Coating composition for photoresist primer

Abstract

A coating composition for use as a photoresist underlayer. A photoresist underlayer composition is provided, comprising a polymer and a crosslinking agent, said polymer comprising repeating units having formula (1):

Description

[0001] This invention patent application is a divisional application of the invention patent application with application number 202110934022.5, application date August 13, 2021, entitled "Coating Composition for Photoresist Underlayer". Technical Field

[0002] This invention relates generally to the field of manufacturing electronic devices, and more specifically to the field of materials used in semiconductor manufacturing. Background Technology

[0003] Photoresist underlayer compositions are used in the semiconductor industry as etch masks for photolithography in advanced technology nodes of integrated circuit manufacturing. These compositions are typically used in three-layer and four-layer photoresist integration schemes, in which an organic or silicon-containing antireflective coating and a patternable photoresist film are arranged on an underlayer with a high carbon content.

[0004] An ideal photoresist underlayer should possess certain specific properties: it should be cast onto the substrate via spin coating, it should be thermosetting upon heating, it should have low degassing and sublimation, it should be soluble in common solvents to ensure good spin bowl compatibility, it should have suitable n&k values ​​to work with antireflective coatings to impart the low reflectivity required for photoresist imaging, and it should have high thermal stability to prevent damage during subsequent processing steps. In addition to these requirements, an ideal photoresist underlayer must provide a planar film upon spin coating and thermosetting on the substrate, with a morphology and sufficient dry etch selectivity for the silicon-containing layers above and below the photoresist underlayer to precisely transfer the light pattern into the final substrate.

[0005] Crosslinkable phenolic varnish resins have been used in undercoat applications. Phenolic varnish resins are condensation products of one or more activated aromatic compounds and another monomer selected from aliphatic or aromatic carbonyl compounds, benzyl ethers, benzyl alcohols, or benzyl halides. The most widely studied phenolic varnish resins are condensation products of activated aromatic derivatives and formaldehyde-type or aromatic aldehyde comonomers. These resins have been used extensively in various photolithographic compositions. A similar class of resins is a condensation product between an activated aromatic derivative and an acyl chloride, wherein the resulting ketone is reduced to benzyl alcohol in a second step to obtain a highly soluble crosslinkable material.

[0006] New photoresist underlayers are still needed that can provide properties such as improved solubility, lower curing temperature, high thermal stability, solvent resistance after curing, improved gap filling, and improved planarization. Summary of the Invention

[0007] A photoresist underlayer composition is provided, comprising a polymer having repeating units having formula (1):

[0008]

[0009] Where Ar is a monocyclic or polycyclic C. 5-60 An aromatic group, wherein the aromatic group comprises one or more aromatic cyclic heteroatoms, substituents comprising heteroatoms, or combinations thereof; R 1 It is hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl; and R 2 Is it substituted or unsubstituted C? 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl, wherein R 1 and R 2 They can be chosen to form a ring together.

[0010] A method for forming a pattern is also provided, the method comprising: (a) applying a layer of photoresist underlay composition on a substrate; (b) curing the applied photoresist underlay composition to form a photoresist underlay; and (c) forming a photoresist layer on the photoresist underlay. Detailed Implementation

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

[0012] As used herein, the terms “a” 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 indicated, “or” means “and / or”. The full scope disclosed herein includes endpoints, and these endpoints may be independently combined with each other. The suffix “(s)” is intended to include both the singular and plural forms of the term it modifies, thereby including at least one of the terms. “Optional” or “optionally” 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 said other element or an intervening element that may exist therein. Conversely, when an element is referred to as being “directly on” another element, no intervening element is present. It should be understood that the components, elements, limitations and / or features of the described aspects can be combined in any suitable manner in all aspects.

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

[0014] As used herein, the term "alkyl group" refers to an organic compound having at least one carbon atom and at least one hydrogen atom, optionally substituted by one or more substituents at the indicated location; "alkyl" refers to a straight-chain or branched saturated hydrocarbon having a specified number of carbon atoms and a valence of 1; "alkylene" refers to an alkyl group having a valence of 2; "hydroxyalkyl" refers to an alkyl group substituted with at least one hydroxyl group (-OH); "alkoxy" refers to "alkyl-O-"; "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; "cycloalkylene" refers to a cycloalkyl group having a valence of 2; "alkenyl" refers to a straight-chain or branched monovalent hydrocarbon group having at least one carbon-carbon double bond; "alkenyloxy" refers to "alkenyl-O-"; "alkenylene" refers to an alkenyl group having a valence of at least 2; "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" is used as in the literature, especially IUPAC. The conventional concept of aromaticity as defined in 19 refers to a monocyclic or polycyclic aromatic ring system containing a carbon atom in one or more rings, and optionally may contain 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 a carbon atom in one or more aromatic rings, and may contain a group having an aromatic ring fused to at least one cycloalkyl or heterocyclic alkyl ring; “arylene” refers to an aryl group having a valence of at least 2; “alkylaryl” refers to an aryl group that has been substituted with an alkyl group; “arylalkyl” refers to an alkyl group that has been substituted with an aryl group; “aryloxy” refers to “aryl-O-”; and “arylthio” refers to “aryl-S-”.

[0015] The prefix "hetero" means that the compound or group contains 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 of the one or more heteroatoms is independently selected from N, O, S, Si, or P; "heteroatom-containing group" means a substituent containing at least one heteroatom; "heteroalkyl" means an alkyl group having 1 to 4 heteroatoms in place of a carbon atom; "heterocyclic alkyl" means a cycloalkyl group having one or more N, O, or S atoms in place of a carbon atom; "heterocyclic alkyl" means a heterocyclic alkyl group having a valence of at least 2; "heteroaryl" means an aryl group having 1 to 3 separate rings or fused rings having one or more N, O, or S atoms in place of a carbon atom as ring members; and "heteroaryl" means a heteroaryl group having a valence of at least 2.

[0016] The term "halogen" refers to a monovalent substituent of fluorine (fluorinated), chlorine (chloroinated), bromine (brominated), or iodine (iodinated). The prefix "halogenated" indicates a group containing 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.

[0017] The symbol “*” represents the binding site (i.e., attachment site) of the repeating unit.

[0018] "Substituted" means that at least one hydrogen atom on the stated group is replaced by another group, provided that the valence of the specified atom is not exceeded. When the substituent is oxo (i.e., =O), both hydrogen atoms on the carbon atom are replaced. Combinations of substituents or variables are permitted. Exemplary groups that may exist at the "substituted" position include, but are not limited to, nitro (-NO2), cyano (-CN), hydroxyl (-OH), oxo (=O), amino (-NH2), mono- or di-(C 1-6 )alkylamino, alkanoyl (such as C 2-6 Alkyl groups such as acyl groups, formyl groups (-C(=O)H), carboxylic acids or their alkali metal or ammonium salts, C 2-6 Alkyl esters (-C(=O)O-alkyl or -OC(=O)-alkyl), C 7-13 Aryl esters (-C(=O)O-aryl or -OC(=O)-aryl), amide groups (-C(=O)NR2, where R is hydrogen or C... 1-6 Alkyl), formamido (-CH2C(=O)NR2, where R is hydrogen or C 1-6 Alkyl groups, halogens, mercapto groups (-SH), C 1-6 Alkylthio (-S-alkyl), cyanothio (-SCN), C 1-6 Alkyl, C 2-6 alkenyl, C 2-6 alkynyl group, C 1-6 Haloalkyl, C 1-9 Alkoxy, C 1-6 Halogenated alkoxy groups, C 3-12 cycloalkyl, C 5-18 Cycloalkenyl, C having at least one aromatic ring 6-12 Aryl groups (e.g., phenyl, biphenyl, naphthyl, etc., each ring being substituted or unsubstituted aromatics), having 1 to 3 separate or fused rings and 6 to 18 ring carbon atoms. 7-19 Arylalkyl, arylalkoxy having 1 to 3 separate or fused rings and 6 to 18 ring carbon atoms, C 7-12 alkylaryl, C 4-12 Heterocyclic alkyl, C 3-12 heteroaryl, C 1-6 alkylsulfonyl (-S(=O)2-alkyl), C 6-12Arylsulfonyl (-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.

[0019] As noted above, there is still a need for new photoresist underlayers that can provide properties such as improved solubility, lower curing temperature, high thermal stability, solvent resistance after curing, improved gap filling, and improved planarization.

[0020] Incorporating carboxylic acid ester groups into the polymer units of a photoresist underlayer material can significantly improve material solubility and lower the crosslinking initiation temperature for curing without significantly impairing etch resistance and reflectivity parameters. Specifically, the compositions of the present invention disclosed herein achieve excellent planarization properties and have etch rates that can be tuned based on the polymer structure. Photoresist underlayer compositions comprising carboxylic acid ester-containing polymers can be crosslinked and / or can be crosslinkable, preferably wherein the polymer is crosslinkable in the absence of irradiation. For example, the photoresist underlayer compositions of the present invention may contain a thermal acid generator and preferably do not contain a photoacid generator. Crosslinking can be carried out via a crosslinking agent or through self-crosslinking.

[0021] According to one embodiment, the photoresist underlayer composition comprises a polymer having repeating units of formula (1):

[0022]

[0023] In equation (1), Ar is a monocyclic or polycyclic C. 5-60 An aromatic group, wherein the aromatic group comprises one or more aromatic cyclic heteroatoms, substituents comprising heteroatoms, or combinations thereof. For convenience, the monocyclic or polycyclic C 5-60 Aromatic groups may be referred to herein as "Ar groups". Typically, one or more heteroatoms can be independently selected from N, O, or S. When C 5-60 When the aromatic group is polycyclic, the one or more cyclic groups can be fused (such as naphthyl), directly linked (such as biaryl, biphenyl, etc.), and / or bridged by heteroatoms (such as triphenylamino or diphenylene ether). In one embodiment, the polycyclic aromatic group may comprise a combination of fused and directly linked rings (such as binaphthyl). It should be understood that monocyclic or polycyclic C 5-60 One or more heteroatoms of an aromatic group may exist as an aromatic ring member replacing a carbon atom (e.g., a heteroaryl group), as one or more heteroatoms of a heteroatom-containing substituent (e.g., a hydroxyl substituent), or a combination thereof.

[0024] Single or multiple ring C 5-60 The aromatic group can be substituted or unsubstituted. Exemplary substituents include, but are not limited to, substituted or unsubstituted C groups. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne group, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 7-30 Alkyl aryl, substituted or unsubstituted C 3-30 heteroaryl, substituted or unsubstituted C 4-30 Heteroarylalkyl, halogen, -OR 11 、-SR 12 , or -NR 13 R 14 , where R 11 To R 14 Each is independently hydrogen, substituted or unsubstituted C. 1-30 Alkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl.

[0025] In one embodiment, single-ring or multi-ring C 5-60 The aromatic group can be a monocyclic or polycyclic C 6-60 arylene or monocyclic or polycyclic C 5-60 Hybrid aryl. When C 5-60 The aromatic group is a monocyclic or polycyclic carbon. 6-60 In the aryl form, at least one hydrogen atom is replaced by a heteroatom-containing substituent as detailed above, such as -OR 11 、-SR 12 , or -NR 13 R 14 , where R 11 To R 14 Each is independently a hydrogen, substituted or unsubstituted C. 1-30 Alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C2-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 Heteroaryl alkyl. Preferably, Ar is a polycyclic C. 10-60 aryl or polycyclic C 7-60 Heteroaryl groups. Exemplary Ar groups include, but are not limited to, substituted or unsubstituted carbazole dimethyl, substituted phenylene, substituted biphenylene, substituted naphthylene, and substituted pyrene.

[0026] In one embodiment, single-ring or multi-ring C 5-60 Aromatic groups can be -OR 11 、-SR 12 , or -NR 13 R 14 Replacement of monocyclic or polycyclic C 6-60 Alpha-aryl, of which R 11 To R 14 Each is independently a hydrogen, substituted or unsubstituted C. 1-30 Alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl groups. For example, monocyclic or polycyclic C. 5-60 The aromatic group can be a monocyclic or polycyclic C that has been substituted with a hydroxyl group. 6-60 Alpha-aryl.

[0027] It should be understood that when "single-ring or multi-ring C" 6-60 When the "aryl" group is polycyclic, the number of carbon atoms is sufficient for the group to be chemically feasible. For example, "monocyclic or polycyclic C..." 6-60 "Aromatic" can refer to "monocyclic C 6-60 aryl or polycyclic C 10-60 "Asyl"; or for example, "monocyclic C" 6-30 aryl or polycyclic C 12-60 "Aspartic acid".

[0028] It should be understood that when "single-ring or multi-ring C" 5-60 When a "heteroaryl" group is polycyclic, the number of carbon atoms is sufficient for the group to be chemically feasible. For example, "monocyclic or polycyclic C..." 5-60 "Hybrid aryl" can refer to "monocyclic C 5-60 Heteroaryl or polycyclic C10-60 "Hybrid aryl"; or for example, "monocyclic C" 5-30 Heteroaryl or polycyclic C 12-60 "hybrid aryl".

[0029] In equation (1), R 1 It is hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl. Preferably, R 1 It is hydrogen, C 1-10 Alkyl, C 1-10 fluoroalkyl, C 6-12 Aryl, or C 6-12 Fluoroaryl groups, in which hydrogen is a typical component.

[0030] In equation (1), R 2 Is it substituted or unsubstituted C? 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl. Preferably, R 2 Is it substituted or unsubstituted C? 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted C 2-20 Heterocyclic alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 Alkyne, substituted or unsubstituted C6-24 aryl, or substituted or unsubstituted C 5-20 Mixed aromatic compounds.

[0031] Optional, R 1 and R 2 They can form a ring together.

[0032] In one embodiment, the Ar group can be a group having formula (2):

[0033]

[0034] A1, A2, and A3 may or may not exist, and each independently represents one to three fused aromatic rings.

[0035] In equation (2), R 3 and R 4 Each is independently either substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl, halogen, -OR 21 、-SR 22 , or -NR 23 R 24 The premise is R 3 Or R 4 At least one of them is -OR 21 、-SR 22 , or -NR 23 R 24 .

[0036] In equation (2), R 21 To R 24 Each is independently a hydrogen, substituted or unsubstituted C. 1-30 Alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 3-30heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl.

[0037] In equation (2), m is an integer from 0 to 4, and n is an integer from 0 to 4, provided that the sum of m and n is an integer greater than 0. For example, the sum of m and n can be 1, 2, 3, or 4 or greater, preferably 1 or 2.

[0038] In another embodiment, the Ar group may be a group having formula (3a), (3b), or (3c):

[0039]

[0040] A4 may or may not be present, and represents 1 to 3 fused aromatic rings. Preferably, A4 represents 1 to 3 aromatic rings, more preferably 1 to 2 fused aromatic rings, and most preferably 1 fused aromatic ring.

[0041] In equations (3a), (3b), or (3c), Z 1 and Z 2 Each is independently C or N, provided that A4 contains at least one heteroaryl ring, Z 1 and Z 2 At least one of them is N, or a combination thereof.

[0042] In equations (3a), (3b), or (3c), R 5 Each is independently either substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl. In formulas (3a), (3b), and (3c), p is an integer from 0 to 4, typically 0 or 1.

[0043] In another embodiment, the Ar group may be a group having formula (4):

[0044]

[0045] The prerequisite is that the Ar group contains one or more aromatic cyclic heteroatoms, substituents containing heteroatoms, or combinations thereof.

[0046] In equation (4), L 1 It is a single bond, -O-, -S-, -S(O)-, -SO2-, -C(O)-, -CR 41 R 42 -、-NR 43 - or -PR 44 -, where R 41 To R 44 Each is independently a hydrogen, substituted or unsubstituted C. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl. Preferably, L 1 Is it -O- or -NR? 43 -, more preferably -NR 43 -

[0047] In equation (4), L 2 It does not exist; it is a single bond; it is -O-; -S-; -S(O)-; -SO2-; -C(O)-; or it is a substituted or unsubstituted C. 1-2 Alkylene, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 5-30 Hybrid aryl. Preferably, L 2 It is a single key.

[0048] In equation (4), R 8 and R 9 Each is independently either substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C4-30 Heteroarylalkyl, halogen, -OR 45 、-SR 46 , or -NR 47 R 48 In equation (4), a is an integer from 0 to 4, typically from 0 to 2, and more typically from 0; and b is an integer from 0 to 4, typically from 0 to 2, and more typically from 0.

[0049] In equation (4), R 41 To R 48 Each is independently a hydrogen, substituted or unsubstituted C. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl.

[0050] The polymers of the present invention can be produced by reacting one or more monocyclic or polycyclic C atoms in the presence of an acid catalyst and optionally in a suitable solvent. 5-60 It is prepared by reacting an aromatic compound (aromatic monomer) with one or more dicarbonyl compounds (dicarbonyl monomers) having formula (5).

[0051]

[0052] Where R 1 It is hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl. In formula (5), R 2 It is hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl.

[0053] Aromatic monomers are monocyclic or polycyclic C 5-60 An aromatic compound, wherein the aromatic compound comprises one or more aromatic cyclic heteroatoms, substituents comprising heteroatoms, or combinations thereof. Example C 5-60 Aromatic compounds include, but are not limited to, substituted benzene, substituted biphenyl, substituted naphthalene, substituted binaphthalene, substituted anthracene, substituted benzo[a]anthracene, substituted fluorene, substituted fluoranthracene, substituted benzo[b]fluoranthracene, substituted dibenzo(a,h)anthracene, substituted phenanthrene, substituted finasteride, substituted tetraphenyl, and substituted... Substituted benzo[a]pyrene, substituted pentane, substituted benzo[a]pyrene, substituted cycloene, substituted benzo[a]perylene, substituted guanine, substituted ovobenzene, substituted benzo[c]fluorene, substituted or unsubstituted benzothiophene, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted carbazole, substituted or unsubstituted indole, substituted or unsubstituted quinoline, substituted or unsubstituted isoquinoline, substituted or unsubstituted purine, substituted or unsubstituted phenoxazine, substituted or unsubstituted phenothiazine, substituted or unsubstituted oxyphenothiazine, substituted or unsubstituted dioxophethiazine, etc.

[0054] The monomers and optional solvents can be combined in any order. The acid catalyst is typically added to the reaction mixture after the monomers and any optional solvent. After the addition of the acid catalyst, the reaction mixture is typically heated under reflux for a period of time, such as 1 to 48 hours. After heating, the reaction products are separated from the reaction mixture, such as by precipitation, and typically dried and optionally purified before use. The molar ratio of total aromatic monomers to total dicarbonyl monomers is 0.5:1 to 2:1, and typically 1:1 to 1.5:1.

[0055] In one embodiment, the polymer is prepared without using an aldehyde or ketone compound other than a dicarbonyl compound having formula (5). For example, the polymer does not contain repeating units derived from an aldehyde having the formula Ar′-CHO, where Ar′ is a substituted or unsubstituted C. 6-30 Aromatic groups.

[0056] Various solvents can be used to prepare the polymers of the present invention, such as, but not limited to, alcohols, glycol ethers, lactones, esters, ethers, ketones, water, and aromatic hydrocarbons. Preferably, relatively polar solvents are used, such as alcohols, glycol ethers, lactones, esters, ethers, ketones, or water. Mixtures of solvents can be used. Exemplary solvents include, but are not limited to, methanol, ethanol, propanol, propylene glycol, propylene glycol monomethyl ether (PGME), propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate (PGMEA), γ-butyrolactone (GBL), γ-valerolactone, δ-valerolactone, ethyl lactate, 1,4-dioxane, cyclohexanone, cyclopentanone, methyl ethyl ketone, water, mesitylene, xylene, anisole, 4-methyl anisole, etc. Preferred solvents are methanol, ethanol, propanol, propylene glycol, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ethyl lactate, 1,4-dioxane, cyclohexanone, and water.

[0057] Various acids can be suitably used as catalysts in the preparation of the polymers of the present invention. Exemplary acids include, but are not limited to, organic carboxylic acids and dicarboxylic acids such as propionic acid and oxalic acid, inorganic acids and sulfonic acids, and preferably, the acid catalyst is an inorganic acid or sulfonic acid. Suitable inorganic acids are HF, HCl, HBr, HNO3, H2SO4, H3PO4, and HClO4. Suitable sulfonic acids include alkane sulfonic acids and aryl sulfonic acids, such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, phenylsulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and cresolsulfonic acid. Preferred acid catalysts are HCl, HBr, HNO3, H2SO4, H3PO4, methanesulfonic acid, ethanesulfonic acid, phenylsulfonic acid, phenolsulfonic acid, and p-toluenesulfonic acid (pTSA).

[0058] In another embodiment, the polymer may comprise repeating units having formula (6):

[0059]

[0060] Where R 1 and R 2 It is as defined in equation (1).

[0061] The polymers of the present invention typically have a weight-average molecular weight (Mb) of 500 to 20,000 Daltons (Da), preferably 500 to 15,000 Da, and more preferably 500 to 10,000 Da. w ), such as using polystyrene standards to determine by gel permeation chromatography (GPC).

[0062] The photoresist underlayer composition may further comprise a solvent and optionally one or more additives selected from curing agents, crosslinking agents, and surfactants. Those skilled in the art will understand that other additives may be suitably used in the compositions of this invention.

[0063] The solvent can be an organic solvent typically used in the electronics industry, such as PGME, PGMEA, methyl 3-methoxypropionate (MMP), ethyl lactate, n-butyl acetate, anisole, N-methylpyrrolidone, γ-butyrolactone (GBL), ethoxybenzene, benzyl propionate, benzyl benzoate, cyclohexanone, cyclopentanone, propylene carbonate, xylene, mesitylene, cumene, limonene, and mixtures thereof. Typically, the total solids of the photoresist underlayer composition are 0.5 wt% to 20 wt% of the total weight of the photoresist underlayer composition, typically 0.5 wt% to 10 wt%, with the remainder being solvent.

[0064] Optionally, the photoresist underlayer composition of the present invention may further comprise one or more curing agents to aid in the curing of the deposited polymer film. The curing agent is any component that causes the photoresist underlayer composition to cure on the substrate surface. A preferred curing agent is a thermal acid generator (TAG). A TAG is any compound that releases acid upon exposure to heat. Thermal acid generators are well known in the art and are generally commercially available, such as from King Industries, Norwalk, Connecticut. Exemplary thermal 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 certain photoacid generators are capable of releasing acid upon heating and can be used as thermal acid generators. The amount of such curing agent that can be used in the compositions of the present invention may be, for example, greater than 0 wt% to 10 wt% based on the total solids of the photoresist underlayer composition, and typically greater than 0 wt% to 3 wt%.

[0065] Any suitable crosslinking agent can be used in the compositions of the present invention, provided that such crosslinking agent has at least two, and preferably at least three, portions capable of reacting with the polymers of the present invention under suitable conditions (such as acidic conditions). Exemplary crosslinking agents include, but are not limited to, phenolic varnish resins, epoxy-containing compounds, melamine compounds, guanidine compounds, isocyanate-containing compounds, benzocyclobutene, benzoxazine, etc., and typically have two or more, more typically three or more, selected from hydroxymethyl, C 1-10 alkoxymethyl, and C 2-10 Any of the substituents of the acyloxymethyl group. Examples of suitable crosslinking agents are those shown in formulas (7) and (8).

[0066]

[0067] Such crosslinking agents are well known in the art and are commercially available from multiple sources. The amount of such crosslinking agent that can be used in the compositions of the present invention can be, for example, greater than 0 wt% to 30 wt% based on the total solids of the composition, and typically greater than 0 wt% to 10 wt%.

[0068] The photoresist underlayer composition of the present invention may optionally comprise one or more surface leveling agents (or surfactants) and antioxidants. Typical surfactants include those exhibiting amphiphilic properties, meaning they can be both hydrophilic and hydrophobic simultaneously. Amphiphilic surfactants have one or more hydrophilic head groups (which have a strong affinity for water) and a long hydrophobic tail (which is organophilic and repels water). Suitable surfactants can be ionic (i.e., anionic, cationic) or nonionic. Other examples of surfactants include silicone surfactants, poly(oxyethylene) surfactants, and fluorinated compound surfactants. Suitable nonionic surfactants include, but are not limited to, octyl and nonylphenol ethoxylates, such as... X-114, X-100, X-45, X-15, and branched secondary alcohol ethoxylates, such as TERGITOL TM TMN-6 (The Dow Chemical Company, Midland, .M., USA) and PF-656 (Omnova Solutions, Beachwood, .O., 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, 2000 North American edition, published by Manufacturers Confectioners Publishing Co., GlenRock, NJ. Nonionic surfactants, as derivatives of acetylenic diols, may also be suitable. Such surfactants are commercially available from Air Products and Chemicals, Inc., Allentown, Pennsylvania, under the trade name... and For sale. Other suitable surfactants include other polymer compounds, such as triblock EO-PO-EO copolymers. 25R2, L121, L123, L31, L81, L101, and P123 (BASF, Inc.). If used, such surfactants may be present in the composition in small amounts, for example, greater than 0 wt% to 1 wt%, based on the total solids of the photoresist underlayer composition.

[0069] Antioxidants can be added to compositions to prevent or minimize the oxidation of organic materials in the composition. Suitable antioxidants include, for example, phenol-based antioxidants, antioxidants composed of organic acid derivatives, sulfur-containing antioxidants, phosphorus-based antioxidants, amine-based antioxidants, antioxidants composed of amine-aldehyde condensates, and antioxidants composed of amine-ketone condensates. Examples of phenol-based antioxidants include substituted phenols, such as 1-oxy-3-methyl-4-isopropylbenzene, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, butylated hydroxyanisole, 2-(1-methylcyclohexyl)-4,6-dimethylphenol, 2,4-dimethyl-6-tert-butylphenol, 2-methyl-4,6-dinonylphenol, etc. 2,6-Di-tert-butyl-α-dimethylamino-p-cresol, 6-(4-hydroxy-3,5-di-tert-butylaniline)2,4-bisoctyl-thio-1,3,5-triazine, n-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenyl)propionate, octylphenol, aralkyl-substituted phenols, alkylated p-cresols and hindered phenols; bisphenols, triphenols and polyphenols, such as 4,4′-dihydroxydiphenyl, methylenebis(dimethyl-4,6-phenol), 2,2′ -methylene-bis-(4-methyl-6-tert-butylphenol), 2,2′-methylene-bis-(4-methyl-6-cyclohexylphenol), 2,2′-methylene-bis-(4-ethyl-6-tert-butylphenol), 4,4′-methylene-bis-(2,6-di-tert-butylphenol), 2,2′-methylene-bis-(6-α-methyl-benzyl-p-cresol), methylene-crosslinked polyalkylphenols, 4,4′-butylene-bis-(3-methyl-6-tert-butylphenol), 1, 1-Bis-(4-hydroxyphenyl)cyclohexane, 2,2′-dihydroxy-3,3′-di-(α-methylcyclohexyl)-5,5′-dimethyldiphenylmethane, alkylated bisphenols, hindered bisphenols, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris-(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, and tetra-[methylene-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate]methane. Suitable antioxidants are commercially available, for example, Irganox. TMAntioxidant (Ciba Specialty Chemicals Corp.). If used, the antioxidant may be present in the composition in an amount greater than, for example, greater than 0 wt% to 1 wt% of the total solids of the photoresist underlayer composition.

[0070] Another aspect of the present invention provides a coated substrate comprising a layer of a photoresist underlay composition disposed on the substrate; and a photoresist layer disposed on the layer of the photoresist underlay composition. The coated substrate may further comprise a silicon-containing layer and / or an organic antireflective coating disposed above the photoresist underlay composition and below the photoresist layer.

[0071] Another aspect of the present invention provides a method for forming a pattern. The method includes: (a) applying a layer of a photoresist underlay composition onto a substrate; (b) curing the applied photoresist underlay composition to form a photoresist underlay; and (c) forming a photoresist layer on the photoresist underlay. The method may further include forming a silicon-containing layer and / or an organic antireflective coating on the photoresist underlay prior to forming the photoresist layer. The method may further include patterning the photoresist layer and transferring the pattern from the patterned photoresist layer to the photoresist underlay and a layer beneath the photoresist underlay.

[0072] A wide variety of substrates can be used in the patterning method, 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 interconnection levels, including single-chip wafers, multi-chip wafers, packages for various levels, or other components requiring solder connections. Such substrates can be of any suitable size. Typical wafer substrate diameters are 200 mm to 300 mm, although 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 optionally include active or operable portions of a semiconductor device. A semiconductor device refers to a semiconductor substrate on which at least one microelectronic device has been mass-produced or is being mass-produced.

[0073] 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. The layers may include, for example, one or more conductive layers such as alloys, nitrides, or silicides of such metals as aluminum, copper, molybdenum, tantalum, titanium, and tungsten; layers of doped amorphous silicon or doped polycrystalline silicon; one or more dielectric layers such as layers of silicon oxide, silicon nitride, silicon oxynitride, or metal oxides; semiconductor layers such as monocrystalline silicon; and combinations thereof. The layers may be formed using various techniques, such as chemical vapor deposition (CVD), such as plasma-enhanced CVD (PECVD), low-pressure CVD (LPCVD), or epitaxial growth; physical vapor deposition (PVD), such as sputtering or evaporation; or electroplating.

[0074] Photoresist undercoat compositions can be applied to a substrate by any suitable means, such as spin coating, slot die coating, blade coating, curtain coating, roll coating, spray coating, dip coating, etc. In the case of semiconductor wafers, spin coating is preferred. In a typical spin coating method, the photoresist undercoat composition 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 layer of photoresist undercoat composition on the substrate. Those skilled in the art will understand that the thickness of the coated photoresist undercoat composition can be adjusted by varying the rotation speed and the total solids content of the photoresist composition. The photoresist undercoat formed from the photoresist undercoat composition typically has a dried layer thickness of 5 nm to 50 μm, typically 25 nm to 3 μm, and more typically 50 to 500 nm. The photoresist undercoat composition can be applied to substantially fill, preferably fill, and more preferably completely fill multiple gaps in the substrate.

[0075] Optionally, the applied photoresist underlayer composition is soft-baked at a relatively low temperature to remove any solvents and other relatively volatile components from the composition. Exemplary baking temperatures can be from 60°C to 170°C, although other suitable temperatures may be used. This baking to remove residual solvents can be performed from 10 seconds to 10 minutes, although longer or shorter times may be used appropriately. When the substrate is a wafer, this baking step can be performed by heating the wafer on a hot plate.

[0076] The applied photoresist underlayer composition is then cured to form a photoresist underlayer. The photoresist underlayer composition should be fully cured such that it does not mix with, or minimally mixes with, any subsequently applied layers (such as a photoresist layer or other organic or inorganic layer disposed directly on the photoresist underlayer). The photoresist underlayer 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, although oven curing can be used to obtain equivalent results. The curing temperature should be sufficient to cure the entire layer, for example, sufficient to crosslink a curing agent such as a free acid, or to release acid from a hot acid generator and crosslink the released acid, wherein the curing agent is TAG. Typically, curing is performed at a temperature of 150°C or higher, and preferably between 150°C and 450°C. More preferably, the curing temperature is 180°C or higher, even more preferably 200°C or higher, and even more preferably 200°C to 400°C. The curing time is typically 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes, more preferably 45 seconds to 5 minutes, and even more preferably 45 to 90 seconds. Optionally, a ramp-up or multi-stage curing process can be used. Ramp-up baking typically begins at a relatively low (e.g., ambient) temperature, which increases at a constant or varying ramp rate to a higher target temperature. Multi-stage curing processes involve curing at two or more temperature plateaus, typically with a first stage at a lower baking temperature and one or more additional stages at higher temperatures. The conditions of such ramp-up or multi-stage curing processes are known to those skilled in the art and may allow the omission of a prior soft-baking process.

[0077] After curing the photoresist underlayer composition, one or more processing layers (such as a photoresist layer), hard mask layers (such as a metal hard mask layer), organic or inorganic BARC layers, etc., can be disposed on the cured photoresist underlayer. The photoresist layer can be formed directly on the surface of the photoresist underlayer, or alternatively, it can be formed on the photoresist underlayer over one or more intermediate layers. In this case, one or more intermediate processing layers, such as those described above, can be sequentially formed on the photoresist underlayer, followed by the formation of the photoresist layer. The determination of suitable layers, thicknesses, and coating methods is well known to those skilled in the art.

[0078] A wide variety of photoresists can be suitably used in the methods of the present invention, and are typically positive materials. Suitable photoresists include, for example, EPIC, available from DuPont Electronics & Imaging (Marlborough, Massachusetts).TM The material within a series of photoresists. The photoresist can be applied to the substrate using known coating techniques (such as those described above regarding the underlayer composition, where spin coating is typical). The typical thickness of the photoresist layer is 500 to... 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 layer's adhesion to the substrate. Soft baking can be performed on a heated plate or in an oven, with a heated plate being typical. Typical soft baking is performed at temperatures between 90°C and 150°C for 30 to 90 seconds.

[0079] Optionally, one or more blocking layers may be disposed on the photoresist layer. Suitable blocking layers include top coatings, top antireflective coatings (or TARC layers), etc. Preferably, a top coating is used when patterning the photoresist using immersion lithography. Such top coatings are well known in the art and are generally commercially available, such as OC coatings available from DuPont Electronics and Imaging Corporation. TM 2000. Those skilled in the art will recognize that when an organic antireflective layer is used under a photoresist layer, a TARC layer is not required.

[0080] Next, the photoresist layer is exposed to activating radiation through a photomask to create a solubility difference between the exposed and unexposed areas. The exposure of the photoresist composition to radiation that activates the composition, as described herein, indicates that the radiation can form a latent image in 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. Exposure wavelengths are typically below 400 nm, below 300 nm, such as 248 nm (KrF), 193 nm (ArF), or EUV wavelengths (e.g., 13.5 nm). In a preferred aspect, the exposure wavelength is 193 nm. Exposure energy is typically 10 to 80 mJ / cm². 2 This depends on, for example, the components of the exposure tool and the photosensitive composition.

[0081] After the photoresist layer is exposed, post-exposure baking (PEB) is typically performed. PEB can be performed, for example, on a heated plate or in an oven. PEB is typically performed at temperatures between 80°C and 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). The exposed photoresist layer is then developed using a suitable developer to provide a patterned photoresist layer.

[0082] The pattern of the photoresist layer can then be transferred to one or more underlying layers, including the photoresist substrate, and onto the substrate using appropriate etching techniques, such as plasma etching or wet etching. Plasma etching can use an appropriate gas species for each etched layer. Suitable wet chemical etching chemistry includes, for example, mixtures containing ammonium hydroxide, hydrogen peroxide, and water (e.g., SC-1 cleaning solution); mixtures containing hydrochloric acid, hydrogen peroxide, and water (e.g., SC-2 cleaning solution); mixtures containing sulfuric acid, hydrogen peroxide, and water (e.g., SPM cleaning solution); mixtures containing phosphoric acid, hydrogen peroxide, and water; mixtures containing hydrofluoric acid and water; mixtures containing hydrofluoric acid, phosphoric acid, and water; mixtures containing hydrofluoric acid, nitric acid, and water; mixtures containing tetramethylammonium hydroxide and water; etc.

[0083] Depending on the number of layers and materials involved, pattern transfer can involve multiple etching steps using different techniques. After pattern transfer to the substrate using conventional techniques, the patterned photoresist layer, photoresist underlayer, and other optional layers in the photolithographic stack can be removed. Optionally, one or more layers of the stack can be removed or consumed after pattern transfer to the lower layer and before pattern transfer to the substrate. The substrate is then further processed according to known methods to form an electronic device.

[0084] Photoresist underlayer compositions can also be used in self-aligned dual patterning processes. In this process, a layer of the photoresist underlayer composition described above is coated onto a substrate, such as by spin coating. Any remaining organic solvents are removed and the coating is cured to form the photoresist underlayer. A suitable intermediate layer, such as a silicon-containing hard mask layer, is optionally coated onto the photoresist underlayer. A suitable photoresist layer is then coated onto the intermediate layer, such as by spin coating. The photoresist layer is then imaged (exposed), and the exposed photoresist layer is then developed using a suitable developer to provide a patterned photoresist layer. Next, the pattern is transferred from the photoresist layer to the intermediate layer and the photoresist underlayer using a suitable etching technique to expose a portion of the substrate. Typically, the photoresist is also removed during this etching step. Next, a conformal silicon-containing layer is placed over the patterned photoresist underlayer and the exposed portion of the substrate. Such silicon-containing layers are typically inorganic silicon layers, such as SiON or SiO2, conventionally deposited by CVD. This type of conformal coating is formed on the exposed portion of the substrate surface and on a silicon-containing layer above the photoresist underlay pattern, i.e., this silicon-containing layer substantially covers the sides and top of the photoresist underlay pattern. Next, the silicon-containing layer is partially etched (trimmed) to expose the top surface of the patterned photoresist underlay and a portion of the substrate. After this partial etching step, the pattern on the substrate comprises multiple features, each containing lines or pillars of the photoresist underlay, with the silicon-containing layer directly adjacent to the side of each photoresist underlay feature. Next, the exposed areas of the photoresist underlay are removed, such as by etching, to expose the substrate surface beneath the photoresist underlay pattern, and a patterned silicon-containing layer is provided on the substrate surface, wherein this patterned silicon-containing layer is twice the size (i.e., more than twice the number of lines and / or pillars) compared to the original patterned photoresist underlay.

[0085] The photoresist underlay formed from the photoresist underlay composition of the present invention exhibits excellent planarization, good solvent resistance, and tunable etch rate. The preferred photoresist underlay composition of the present invention can therefore be used in various semiconductor manufacturing processes.

[0086] The inventive concept is further illustrated by the following examples. All compounds and reagents used herein are commercially available, except for the procedures provided below.

[0087] Example

[0088] Polymer Synthesis

[0089] Synthesis Example 1

[0090] 10.0 g of carbazole (1.5 equivalents), 3.67 g of glyoxylic acid monohydrate (1 equivalent), and 50 mL of propylene glycol monomethyl ether acetate (PGMEA) were added to a round-bottom flask. The reaction mixture was heated to 60 °C and stirred for 5 min, followed by the addition of 0.30 g of methanesulfonic acid in a single batch. The reaction mixture was then heated to 120 °C for 16 h. After this reaction time, the reaction mixture was cooled to room temperature and poured into 9 / 1 (v / v) methanol / water to give a solid polymer product. The product was filtered and washed with methanol, then air-dried for 4 h and vacuum-dried at 50 °C for an additional 20 h to give Synthetic Example 1 (P-1) (66% yield, Mw = 2220, PDI = 1.9).

[0091] Synthesis Example 2

[0092] Add 5.0 g of carbazole (1.5 equivalents), 1.85 g of glyoxylic acid monohydrate (1 equivalent), 6.65 g of 1-butanol (3 equivalents), and 15 mL of 1,4-dioxane to a round-bottom flask. Heat the reaction mixture to 60 °C and stir for 5 min, then add 1.45 g of methanesulfonic acid in a single batch. Heat the reaction mixture to 100 °C for 16 h. After this reaction time, cool the reaction mixture to room temperature and pour it into 9 / 1 (v / v) methanol / water to give a solid polymer product. Filter the product and wash with methanol, then air-dry for 4 h and vacuum-dry at 50 °C for an additional 20 h to give Synthetic Example 2 (P-2) (87% yield, Mw = 1510, PDI = 1.4).

[0093] Synthesis Examples 3 to 6

[0094] Synthetic Examples 3 (P-3) to 6 (P-6) were prepared using the same procedure as above and with the corresponding alcohols (P-3: octanol; P-4: 2-(2-methoxyethoxy)ethanol; P-5: benzyl alcohol; P-6: 3,7-dimethyl-1-octanol) to obtain the desired polymers.

[0095]

[0096] Synthesis Example 7

[0097] 6.0 g of carbazole (1.25 equivalents), 2.53 g of pyruvate (1 equivalent), and 25 mL of PGMEA were added to a round-bottom flask. The reaction mixture was heated to 60 °C and stirred for 5 min, followed by the addition of 1.70 g of methanesulfonic acid in a single batch. The reaction mixture was then heated to 120 °C for 16 h. After this reaction time, the reaction mixture was cooled to room temperature and poured into 9 / 1 (v / v) methanol / water to give a solid polymer product. The product was filtered off and washed with excess methanol, then air-dried for 4 h and vacuum-dried at 50 °C for an additional 20 h to give Synthetic Example 7 (P-7) (76% yield, Mw = 3080, PDI = 1.7).

[0098] Synthesis Example 8

[0099] 6.0 g of carbazole (1.25 equivalents), 3.33 g of ethyl pyruvate (1 equivalent), and 25 mL of PGMEA were added to a round-bottom flask. The reaction mixture was heated to 60 °C and stirred for 5 min, followed by the addition of 1.70 g of methanesulfonic acid in a single batch. The reaction mixture was then heated to 120 °C for 16 h. After this reaction time, the reaction mixture was cooled to room temperature and poured into 9 / 1 (v / v) methanol / water to give a solid polymer product. The product was filtered off and washed with excess methanol, then air-dried for 4 h and vacuum-dried at 50 °C for an additional 20 h to give Synthetic Example 8 (P-8) (67% yield, Mw = 2630, PDI = 1.5).

[0100] Synthesis Example 9

[0101] 5.0 g of carbazole (1.5 equivalents), 3.11 g of methyl trifluoromethyl pyruvate (1 equivalent), and 20 mL of PGMEA were added to a round-bottom flask. The reaction mixture was heated to 60 °C and stirred for 5 min, followed by the addition of 1.50 g of methanesulfonic acid in a single batch. The reaction mixture was then heated to 120 °C for 16 h. After this reaction time, the reaction mixture was cooled to room temperature and poured into 9 / 1 (v / v) methanol / water to give a solid polymer product. The product was filtered off and washed with excess methanol, then air-dried for 4 h and vacuum-dried at 50 °C for an additional 20 h to give Synthetic Example 9 (P-9) (65% yield, Mw = 10200, PDI = 2.9).

[0102]

[0103] Synthesis Example 10

[0104] 6.0 g of carbazole (1.5 equivalents), 3.59 g of phenylglyoxylic acid (1 equivalent), and 25 mL of PGMEA were added to a round-bottom flask. The reaction mixture was heated to 60 °C and stirred for 5 min, followed by the addition of 1.70 g of methanesulfonic acid in a single batch. The reaction mixture was then heated to 120 °C for 16 h. After this reaction time, the reaction mixture was cooled to room temperature and poured into 9 / 1 (v / v) methanol / water to give a solid polymer product. The product was filtered off and washed with excess methanol, then air-dried for 4 h and vacuum-dried at 50 °C for an additional 20 h to give Synthetic Example 10 (P-10) (40% yield, Mw = 1250, PDI = 1.2).

[0105] Synthesis Example 11

[0106] 10.0 g of 1-naphthol (1.2 equivalents), 5.32 g of glyoxylic acid monohydrate (1 equivalent), and 40 mL of PGMEA were added to a round-bottom flask. The reaction mixture was heated to 60 °C and stirred for 5 min, followed by the addition of 3.35 g of methanesulfonic acid in a single batch. The reaction mixture was then heated to 120 °C for 20 h. After this reaction time, the reaction mixture was cooled to room temperature and poured into 9 / 1 (v / v) methanol / water to give a solid polymer product. The product was filtered off and washed with excess methanol, then air-dried for 4 h and vacuum-dried at 50 °C for an additional 20 h to give Synthetic Example 11 (P-11) (88% yield, Mw = 3640, PDI = 2.0).

[0107] Synthesis Example 12

[0108] 10.0 g of 1-naphthol (1.2 equivalents), 5.32 g of glyoxylic acid monohydrate (1 equivalent), 15.5 g of 1-butanol (3 equivalents), and 25 mL of 1,4-dioxane were added to a round-bottom flask. The reaction mixture was heated to 60 °C and stirred for 5 min, followed by the addition of 3.35 g of methanesulfonic acid in a single batch. The reaction mixture was then heated to 100 °C for 16 h. After this reaction time, the reaction mixture was cooled to room temperature and poured into 9 / 1 (v / v) methanol / water to give a solid polymer product. The product was filtered off and washed with excess methanol, then air-dried for 4 h and vacuum-dried at 50 °C for an additional 20 h to give Synthetic Example 12 (P-12) (59% yield, Mw = 1750, PDI = 1.4).

[0109]

[0110] Synthesis Example 13

[0111] 6.0 g of 1-naphthol (1.5 equivalents), 2.45 g of pyruvate (1 equivalent), and 25 mL of PGMEA were added to a round-bottom flask. The reaction mixture was heated to 60 °C and stirred for 5 min, followed by the addition of 2.00 g of methanesulfonic acid in a single batch. The reaction mixture was then heated to 120 °C for 20 h. After this reaction time, the reaction mixture was cooled to room temperature and poured into 9 / 1 (v / v) methanol / water to give a solid polymer product. The product was filtered off and washed with excess methanol, then air-dried for 4 h and vacuum-dried at 50 °C for an additional 20 h to give Synthetic Example 13 (P-13) (59% yield, Mw = 810, PDI = 1.5).

[0112] Synthesis Example 14

[0113] 6.0 g of 1-naphthol (1.5 equivalents), 3.22 g of ethyl pyruvate (1 equivalent), and 25 mL of PGMEA were added to a round-bottom flask. The reaction mixture was heated to 60 °C and stirred for 5 min, followed by the addition of 2.00 g of methanesulfonic acid in a single batch. The reaction mixture was then heated to 120 °C for 16 h. After this reaction time, the reaction mixture was cooled to room temperature and poured into 9 / 1 (v / v) methanol / water to give a solid polymer product. The product was filtered off and washed with excess methanol, then air-dried for 4 h and vacuum-dried at 50 °C for an additional 20 h to give Synthetic Example 14 (P-14) (70% yield, Mw = 1010, PDI = 1.7).

[0114] Synthesis Example 15

[0115] 5.0 g of 1-pyrene alcohol (1.5 equivalents), 1.40 g of glyoxylic acid monohydrate (1 equivalent), and 20 mL of PGMEA were added to a round-bottom flask. The reaction mixture was heated to 60 °C and stirred for 5 min, followed by the addition of 1.30 g of methanesulfonic acid in a single batch. The reaction mixture was then heated to 120 °C for 20 h. After this reaction time, the reaction mixture was cooled to room temperature and poured into 9 / 1 (v / v) methanol / water to give a solid polymer product. The product was filtered off and washed with excess methanol, then air-dried for 4 h and vacuum-dried at 50 °C for an additional 20 h to give Synthetic Example 15 (P-15) (62% yield, Mw = 1790, PDI = 1.6).

[0116]

[0117] Comparative polymer synthesis

[0118] Comparison Example Synthesis 1

[0119] Add 5.0 g of carbazole (1.5 equivalents), 0.60 g of paraformaldehyde (1 equivalent), and 20 mL of PGMEA to a round-bottom flask. Heat the reaction mixture to 60 °C and stir for 5 min, then add 1.45 g of methanesulfonic acid in a single batch. Heat the reaction mixture to 120 °C for 16 h. After this reaction time, cool the reaction mixture to room temperature and pour it into 9 / 1 (v / v / ) methanol / water to give a solid polymer product. Filter off the product and wash with excess methanol, then air-dry for 4 h and vacuum-dry at 50 °C for an additional 20 h to give Comparative Synthesis Example 1 (CP-1) (80% yield, Mw = 2730, PDI = 2.5).

[0120] Comparison Example Synthesis 2

[0121] Add 5.0 g of carbazole (1.5 equivalents), 1.85 g of glyoxylic acid monohydrate (1 equivalent), and 25 mL of 1,4-dioxane to a round-bottom flask. Heat the reaction mixture to 60 °C and stir for 5 min, then add 1.45 g of methanesulfonic acid in a single batch. The reaction mixture is then heated to 100 °C for 16 h. After this reaction time, cool the reaction mixture to room temperature and pour it into 9 / 1 (v / v) methanol / water to give a solid polymer product. Filter off the product and wash with excess methanol, then air-dry for 4 h and vacuum-dry at 50 °C for an additional 20 h to give Comparative Synthesis Example 2 (CP-2) (58% yield, Mw = 1610, PDI = 1.3).

[0122] Comparison Example Synthesis 3

[0123] 5.0 g of 1-naphthol (1 equivalent), 1.04 g of paraformaldehyde (1 equivalent), and 25 mL of PGMEA were added to a round-bottom flask. The reaction mixture was heated to 60 °C and stirred for 5 min, followed by the addition of 0.20 g of methanesulfonic acid in a single batch. The reaction mixture was then heated to 120 °C for 16 h. After this reaction time, the reaction mixture was cooled to room temperature and poured into 9 / 1 (v / v) methanol / water to give a solid polymer product. The product was filtered off and washed with excess water and methanol, then air-dried for 4 h and vacuum-dried at 50 °C for an additional 20 h to give Comparative Synthesis Example 3 (CP-3) (52% yield, Mw = 2240, PDI = 2.0).

[0124] Comparison Example Synthesis 4

[0125] 5.0 g of 1-pyrene alcohol (1 equivalent), 0.69 g of paraformaldehyde (1 equivalent), and 20 mL of propylene glycol monomethyl ether (PGME) were added to a round-bottom flask. The reaction mixture was heated to 60 °C and stirred for 5 min, followed by the addition of 2.20 g of methanesulfonic acid in a single batch. The reaction mixture was then heated to 120 °C for 1 h. After this reaction time, most of the reaction mixture solidified. The solid was removed from the flask and washed with excess water and methanol, then air-dried for 4 h and vacuum-dried at 50 °C for an additional 20 h to obtain Comparative Synthesis Example 4 (CP-4).

[0126]

[0127] Physical test

[0128] The number-average molecular weight and weight-average molecular weight of the polymer (Mi and Mi, respectively) n and M w ) and polydispersity (PDI) value (M w / M n The measurements were performed by gel permeation chromatography (GPC) on an Agilent 1100 series LC system equipped with an Agilent 1100 series refractive index and a MiniDAWN light scattering detector (Wyatt Technology Co.). The sample was dissolved in HPLC-grade THF at a concentration of approximately 10 mg / mL and filtered through a 0.45 μm syringe filter before being injected through four Shodex columns (KF805, KF804, KF803, and KF802). A flow rate of 1 mL / min and a temperature of 35 °C were maintained. The columns were calibrated using a narrow molecular weight PS standard (EasiCal PS-2, Polymer Laboratories, Inc.).

[0129] Differential scanning calorimetry (DSC) was used to determine the glass transition temperature on the bulk polymer. Samples (1–3 mg) were heated to 150 °C and allowed to stand at 150 °C for 10 min to remove residual solvent from the first cycle, then cooled to 0 °C and rapidly increased to 300 °C at a heating rate of 10 °C / min. The glass transition temperature was identified using a second heating profile and a reversible heating profile.

[0130] Table 1 shows the molecular weight, solubility, and thermal characterization of polymers P-1 to P-10 and comparative polymers CP-1 and CP-2.

[0131] Table 1.

[0132] Example <![CDATA[M w ]]> PDI <![CDATA[Solubility a > <![CDATA[T g (℃) b ]]> P-1 2220 1.9 +++ 164 P-2 1510 1.4 +++ 108 P-3 1930 1.4 +++ 67 P-4 1760 1.5 +++ 114 P-5 1540 1.4 +++ 84 P-6 1980 1.4 +++ 29 P-7 3080 1.7 +++ 166 P-8 2360 1.5 +++ 157 P-9 10200 2.9 +++ N / A P-10 1250 1.2 +++ N / A CP-1 2730 2.5 X N / A CP-2 1610 1.3 X N / A

[0133] a. Solubility in PGMEA at 10 wt%. +++ indicates complete dissolution, X indicates slight dissolution or no dissolution at this concentration.

[0134] b. Heating rate of 10 °C / min as measured by DSC; N / A indicator "not observed".

[0135] Table 2 shows the molecular weight, solubility, and thermal characterization of polymers P-11 to P-15 and comparative polymers CP-3 and CP-4.

[0136] Table 2.

[0137] Example <![CDATA[M w ]]> PDI <![CDATA[Solubility a > <![CDATA[T g (℃) b ]]> P-11 3640 2.0 +++ 177 P-12 1750 1.4 +++ 156 P-13 810 1.5 +++ 117 P-14 1010 1.7 +++ 141 P-15 1790 1.6 +++ 186 CP-3 2240 2.0 +++ N / A CP-4 - - X N / A

[0138] a. Solubility in PGMEA at 10 wt%. +++ indicates complete dissolution, X indicates slight dissolution or no dissolution at this concentration.

[0139] b. Heating rate of 10 °C / min as measured by DSC; N / A indicator "not observed".

[0140] As can be seen from Tables 1 and 2, the compositions of the present invention have better solubility and lower glass transition temperature compared with the comparative examples.

[0141] Preparations

[0142] The photoresist underlayer composition was prepared by combining the polymers listed in Tables 1 and 2 with the components outlined in Table 3 to form a photoresist underlayer composition. The composition was filtered through a 0.2 μm PTFE syringe filter prior to coating. The amounts of polymer 1, polymer 2, additive 1, additive 2, and solvent are listed in grams (g).

[0143] Table 3.

[0144]

[0145] The structures of polymer A-1, additive B-1, additive C-1, solvent D-1, and solvent D-2 are as follows.

[0146]

[0147] Coating and film testing

[0148] The photoresist underlayer composition was coated at 100-200 nm and baked at 240 °C for 60 s. The film thickness was measured by ellipsometry.

[0149] Solvent resistance

[0150] Solvent resistance was measured as an indicator of film crosslinking. The composition was coated onto an 8-inch silicon wafer using ACT-8Clean Track (Tokyo Electron Co.) and baked. OptiProbe from Therma-wave Co. was used. TM Membrane thickness was measured. Propylene glycol monomethyl ether acetate (PGMEA) was applied to the membrane for 90 seconds, followed by post-peel baking (PSB) at 105°C for 60 seconds. Solvent resistance was calculated according to Equation 1:

[0151] [(FT before stripping) - (FT after PSB)] / (FT before stripping) * 100% Equation 1

[0152] Where FT is the film thickness. Solvent resistance is reported in Table 5, where A is defined as 99%–100% solvent resistance and B is defined as 90%–99% solvent resistance.

[0153] Etching rate

[0154] Etching rates were determined for photoresist underlayer compositions coated and baked on 8-inch silicon wafers with film thicknesses of 100-200 nm. The dry etch rate of the substrate film was determined using a Plasma-Therm 700+ series etching tool under the conditions shown in Table 4. The cured photoresist underlayer compositions were etched using O2 or CF4 plasma. Film thickness was measured as a function of time before and after etching, and the etch rate was calculated. The etch rates of the photoresist underlayer compositions are shown in Table 5.

[0155] Table 4.

[0156] precursor <![CDATA[CF4]]> <![CDATA[Ar / O2]]> Flow rate (sccm) 50 60 / 20 Power (W) 500 300 Pressure (mT) 10 10 Time (s) 30,60,120 30,60,90

[0157] Flattening test

[0158] The photoresist underlay compositions of the present invention were evaluated to determine their planarization properties. Templates were created at CNSE Nano-FAB (Albany, NY). These templates had a SiO2 film thickness of 100 nm and various spacings and patterns, with a die size of 1 cm x 1 cm. Each die began with a stepped pattern spaced at 100 nm intervals, followed by a 2000 μm unpatterned open area, and then various line / space patterns covering trenches with spacings from 45 nm / 90 nm to 2 μm / 5 μm. The first stepped pattern was used to assess planarization performance. Before coating the samples with the compositions of the present invention, the template samples were baked at 150 °C for 60 seconds as a dehydration bake. Each photoresist underlay composition was coated onto the template samples using a spin coater at a rotation speed of 1500 rpm ± 200 rpm. The target film thickness after curing was 100 nm, and the composition dilution was adjusted accordingly to approximate the target film thickness after curing. The film was cured by placing the wafer on a hot plate at 240 °C for 60 seconds. The planarization quality of the membrane across the steps was evaluated using a KLA Tencor P-7stylus profilometer.

[0159] In Table 5, planarization quality is defined as follows: A indicates a height variation of less than 20 nm, B indicates a height variation between 20 and 28 nm, and C indicates a height variation greater than 28 nm. Lower values ​​indicate superior planarization performance, so A represents the best planarization, followed by B, and C represents the worst planarization performance.

[0160] Table 5.

[0161]

[0162] As can be seen from Table 5, the photoresist underlayer composition of the present invention has excellent planarization properties and can be finely tuned to a higher, lower, or matching etch rate by blending or mixing resins.

[0163] While this disclosure has been described in conjunction with exemplary embodiments now considered to be practical, it should be understood that the invention is not limited to the disclosed embodiments, but rather is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A photoresist underlayer composition comprising: Polymer and crosslinking agent, said polymer comprising repeating units having formula (1): in Ar is a monocyclic or polycyclic C 5-60 Aromatic groups, wherein the C 5-60 Aromatic groups contain one or more aromatic cyclic heteroatoms, substituents containing heteroatoms, or combinations thereof; R 1 It is hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne group, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl; and R 2 Is it substituted or unsubstituted C? 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne group, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 heteroarylalkyl, Where R 1 and R 2 They can be arbitrarily combined to form a ring. The polymer has a weight-average molecular weight (M) of 500 to 20,000 Daltons. w For example, using polystyrene standards determined by gel permeation chromatography. The photoresist underlayer composition does not contain photoacid generators.

2. The photoresist underlayer composition as described in claim 1, wherein, Single or multiple ring C 5-60 Aromatic groups are: Single or multiple ring C 5-60 heteroaryl; or -OR 11 -SR 12 , or -NR 13 R 14 Replacement of monocyclic or polycyclic C 6-60 Alpha-aryl, of which R 11 to R 14 Each is independently hydrogen, substituted or unsubstituted C. 1-30 Alkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 heteroarylalkyl, The single-ring or multi-ring C 5-60 The heteroaryl group is optionally substituted by at least one of the following: substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne group, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 7-30 Alkyl aryl, substituted or unsubstituted C 3-30 heteroaryl, substituted or unsubstituted C 4-30 Heteroarylalkyl, halogen, -OR 11 -SR 12 , or -NR 13 R 14 , where R 11 to R 14 Each is independently hydrogen, substituted or unsubstituted C. 1-30 Alkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl.

3. The photoresist underlayer composition as described in claim 1 or 2, wherein, Ar contains groups having formula (2): in, A1, A2, and A3 are either present or absent, and each independently represents one to three fused aromatic rings; R 3 and R 4 Each is a substituted or unsubstituted C independently. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne group, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl, halogen, -OR 21 -SR 22 , or -NR 23 R 24 ;and The premise is R 3 Or R 4 At least one of them is -OR 21 -SR 22 , or -NR 23 R 24 ; R 21 to R 24 Each is independently a hydrogen, substituted or unsubstituted C. 1-30 Alkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl; m is an integer from 0 to 4; n is an integer from 0 to 4; and The premise is that the sum of m and n is an integer greater than 0.

4. The photoresist underlayer composition as described in claim 1, wherein, Ar contains groups having formula (3a), (3b), or (3c): in, A4 is either present or absent, and represents 1 to 3 fused aromatic rings; Z 1 and Z 2 Each can be either C or N independently; R 5 Each is a substituted or unsubstituted C independently. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne group, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl; and p is an integer from 0 to 4. A4 contains: (i) at least one heteroaryl ring. (ii)Z 1 and Z 2 At least one of them is N, or Its combination.

5. The photoresist underlayer composition as described in claim 1, wherein, Ar contains groups having formula (4): in, L 1 It is a single bond, -O-, -S-, -S(O)-, -SO2-, -C(O)-, -CR 41 R 42 -、-NR 43 - or -PR 44 -; L 2 It does not exist; it is a single bond; it is -O-; -S-; -S(O)-; -SO2-; -C(O)-; or it is a substituted or unsubstituted C. 1-2 Alkylene, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 5-30 heteroaryl; R 8 and R 9 Each is a substituted or unsubstituted C independently. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne group, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl, halogen, -OR 45 -SR 46 , or -NR 47 R 48 ; R 41 to R 48 Each is independently a hydrogen, substituted or unsubstituted C. 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl; a is an integer from 0 to 4; and b is an integer between 0 and 4.

6. The photoresist underlayer composition as described in claim 1, wherein, The single-ring or multi-ring C 5-60 Aromatic groups are monocyclic or polycyclic carbons substituted with hydroxyl groups. 6-60 Alpha-aryl.

7. The photoresist underlayer composition as described in claim 1, wherein, The polymer comprises repeating units having formula (6): where R 1 and R 2 It is as defined in any one of claims 1 to 6.

8. The photoresist underlayer composition of claim 1, further comprising one or more of a curing agent or a surfactant.

9. A method for forming a pattern, the method comprising: (a) Applying a layer of a photoresist underlayer composition to a substrate, wherein the photoresist composition does not contain a photoacid generator; (b) curing the applied photoresist underlayer composition to form a photoresist underlayer; and (c) forming a photoresist layer on the photoresist underlayer. The photoresist underlayer composition comprises a polymer having repeating units of formula (1): in Ar is a monocyclic or polycyclic C 5-60 Aromatic groups, wherein the C 5-60 Aromatic groups contain one or more aromatic cyclic heteroatoms, substituents containing heteroatoms, or combinations thereof; R 1 It is hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne group, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl; and R 2 Is it substituted or unsubstituted C? 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocyclic alkyl, substituted or unsubstituted C 2-30 alkenyl, substituted or unsubstituted C 2-30 Alkyne group, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 3-30 heteroaryl, or substituted or unsubstituted C 4-30 heteroarylalkyl, where R 1 and R 2 They can be arbitrarily combined to form a ring. The polymer has a weight-average molecular weight (M) of 500 to 20,000 Daltons. w (e.g., using polystyrene standards determined by gel permeation chromatography).

10. The method of claim 9, further comprising forming a silicon-containing layer, an organic antireflective coating, or a combination thereof on the photoresist underlayer prior to forming the photoresist layer.

11. The method of claim 9 or 10, further comprising patterning the photoresist layer and transferring the pattern from the patterned photoresist layer to the photoresist underlayer and a layer below the photoresist underlayer.

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