Example 16 PHS (2.0) GMA (2.0) A-4 (0.4) - PGMEA (47.8) / PGME (47.8) Example 17 PHS (1.6) DGA (2.0) A-4 (0.4) - PGMEA (48.0) / PGME (48.0) Comparison Example 1 CN (1.7) GMA (2.3) - - PGMEA (96.0) Comparison Example 2 CN (4.0) - - - PGMEA (96.0) Comparison Example 3 PHS (2.0) GMA (2.0) - - PGMEA (96.0)

[0124] The following abbreviations are used in Table 1: PHS = Poly(hydroxystyrene) (Mw(GPC) = 4,299 g / mol, Waco Chemicals); CN = Catechol phenolic varnish (Mw(GPC) = 2,290 g / mol); GMA = Poly(glycidyl methacrylate) (Mw(GPC) = 3,922 g / mol); DGA = 4,4'-methylenebis(N,N-diglycidyl aniline); PGMEA = Propylene glycol methyl ether acetate; and PGME = Propylene glycol methyl ether. Solvent resistance peeling assessment

[0125] Each component in Table 1 was filtered through a 0.2 µm PTFE syringe filter and spin-coated onto the corresponding 200-mm bare silicon wafer at 1500 rpm on an ACT-8 Clean Track (Tokyo Electron Co.), and then cured at 215°C for 60 seconds to form a cured coating as a film. The initial film thickness was measured using a Therma-Wave OptiProbe™ measurement tool. Solvent peel resistance was determined by applying the PGMEA remover to each of the corresponding films for 90 seconds, followed by peeling at 105°C and baking for 60 seconds. The thickness of each corresponding film was measured again to determine the amount of film thickness lost by applying the PGMEA remover. Table 2 shows the results of the film thickness measurements before and after contact with the PGMEA remover, where the results are expressed as a percentage (%remaining film) of the film thickness remaining on the wafer after contact with the PGMEA remover. The amount of remaining film after treatment with the PGMEA remover indicates the degree of crosslinking of the cured coating. [Table 2] Remaining membrane (%) Example 1 100.0 Example 2 99.9 Example 3 100.0 Example 4 99.4 Example 5 99.9 Example 6 99.3 Example 7 99.9 Example 8 100.0 Example 9 100.0 Example 10 100.0 Example 11 99.3 Example 12 99.9 Example 13 99.9 Example 14 99.9 Example 15 100.0 Example 16 99.9 Example 17 99.9 Comparison Example 1 99.9 Comparison Example 2 0.0 Comparison Example 3 99.9 Wet stripping assessment

[0126] Each composition in Table 1 was filtered through a 0.2 µm PTFE syringe filter and spin-coated at 1500 rpm onto the corresponding wafer (a silicon wafer coated with a 9 nm thick TiN film prepared by atomic layer deposition), and baked at 215°C for 60 seconds using an ACT-8 Clean Track (Tokyo Electron Ltd.). The film thickness of each coated film after baking was measured (approximately 900 Å) using an OptiProbe™ instrument from Therma-wave Co. The SC-1 wet peelability of the coated samples was then evaluated using a mixture of 30% NH4OH / 30% H2O2 / water with a w / w / w ratio of 1:1:5. The SC-1 mixture was then heated to 50°C. Each coated wafer was immersed in the peeling solution for 2, 5, and 8 minutes. After the specified time, the wafers were removed from the SC-1 mixture and rinsed with deionized water. The membrane quality of the samples was provided based on the immersion times (2, 5, and 8 minutes) in Table 3, with visual inspection used to evaluate the samples as described below. [Table 3] SC-1 resistance (2 minutes) SC-1 resistance (5 minutes) SC-1 resistance (8 minutes) Example 1 A A A Example 2 A A B Example 3 A A A Example 4 A A A Example 5 A B B Example 6 A B B Example 7 A A B Example 8 A A A Example 9 A A A Example 10 A A A Example 11 A A A Example 12 A C - Example 13 A A A Example 14 A C - Example 15 A C - Example 16 A A A Example 17 A A A Comparison Example 1 A C - Comparison Example 2 C - - Comparison Example 3 B C -

[0127] For the assessment in Table 3, the following abbreviations were used: A: pristine membrane, B: partially degraded membrane, C: completely delaminated membrane. Each sample was assessed by visual inspection using the eye.

[0128] As can be seen from Table 3, compared with the samples prepared by the comparative examples and without additives, the samples of Examples 1 to 17 containing the corresponding additive compounds began to separate at a later time in the SC-1 bath. After 2, 5, and 8 minutes in the SC-1 bath, the samples of Examples 1, 3, 4, 8-11, 13, 16, and 17 remained in their original state. The samples of Examples 5 and 6 showed only partial film separation after 5 minutes in the SC-1 bath, while the sample of Comparative Example 1 completely separated after 5 minutes in the SC-1 bath. Furthermore, Examples 12, 14, and 15 remained in their original state after 2 minutes in the SC-1 bath, while Comparative Example 3 partially separated after 2 minutes in the SC-1 bath. Evaluation of the underlying pattern profile after SC-1

[0129] Samples from Example 1 and Comparative Example 1 were spin-coated onto corresponding wafers (silicon wafers coated with a 9 nm thick TiN film prepared by atomic layer deposition) at 1500 rpm and then cured at 215°C for 60 seconds to form a 900 Å thick film. Each coated wafer was etched with O2 for 25 seconds. After the etch-back process, the samples were immersed in a mixture of 30% NH4OH / 30% H2O2 / water with a w / w / w ratio of 1:1:5. The SC-1 mixture was then heated to 50°C for five minutes. XSEM images of each sample were obtained after both the O2 etching and SC-1 treatment. The results are shown in Table 4, where the film profiles are described as upright or collapsed. [Table 4] Membrane shape (After O2 etching) Membrane shape (After SC-1 processing) Example 1 upright upright Comparison Example 1 upright Collapsed

[0130] As shown in Table 4, the sample of Example 1 maintained its film shape after O2 etching and SC-1 treatment. In contrast, the sample of Comparative Example 1 maintained its film shape only after O2 etching, while the film profile collapsed after SC-1 treatment. These results indicate that the photoresist underlayer composition of the present invention can provide improved resilience to the damaging effects of SC-1 treatment.

[0131] Although this disclosure has been described in conjunction with exemplary embodiments which are 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. [Simplified Explanation of the Diagram]

[0009] None [Biomaterial Storage]

[0133] None

Claims

1. A photoresist underlayer composition comprising: a first material comprising two or more hydroxyl groups; a second material comprising two or more glycidyl groups; an additive, wherein the additive comprises a compound having formula (5), a compound having formula (6), or a combination thereof; and a solvent, 1. Among them, In formulas (5) and (6), AA represents a single or double bond; X is a single bond, -C(O)-, an unsubstituted C1 alkyl group, or a hydroxyl-substituted C1 alkyl group; Ar5, Ar6, and Ar7 are each independently a C6-60 aryl or C1-60 heteroaryl group; wherein Ar5, Ar6, and Ar7 are each independently substituted by at least two groups having the formula -OR2; and, if necessary, wherein Ar5, Ar6, and Ar7 are each independently further substituted; R1 and R2 are each independently hydrogen, a substituted or unsubstituted C1-30 alkyl group, a substituted or unsubstituted C3-30 cycloalkyl group, -C(O)OR5a, Or glycidyl; each RA is independently a substituted or unsubstituted C1-10 alkyl, substituted or unsubstituted C1-10 heteroalkyl, substituted or unsubstituted C3-10 cycloalkyl, substituted or unsubstituted C2-10 heterocycloalkyl, substituted or unsubstituted C6-12 aryl, or substituted or unsubstituted C1-10 heteroaryl; each R5a is independently hydrogen, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 heteroalkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C6-3 0 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C1-30 heteroaryl, substituted or unsubstituted C2-30 heteroarylalkyl, or substituted or unsubstituted C2-30 alkylheteroaryl; R3 hydrogen, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C1-30 heterocycloalkyl, carboxylic acid group or its derivative, or -C(O)OR5b; R5b substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 heteroalkyl, substituted or unsubstituted C3-30 cycloalkyl Alkyl, substituted or unsubstituted C2-30 heterocyclic alkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C1-30 heteroaryl, substituted or unsubstituted C2-30 heteroarylalkyl, or substituted or unsubstituted C2-30 alkyl heteroaryl; a-series integers from 2 to 4; m-series integers from 1 to 6; n-series 0 or 1; p-series integers from 0 to 2; and Y2-series hydrogen, substituted or unsubstituted C6-60 aryl, or substituted or unsubstituted C1-60 heteroaryl.

2. The photoresist underlayer composition as described in claim 1, wherein, The additive contains a compound represented by formula (5a):

2. Among them, In formula (5a), AA represents a single or double bond; X is a single bond, -C(O)-, an unsubstituted C1 alkyl group, or a hydroxylated C1 alkyl group; R1 and R2 are each independently hydrogen, a substituted or unsubstituted C1-30 alkyl group, a substituted or unsubstituted C3-30 cycloalkyl group, -C(O)OR5a, or a glycidyl group; each RA is independently a substituted or unsubstituted C1-10 alkyl group, a substituted or unsubstituted C1-10 heteroalkyl group, or a substituted or unsubstituted C1-10 heteroalkyl group. Alkyl, substituted or unsubstituted C3-10 cycloalkyl, substituted or unsubstituted C2-10 heterocyclic alkyl, substituted or unsubstituted C6-12 aryl, or substituted or unsubstituted C1-10 heteroaryl; each RB is independently a substituted or unsubstituted C1-10 alkyl, substituted or unsubstituted C1-10 heteroalkyl, substituted or unsubstituted C3-10 cycloalkyl, substituted or unsubstituted C2-10 heterocyclic alkyl, substituted or unsubstituted C6- 12 aryl, or substituted or unsubstituted C1-10 heteroaryl; each R5a is independently hydrogen, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 heteroalkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted The following are substituted C7-30 alkyl aryl groups, substituted or unsubstituted C1-30 heteroaryl groups, substituted or unsubstituted C2-30 heteroarylalkyl groups, or substituted or unsubstituted C2-30 alkyl heteroaryl groups; a-series integers from 2 to 4; b-series integers from 2 to 5; n-series 0 or 1; p-series integers from 0 to 2; q-series integers from 0 to 3; and Y2-series hydrogen, substituted or unsubstituted C6-60 aryl groups, or substituted or unsubstituted C1-60 heteroaryl groups.

3. The photoresist underlayer composition as described in claim 1, wherein, The additive contains a compound represented by formula (6a):

3. Among them, In formula (6a), each R2 is independently hydrogen, a substituted or unsubstituted C1-30 alkyl, a substituted or unsubstituted C3-30 cycloalkyl, -C(O)R5a, or glycidyl; each RA is independently a substituted or unsubstituted C1-10 alkyl, a substituted or unsubstituted C1-10 heteroalkyl, a substituted or unsubstituted C3-10 cycloalkyl, a substituted or unsubstituted C2-10 heterocycloalkyl, a substituted or unsubstituted C6-12 aryl, or a substituted or unsubstituted C1-10 heteroaryl; each RB is independently a substituted or unsubstituted C1-10 alkyl. Substituted or unsubstituted C1-10 heteroalkyl, substituted or unsubstituted C3-10 cycloalkyl, substituted or unsubstituted C2-10 heterocycloalkyl, substituted or unsubstituted C6-12 aryl, or substituted or unsubstituted C1-10 heteroaryl; each R5a is independently hydrogen, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 heteroalkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted Substituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C1-30 heteroaryl, substituted or unsubstituted C2-30 heteroarylalkyl, or substituted or unsubstituted C2-30 alkylheteroaryl; R3-series hydrogen, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C1-30 heterocycloalkyl, carboxylic acid group or its derivative, or -C(O)OR5b; R5b-series substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 heteroalkyl, Substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C1-30 heteroaryl, substituted or unsubstituted C2-30 heteroarylalkyl, or substituted or unsubstituted C2-30 alkyl heteroaryl; c series integers from 2 to 5; d series integers from 2 to 5; p series integers from 0 to 2; and q series integers from 0 to 3.

4. The photoresist underlayer composition as described in claim 1, further comprising a third polymer comprising repeating units derived from monomers having formulas (7), (8) or combinations thereof:

4. Wherein, in formulas (7) and (8), each Ra is independently hydrogen, fluorine, substituted or unsubstituted C1-5 alkyl, or substituted or unsubstituted C1-5 fluoroalkyl; A is a single bond or a substituted or unsubstituted C1-2 alkyl group; each Rk is independently halogen, hydroxyl, carboxyl, mercapto, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 heteroalkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C2-30 alkenyl, Substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C1-30 heteroaryl, substituted or unsubstituted C2-30 heteroarylalkyl, or substituted or unsubstituted C2-30 alkylheteroaryl, wherein Rk may further comprise one or more of -O-, -C(O)-, -NR7a-, -S-, -S(O)-, or -S(O)2-, wherein R7a is a substituted or unsubstituted C1-30 Alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C1-20 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C4-30 heteroaryl, substituted or unsubstituted C5-30 heteroarylalkyl, or substituted or unsubstituted C5-30 alkylheteroaryl; n is an integer from 0 to 3; L2 is a divalent linker; R10 to R15 are each independently substituted or unsubstituted. The C1-20 alkyl, substituted or unsubstituted C3-20 cycloalkyl, substituted or unsubstituted C3-20 heterocycloalkyl, substituted or unsubstituted C2-20 alkenyl, substituted or unsubstituted C3-20 cycloalkenyl, substituted or unsubstituted C3-20 heterocycloalkenyl, substituted or unsubstituted C6-20 aryl, or substituted or unsubstituted C4-20 heteroaryl; if desired, any two or more of R10 to R12 together form a ring; and if desired, any two or more of R13 to R15 together form a ring.

5. The photoresist underlayer composition as described in claim 1, further comprising a compound having formula (9), formula (10), or a combination thereof:

5. Among them, In formulas (9) and (10), R16 to R18 and R21 to R23 are each independently a substituted or unsubstituted C1-20 alkyl, a substituted or unsubstituted C3-20 cycloalkyl, a substituted or unsubstituted C3-20 heterocycloalkyl, a substituted or unsubstituted C2-20 alkenyl, a substituted or unsubstituted C3-20 cycloalkenyl, a substituted or unsubstituted C3-20 heterocycloalkenyl, a substituted or unsubstituted C6-20 aryl, or a substituted or unsubstituted C4-20 heteroaryl; any two or more of R16 to R18 may, as desired, form a ring together, and any two or more of R21 to R23 may, as desired, form a ring together. Cyclic formation; R19 and R20 are each independently hydrogen, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 heteroalkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C1-30 heteroaryl, substituted or unsubstituted C2-30 heteroarylalkyl, or substituted or unsubstituted C2-30 alkylheteroaryl; A2 series single bond or substituted or unsubstituted C1-2 Alkyl groups; each R1 is independently a halogen, hydroxyl, carboxylic acid, mercapto, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 heteroalkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C2-30 heterocycloalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C1-30 heteroaryl, substituted or unsubstituted C2-30 heteroarylalkyl, or substituted or unsubstituted C2-30 alkyl heteroaryl; wherein R1 is further encapsulated as needed. Contains one or more of -O-, -C(O)-, -NR10a-, -S-, -S(O)-, or -S(O)2-, wherein R10a is a substituted or unsubstituted C1-30 alkyl, a substituted or unsubstituted C3-30 cycloalkyl, a substituted or unsubstituted C1-20 heterocycloalkyl, a substituted or unsubstituted C6-30 aryl, a substituted or unsubstituted C7-30 arylalkyl, a substituted or unsubstituted C7-30 alkylaryl, a substituted or unsubstituted C4-30 heteroaryl, a substituted or unsubstituted C5-30 heteroarylalkyl, or a substituted or unsubstituted C5-30 alkyl heteroaryl; and p is an integer from 0 to 11.

6. The photoresist underlayer composition as described in claim 1, wherein, The additive contains one or more of the following compounds:

7. The photoresist underlayer composition as described in claim 1, wherein, The first material comprises a first polymer, wherein the first polymer contains the two or more hydroxyl groups; and the second material is a second polymer, wherein the second polymer contains the two or more glycidyl groups.

8. A coated substrate comprising: A layer of photoresist underlayer composition as described in any one of claims 1 to 7 disposed on a substrate; And the photoresist layer disposed on the layer of the photoresist underlayer composition.

9. 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 7 is applied to the substrate to form a coated underlayer; A photoresist layer is formed on the coated substrate; the photoresist layer is patterned; and the pattern is transferred from the patterned photoresist layer to the coated substrate and to a layer below the coated substrate.

10. The method as described in claim 9, further comprising: Prior to forming the photoresist layer, a silicon-containing layer, an organic antireflective coating, or a combination thereof is formed on the coated substrate; And after the exposed photoresist layer has been developed and before the pattern has been transferred to the coated underlayer, the pattern has been transferred to the silicon-containing layer, the organic antireflective coating, or a combination thereof.