Photoresist underlayer composition to promote adhesion

Abstract

The invention relates to a photoresist underlayer composition for promoting adhesion. Disclosed is a photoresist underlayer composition comprising: a poly (arylene ether) derived from a first compound comprising two or more cyclopentadienone moieties and a second compound comprising an aryl moiety and two or more alkyne groups; additive and solvent having formula (15): # imgabs0 #

Description

[0001] This invention patent application is a divisional application of the invention patent application with application number 202111515012.4, application date December 13, 2021, and name “Photoresist underlying composition that promotes adhesion”. Technical Field

[0002] The present invention relates generally to the field of electronic devices, and more particularly to the field of materials and methods for semiconductor fabrication. Background Art

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

[0004] An ideal photoresist base material should have certain specific characteristics: it should be able to be cast onto a substrate by a spin coating process, should be thermally cured when heated, have low outgassing and sublimation, should be soluble in common solvents for good spin bowl compatibility, should have appropriate n and k values ​​to work with anti-reflective coatings to impart the low reflectivity required for photoresist imaging, and should have high thermal stability to avoid damage during subsequent processing steps. In addition to these requirements, an ideal photoresist base material must provide a flat film when spin-coated and thermally cured on a substrate, with topography and sufficient dry etch selectivity to silicon-containing layers above and below the photoresist base film to accurately transfer the optical pattern to the final substrate.

[0005] Organic poly(arylene) compounds have been used as spin-on carbon (SOC) materials for patterning in three-layer or four-layer processes. Such poly(arylene)-containing SOC formulations can have high thermal stability, high etch resistance, and good planarization under test conditions. However, the adhesion of poly(arylene)-containing materials to inorganic substrates is challenging and can cause problems in some processing steps. For example, during substrate removal by wet chemical etching, poly(arylene)-containing formulations can delaminate from the substrate, resulting in unacceptable loss of pattern fidelity and substrate damage.

[0006] Therefore, there remains a need for new photoresist underlayer materials that can achieve improved adhesion of SOC formulations. Summary of the Invention

[0007] Provided is a photoresist underlayer composition comprising: poly(arylene ether); and an additive having formula (14):

[0008] D-(L 1 -Ar-[X] n ) m (14); and

[0009] Solvent, wherein, in formula (14), D is substituted or unsubstituted C 1-60 An organic group, optionally wherein D is said substituted or unsubstituted C 1-60 Organic acid salt of organic group; each L 1 are independently a single bond or a divalent linking group, when L 1 When it is a single bond, D can be a substituted or unsubstituted C optionally fused to Ar. 3-30 Cycloalkyl or substituted or unsubstituted C 1-20 Heterocycloalkyl, each Ar is independently a monocyclic or polycyclic C 5-60 Aromatic group, each X is independently -OR 30 、-SR 31 , or -NR 32 R 33 , m is an integer from 1 to 6, each n is independently an integer from 0 to 5, provided that the sum of all n is 2 or greater, R 30 to R 33 are each independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 7-30 Alkylaryl, substituted or unsubstituted C 3-30 Heteroaryl, substituted or unsubstituted C 4-30 Heteroarylalkyl, each of which, except hydrogen, optionally further comprises as part of its structure one or more of: substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 2-30 Alkenylene, substituted or unsubstituted C 4-30 Cycloalkenylene, substituted or unsubstituted C 2-30 Alkynylidene, substituted or unsubstituted C 1-30 Heterocycloalkylene, substituted or unsubstituted C 6-30 Arylene, substituted or unsubstituted C 4-30heteroarylene, -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -S(O)2-, or -NR 34 -, where R 34 is substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 1-20 Heterocycloalkyl, 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 4-30 Heteroaryl, substituted or unsubstituted C 5-30 Heteroarylalkyl, or substituted or unsubstituted C 5-30 alkylheteroaryl, and when n is 2, optionally R of the first group X 30 to R 33 Any one of them is a divalent group, and R of the second group X 30 to R 33 Any one of the above is a divalent group, and the divalent group of the first group X and the divalent group of the second group X together form a ring, wherein the ring optionally further comprises a linking group, the linking group comprising one or more of the following: substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 2-30 Alkenylene, substituted or unsubstituted C 4-30 Cycloalkenylene, substituted or unsubstituted C 2-30 Alkynylidene, substituted or unsubstituted C 6-30 Arylene, -O-, -C(O)-, -C(O)O-, -NR 35 -, -S-, -S(O)-, or -S(O)2-, where R 35 is substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 1-20 Heterocycloalkyl, 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 4-30 Heteroaryl, substituted or unsubstituted C 5-30 Heteroarylalkyl, or substituted or unsubstituted C 5-30 Alkylheteroaryl.

[0010] Also provided is a method for forming a pattern, the method comprising: (a) applying a layer of a photoresist base layer composition on a substrate; (b) curing the applied photoresist base layer composition to form a photoresist base layer; and (c) forming a photoresist layer on the photoresist base layer. DETAILED DESCRIPTION

[0011] Reference will now be made in detail to exemplary embodiments, examples of which are shown in this specification. In this regard, exemplary embodiments of the present invention may have different forms and should not be construed as being limited to the descriptions described herein. Therefore, the following description will only illustrate aspects of this specification by describing exemplary embodiments. As used herein, the term "and / or" includes any and all combinations of one or more of the relevant listed items. When a statement such as "at least one of..." precedes a list of elements, it modifies the entire list of elements and does not modify a single element in the list.

[0012] As used herein, the terms "a / an" and "the" do not represent a limit to quantity and are interpreted as including both the singular and the plural unless otherwise indicated herein or clearly contradictory to the context. Unless otherwise expressly stated, "or" means "and / or". The modifier "about" used in conjunction with quantity includes the value and has the meaning specified by the context (e.g., including the degree of error associated with the measurement of a specific quantity). The full range disclosed herein includes endpoints, and the endpoints are independently combinable with each other. The suffix "(s)" is intended to include both the singular and the plural of the term it modifies, thereby including at least one of the terms. "Optional" or "optionally" means that the event or situation described subsequently may or may not occur, and the description includes examples of the occurrence of the event and examples in which it does not occur. The terms "first", "second" and similar terms do not represent order, quantity, or importance herein, 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 the other element or an intervening element may be present therebetween. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present. It will be understood that the components, elements, limitations, and / or features of the described aspects may be combined in any suitable manner in the various aspects.

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

[0014] As used herein, the term "hydrocarbyl" refers to an organic compound having at least one carbon atom and at least one hydrogen atom, which is optionally substituted where indicated by one or more substituents; "alkyl" refers to a straight or branched chain saturated hydrocarbon having the specified number of carbon atoms and having 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 (-OH) group; "alkoxy" refers to "alkyl-O-"; "carboxylic acid" refers to a group having the formula "-C(=O)-OH"; "cycloalkyl" refers to a group having the formula "-C(=O)-OH"; and "cycloalkyl" refers to a group having the formula "-C(=O)-OH". "Alkyl" refers to a monovalent group having one or more saturated rings in which all ring members are carbon; "cycloalkylene" refers to a cycloalkyl group having a valence of 2; "alkenyl" refers to a linear 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" means a group as used in the literature, particularly in IUPAC. 19, and refers to a monocyclic or polycyclic aromatic ring system comprising carbon atoms in one or more rings and optionally including one or more heteroatoms independently selected from N, O, S, Si, P, or B replacing one or more carbon atoms in said 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 heterocycloalkyl ring; "arylene" refers to an aryl group having a valence of at least 2; "alkylaryl" refers to an aryl group that has been substituted by an alkyl group; "arylalkyl" refers to an alkyl group that has been substituted by an aryl group; "aryloxy" refers to "aryl-O-"; and "arylthio" refers to "aryl-S-".

[0015] The prefix "hetero" means that the compound or group includes at least one member that is a heteroatom (e.g., 1, 2, 3, or 4, or more heteroatoms) replacing a carbon atom, wherein each heteroatom is independently N, O, S, Si, P, or B; a "heteroatom-containing group" refers to a substituent that includes at least one heteroatom; a "heteroalkyl" refers to an alkyl group having 1-4 heteroatoms replacing carbon; a "heterocycloalkyl" refers to a cycloalkyl group having 1-4 heteroatoms as ring members replacing carbon; a "heterocycloalkylene" refers to a heterocycloalkyl group having a valence of 2; a "heteroaryl" refers to an aryl group having 1-4 heteroatoms as ring members replacing carbon; and a "heteroarylene" refers to a heteroaryl group having a valence of 2.

[0016] The term "halogen" means a monovalent substituent of fluorine (fluoro), chlorine (chloro), bromine (bromo), or iodine (iodo). The prefix "halo" means a group comprising one or more of fluorine, chlorine, bromine, or iodine substituents replacing a hydrogen atom. Combinations of halides (e.g., bromine and fluorine) or only fluorine groups can be present.

[0017] The term "fluorinated" means a compound or group having one or more fluorine atoms incorporated therein. For example, when C 1-18 When a fluoroalkyl group is substituted, the fluoroalkyl group can include one or more fluorine atoms, such as a single fluorine atom, two fluorine atoms (e.g., 1,1-difluoroethyl), three fluorine atoms (e.g., 2,2,2-trifluoroethyl), or a fluorine atom on each free valence of a carbon (e.g., a perfluorinated group such as, -CF3, -C2F5, -C3F7, or -C4F9). "Substituted fluoroalkyl" should be understood to mean a fluoroalkyl group that is further substituted with another substituent.

[0018] "Substituted" means that at least one hydrogen atom on the group is replaced by another group, provided that the normal valence of the designated atom is not exceeded. When the substituent is oxo (i.e., =O), then two hydrogens on the carbon atom are replaced. Combinations of substituents or variables are permissible. Exemplary groups that may be present in a "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 Alkanoyl such as acyl), formyl (-C(=O)H), carboxylic acid or its alkali metal or ammonium salt; ester (including acrylate, methacrylate and lactone) such as C 2-6 Alkyl esters (-C(=O)O-alkyl or -OC(=O)-alkyl) and C 7-13 Aryl ester (-C(=O)O-aryl or -OC(=O)-aryl); amide (-C(=O)NR2, where R is hydrogen or C 1-6 alkyl), carboxamido (-CH2C(=O)NR2, wherein R is hydrogen or C 1-6 alkyl), halogen, mercapto (-SH), C 1-6 Alkylthio (-S-alkyl), thiocyano (-SCN), C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Halogenated alkyl, C 1-9 Alkoxy, C 1-6 Halogenated alkoxy, C 3-12 Cycloalkyl, C 5-18 Cycloalkenyl, C 6-12Aryl (e.g., phenyl, biphenyl, naphthyl, etc., each ring is substituted or unsubstituted aromatic), C 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 Alkyl aryl, C 4-12 Heterocycloalkyl, C 3-12 Heteroaryl, C 1-6 Alkylsulfonyl (-S(=O)2-alkyl), C 6-12 Arylsulfonyl (-S(=O)2-aryl), or tosyl (CH3C6H4SO2-). When a group is substituted, the number of carbon atoms indicated is the total number of carbon atoms in the group, excluding those of any substituents. For example, the group -CH2CH2CN is a C2 alkyl substituted with a cyano group.

[0019] As used herein, "inertly substituted" means that the substituent is substantially inert to the polymerization reaction of cyclopentadienone and acetylene and does not readily react under the conditions of use for curing the polymer, such as in water. Such substituents include, for example, -F, -Cl, -Br, -CF3, -OCH3, -OCF3, -O-Ph, C 1-8 Alkyl, or C 3-8 Cycloalkyl.

[0020] As noted above, there continues to be a need for new photoresist underlayer materials, such as SOC formulations having improved adhesion to inorganic substrates. The present inventors have discovered that the photoresist underlayer composition of the present invention comprising: a poly(arylene ether); an additive having formula (1); and a solvent can achieve improved adhesion to an underlying inorganic substrate relative to a similar SOC formulation that does not include the additive having formula (1).

[0021] As used herein, poly(arylene ether) is a matrix polymer having a backbone composed of repeating arylene units and oxygen-linked units in the backbone. As used herein, the term "poly(arylene ether)" refers to a compound having a substituted or unsubstituted aryleneoxy structural unit (-Ar-O-), wherein "Ar" is a divalent group derived from an aromatic hydrocarbon. "Poly(arylene ether)" may refer to a poly(arylene ether), a poly(aryletheretherketone), a poly(arylethersulfone), a poly(etherimide), a poly(etherimidazole), or a poly(etherbenzoxazole). In each of these compounds, there is at least one substituted or unsubstituted aryleneoxy structural unit (-Ar-O-).

[0022] Any compound containing two or more cyclopentadienone moieties capable of undergoing a Diels-Alder reaction can be suitably used as the first monomer for preparing the poly(arylene ether) of the present invention. Alternatively, a mixture of two or more different first monomers, each having two or more cyclopentadienone moieties, can be used as the first monomer. Preferably, only one first monomer is used. Preferably, the first monomer has two to four cyclopentadienone moieties, and more preferably has two cyclopentadienone moieties (also referred to herein as dicyclopentadienone). Suitable first monomers having two or more cyclopentadienone moieties are well known in the art, such as those described in U.S. Patent Nos. 5,965,679; 6,288,188; and 6,646,081; and in International Patent Publications WO 97 / 10193, WO 2004 / 073824, and WO 2005 / 030848 (all of which are incorporated herein by reference in their entirety).

[0023] The first monomer preferably has a structure represented by formula (1)

[0024]

[0025] Each R 10 Independently selected from H, C 1-6 -alkyl and optionally substituted C 5-20 -aryl; and Ar 3 is an aromatic moiety having 5 to 60 carbon atoms. In formula (1), “substituted C 5-20 -aryl" refers to a C 5-20 -Aryl: halogen, C 1-10 -alkyl, C 5-10 -Aryl, -C≡CC 5-10 -aryl or heteroatom-containing groups having 0 to 20 carbon atoms and one or more heteroatoms selected from O, S and N, preferably halogen, C 1-10 -alkyl, C 6-10 -Aryl and -C≡CC 6-10 As used herein, "substituted phenyl" refers to a phenyl moiety substituted with one or more of the following: halogen, C 1-10 -alkyl, C 5-10 -Aryl, -C≡CC 5-10 -aryl or a heteroatom-containing group having 0 to 20 carbon atoms and one or more heteroatoms selected from O, S and N, and preferably a phenyl moiety substituted by one or more of the following: halogen, C 1-10 -alkyl, C 6-10 -Aryl and -C≡CC 6-10-aryl, and more preferably phenyl and -C≡C-phenyl. Exemplary heteroatom-containing groups having 0 to 20 carbon atoms and one or more heteroatoms selected from O, S and N include, but are not limited to, hydroxyl, carboxyl, amino, C 1-20 -amido, C 1-10 -alkoxy, C 1-20 -Hydroxyalkyl, C 1-30 -hydroxyl (alkyleneoxy) etc. Preferably, each R 10 Independently selected from C 1-6 -alkyl, phenyl and substituted phenyl, more preferably, each R 10 is phenyl or substituted phenyl, and more preferably is phenyl or -C6H4-C≡C-phenyl. A variety of aromatic moieties are suitable for use as Ar 3 , such as those disclosed in U.S. Patent No. 5,965,679 (which application is incorporated herein by reference in its entirety). Preferably, Ar 3 having 5 to 40 carbons, and more preferably 6 or 30 carbons. 3 The aryl moiety includes pyridyl, phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, corundum, naphthyl, pentacene, tetraphenyl, benzotetraphenyl, triphenylene, perylene, biphenyl, binaphthyl, diphenyl ether, dinaphthyl ether, and those having the structure shown in formula (2)

[0026]

[0027] wherein x is an integer selected from 1, 2 or 3; y is an integer selected from 0, 1 or 2; each Ar 4 Independently selected from

[0028]

[0029] Each R 11 independently selected from halogen, C 1-6 -alkyl, C 1-6 -haloalkyl, C 1-6 -alkoxy, C 1-6 -haloalkoxy, phenyl and phenoxy; c3 is an integer from 0 to 4; d3 and e are each an integer from 0 to 3; each Z is independently selected from a single covalent chemical bond, O, S, NR 12 PR 12 、P(=O)R 12 、C(=O)、C(R 13 )(R 14 ) and Si(R 13 )(R 14 );R 12 、R 13 and R 14 Independently selected from H, C 1-4-alkyl, C 1-4 -haloalkyl and phenyl. Preferably, x is 1 or 2, and more preferably 1. Preferably, y is 0 or 1, and more preferably 1. Preferably, each R 11 independently selected from halogen, C 1-4 Alkyl, C 1-4 Halogenated alkyl, C 1-4 -alkoxy, C 1-4 -haloalkoxy and phenyl, and more preferably selected from fluoro, C 1-4 -alkyl, C 1-4 -fluoroalkyl, C 1-4 -alkoxy, C 1-4 -fluoroalkoxy and phenyl. Preferably, c3 is 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1. Preferably, d3 and e are each independently 0 to 2, and more preferably 0 or 1. In formula (4), preferably, d3 + e = 0 to 4, and more preferably 0 to 2. Each Z is preferably independently selected from O, S, NR 12 、C(=O)、C(R 13 )(R 14 ), and Si(R 13 )(R 14 ), more preferably selected from O, S, C(═O), and C(R 13 )(R 14 ), and more preferably selected from O, C(=O), and C(R 13 )(R 14 ). Preferably, each R 12 、R 13 and R 14 Independently selected from H, C 1-4 -alkyl, C 1-4 -fluoroalkyl and phenyl; and more preferably selected from H, C 1-4 -alkyl, C 1-2 -fluoroalkyl and phenyl. Preferably, Ar 3 The aryl moiety of Ar has at least one ether bond, more preferably at least one aromatic ether bond, and even more preferably one aromatic ether bond. 3 Having the structure of formula (2). Preferably, each Ar 4 Having formula (3), and more preferably, each Ar 4 It has the formula (3) and Z is O.

[0030] Any compound having an aryl moiety capable of undergoing a Diels-Alder reaction and two or more alkynyl groups can be suitably used as the second monomer for preparing the present polymer. Preferably, the second monomer has an aryl moiety substituted with two or more alkynyl groups. Preferably, a compound having an aryl moiety substituted with two to four, and more preferably two or three, alkynyl moieties is used as the second monomer. Preferably, the second monomer has an aryl moiety substituted with two or three alkynyl groups capable of undergoing a Diels-Alder reaction. Suitable second monomers are those having formula (5)

[0031]

[0032] Among them, Ar 1 and Ar 2 Each is independently C 5-30 -aryl moiety; each R is independently selected from H and optionally substituted C 5-30 -aryl; each R 1 Independently selected from -OH, -CO2H, C 1-10 -alkyl, C 1-10 -haloalkyl, C 1-10 -Hydroxyalkyl, C 2-10 -carboxyalkyl, C 1-10 -alkoxy, CN and halogen; each Y is independently a single covalent chemical bond or selected from -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, -(C(R 9 )2) z -、C 6-30 -aryl and -(C(R 9 )2) z1 -(C 6-30 -aryl)-(C(R 9 )2) z2 - a divalent linking group; each R 9 Independently selected from H, hydroxy, halogen, C 1-10 -alkyl, C 1-10 -haloalkyl and C 6-30 - aryl; a1 = 0 to 4; each a2 = 0 to 4; b1 = 1 to 4; each b2 = 0 to 2; a1 + each a2 = 0 to 6; b1 + each b2 = 2 to 6; d = 0 to 2; z = 1 to 10; z1 = 0 to 10; z2 = 0 to 10; and z1 + z2 = 1 to 10. Each R is preferably independently selected from H and C 6-20 -aryl, more preferably selected from H and C 6-10 aryl, and more preferably selected from H and phenyl. Preferably, each R 1 Independently selected from C 1-10 -alkyl, C 1-10 -haloalkyl, C1-10 -Hydroxyalkyl, C 1-10 -alkoxy and halogen, and more preferably selected from C 1-10 -alkyl, C 1-10 -haloalkyl and halogen. Preferably, each Y is independently a single covalent chemical bond or is selected from -O-, -S-, -S(=O)-, -S(=O)2-, -C(=O)-, -(C(R 9 )2) z -, and C 6-30 -aryl divalent linking group, and more preferably a single covalent chemical bond, -O-, -S-, -S(=O)2-, -C(=O)-, and -(C(R 9 )2) z -. Each R 9 Preferably, each of H, halogen, C 1-10 -alkyl, C 1-10 -haloalkyl, or C 6-30 -aryl, and more preferably fluorine, C 1-6 -alkyl, C 1-6 -fluoroalkyl, or C 6-20 - aryl. Preferably, a1 = 0 to 3, and more preferably 0 to 2. Preferably, each a2 = 0 to 2. Preferably, a1 + a2 = 0 to 4, more preferably 0 to 3, and even more preferably 0 to 2. Preferably, b1 = 1 to 3, and more preferably 1 or 2. Preferably, each b2 = 0 to 2; and more preferably 0 or 1. Preferably, b1 + each b2 = 2 to 4, and more preferably 2 or 3. Preferably, d = 0 or 1, and more preferably 0. Preferably, z = 1 to 6, more preferably 1 to 3, and even more preferably, z = 1. Preferably, z1 and z2 are each 0 to 5. Preferably, z1 + z2 = 1 to 6, and more preferably 2 or 6.

[0033] Ar 1 and Ar 2 Suitable aryl moieties include, but are not limited to, pyridyl, phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, coronenyl, naphthylene, pentaphenylene, tetraphenylene, benzonaphthylene, triphenylene, perylene, biphenylene, binaphthyl, diphenyl ether, dinaphthyl ether, carbazole, and fluorenyl. Preferably, Ar in formula (5) 1 and each Ar 2 Independently C 6-20 Aryl moiety. 1 and each Ar 2 Preferred aryl moieties of are phenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, naphthacene, pentacene, tetraphenyl, triphenylene and perylenyl.

[0034] Preferred second monomers of formula (5) are those of formula (6) and (7):

[0035]

[0036]

[0037] Among them, Ar 1 , R, R 1 , a1 and b1 are as defined above for formula (5); a3 is 0 or 2; a4 is 0 to 2; n1 and n2 are each independently 0 to 4; and Y 1 is a single covalent chemical bond, O, S, S(=O)2, C(=O), C(CH3)2, CF2, and C(CF3)2. Those skilled in the art will understand that the brackets ("[]") in formula (7) refer to the number of aromatic rings fused to the benzene ring. Thus, when n1 (or n2) = 0, the aromatic moiety is phenyl; when n1 (or n2) = 1, the aromatic moiety is naphthyl; when n1 (or n2) = 2, the aromatic moiety can be anthracenyl or phenanthrenyl; when n1 (or n2) = 3, the aromatic moiety can be naphthyl, tetraphenyl, triphenylene or pyrenyl; and when n1 (or n2) = 4, the aromatic moiety can be peryl or benzotetraphenyl. In formula (6), a1 is preferably 0 to 2, and more preferably 0. Preferably, b1 in formula (6) is 1 or 2. R is preferably H or phenyl. In each of equations (6) and (7), each R 1 Preferably independently selected from C 1-10 -alkyl, C 1-10 -haloalkyl, C 1-10 -Hydroxyalkyl, C 1-10 -alkoxy and halogen, and more preferably selected from C 1-10 -alkyl, C 1-10 -haloalkyl and halogen. Ar in formula (6) 1 Preferably, it is phenyl, naphthyl, anthracenyl, pyrenyl and peryl, more preferably phenyl, naphthyl and pyrenyl, and even more preferably phenyl. In formula (7), it is preferred that n1 and n2 are independently selected from 0, 1, 3 and 4, more preferably selected from 0, 1 and 3, and even more preferably selected from 1 and 3. It is further preferred that n1 = n2. In formula (7), Y 1 Preferably, it is a single covalent chemical bond, O, S(═O) 2 , C(═O), C(CH 3 ) 2 , CF 2 , or C(CF 3 ) 2 and more preferably, it is a single covalent chemical bond.

[0038] Particularly preferred monomers of formula (6) are monomers of formulae (8) to (12):

[0039]

[0040]

[0041] Where R and R 1 As described above for formula (6); a5 = 0 to 2; each of a6, a7, a8 and a9 is independently 0 to 4; b5 and b6 are each selected from 1 to 3; and b7, b8 and b9 are each selected from 2 to 4. Preferably, a5 = 0 or 1, and more preferably 0. Preferably, a6 is 0 to 3, more preferably 0 to 2, and even more preferably 0. Preferably, a7 and a9 are each independently 0 to 3, and more preferably 0 to 2. Preferably, b5 and b6 are each selected from 1 and 2. Preferably, b7, b8, and b9 are each 2 or 3. Compound (8) is more particularly preferred. Preferably, in compound (8), each R is independently H or phenyl, and more preferably each R is H or phenyl. More preferably, each R in formulas (8) to (12) 1 Independently selected from C 1-10 -alkyl, C 1-10 -haloalkyl, C 1-10 -Hydroxyalkyl, C 1-10 -alkoxy and halogen, and more preferably selected from C 1-10 -alkyl, C 1-10 -Haloalkyl and halogen.

[0042] In the monomers of formulae (5) to (12), any two alkynyl moieties may be in an ortho, meta, or para relationship to each other, and preferably are in a meta or para relationship to each other. Preferably, the alkynyl moieties in the monomers of formulae (5) to (12) are not in an ortho relationship to each other. Suitable monomers of formulae (5) to (12) are commercially available or can be readily prepared by methods known in the art.

[0043] Exemplary second monomers include, but are not limited to: 1,3-diethynylbenzene; 1,4-diethynylbenzene; 4,4'-diethynyl-1,1'-biphenyl; 3,5-diethynyl-1,1'-biphenyl; 1,3,5-triethynylbenzene; 1,3-diethynyl-5-(phenylethynyl)benzene; 1,3-bis(phenylethynyl)benzene; 1,4-bis(phenylethynyl)-benzene; 1,3,5-tris(phenylethynyl)benzene; 2,4,6-tris(phenylethynyl)anisole; 4,4'-bis(phenylethynyl)-1,1'-biphenyl; 4,4'-diethynyl-diphenyl ether; and mixtures thereof. More preferably, the monomer of formula (5) is selected from the group consisting of: 1,3-diethynylbenzene; 1,4-diethynylbenzene; 1,3,5-triethynylbenzene; 1,3,5-tris-(phenylethynyl)benzene; 4,4'-diethynyl-1,1'-biphenyl; 1,3-bis(phenylethynyl)-benzene; 1,4-bis(phenylethynyl)benzene; 4,4'-bis(phenylethynyl)-1,1'-biphenyl; and mixtures thereof. Even more preferably, the second monomer is selected from the group consisting of: 1,3-diethynylbenzene; 1,4-diethynylbenzene; 4,4'-diethynyl-1,1'-biphenyl; 1,3,5-triethynylbenzene; 1,3,5-tris(phenylethynyl)benzene; and mixtures thereof.

[0044] The poly(arylene ether) of the present invention may optionally further include one or more end-capping monomers as polymerized units. Preferably, only one end-capping monomer is used. As used herein, the term "end-capping monomer" refers to a monomer having a single dienophile moiety, wherein such dienophile moiety is used to cap one or more ends of the present polymer such that the capped ends of the polymer cannot undergo further Diels-Alder polymerization. Preferably, the dienophile moiety is an alkynyl moiety. Optionally, the end-capping monomer may include one or more solubility-enhancing polar moieties, such as those disclosed in U.S. Published Patent Application No. 2016 / 0060393 (which application is incorporated herein by reference in its entirety). Preferably, the end-capping monomer does not contain a solubility-enhancing polar moiety. Preferred end-capping monomers are those having formula (13)

[0045]

[0046] where R 20 and R 21 are each independently selected from H, optionally substituted C 1-10 Alkyl, optionally substituted C 7-12 Arylalkyl, or optionally substituted C 6-10 In some aspects, R 21 Suitable polar moieties are any hydrocarbyl moieties having from 1 to 20 carbon atoms and one or more functional groups selected from: -C(O)-R 130 、-C(O)OR130 , -OH, -NO2, and -NR 130 R 131 , where R 130 and R 131 Each independently selected from H, C 1-10 Alkyl, C 7-16 Arylalkyl, and C 6-10 Preferably, the polar moiety is selected from -C(O)-R 130 、-C(O)OR 130 , -OH and -NR 130 R 131 , and more preferably selected from -C(O)-R 130 、-C(O)OR 130 Such -C(O)-, -OH and -NR 130 R 131 The functional group may be part of another functional group, such as in a carboxylic acid, anhydride, amide, ketone, ester, etc. Preferably the polar moiety is selected from carboxyl, C 2-12 Aliphatic carboxylic acid esters, C 1-10 Hydroxyalkyl, C 6-10 Hydroxyaryl, C 7-20 Aryl carboxylic acid, C 8-20 -Arylcarboxylic acid anhydride, C 7-20 Aryl carboxylate, C 7-20 Arylamide, C 8-20 Aryl imide, C 1-10 aminoalkyl, and C 6-20 More preferably, the polar moiety is selected from carboxyl, C 2-12 Aliphatic carboxylic acid esters, C 1-10 Hydroxyalkyl, C 6-10 Hydroxyaryl, C 7-16 Aryl carboxylic acid, and C 8-16 Aryl carboxylic acid anhydrides. Other end-capping monomers include olefin compounds. When used, the end-capping monomer is typically used in a molar ratio of first monomer to end-capping monomer of 1:0.01 to 1:1.2.

[0047] Exemplary end-capping monomers include, but are not limited to, styrene; α-methylstyrene; β-methylstyrene; norbornadiene; ethynylpyridine; ethynylbenzene; ethynylnaphthalene; ethynylpyrene; ethynylanthracene; ethynylphenanthrene; diphenylacetylene; acetylenedicarboxylic acid; ethynylphenol; 4-ethynyl-1,1'-biphenyl; 1-propynylbenzene; propiolic acid; acetylenedicarboxylic acid; phenylpropiolic acid; ethynylbenzoic acid; ethynylphthalic acid; propargyl alcohol; propargylamine; 2-butyn-1,4-diol; 2-methyl-3-butyn-2-ol; 3-butyn-1-ol; 3-butyn-2 -alcohol; 2-butyn-1-ol; 2-butynoic acid; ethynylphenol; xylitol propiolate; ethynylphthalic anhydride; ethynylphthalimide; ethynylbenzamide; 2-butyne-1,4-diol diacetate; 3-butyn-2-one; 1-ethynyl-1-cyclohexanol; 1-ethynylcyclohexylamine; 1-ethynylcyclopentanol; ethynylaniline; N-(ethynylphenyl)acetamide; 2-carbamoyl-5-ethynylbenzoic acid; ethynyl-nitrobenzene; propynamide; N-hydroxy-propynamide; 2-aminobut-3-ynoic acid; and mixtures thereof. Preferred end-capping monomers are ethynylbenzene, norbornadiene, ethynylnaphthalene, ethynylpyrene, ethynylanthracene, ethynylphenanthrene, and 4-ethynyl-1,1'-biphenyl.

[0048] Poly (arylene ether) can be prepared by Diels-Alder polymerization of one or more first monomers and one or more second monomers and any optional end-capping monomers in a suitable organic solvent. The total mole of the second monomer used is greater than the total mole of the first monomer used. The molar ratio of the total first monomer to the total second monomer is typically 1: 1.01 to 1: 1.5, preferably 1: 1.05 to 1: 1.4, more preferably 1: 1.1 to 1: 1.3, more preferably 1: 1.15 to 1: 1.3, and even more preferably 1: 1.2 to 1: 1.3. The total mole of the first monomer and the total mole of the second monomer are typically calculated as the feed ratio of the monomer, but conventional matrix-assisted laser desorption / ionization (MALDI) time-of-flight (TOF) mass spectrometry can also be used, wherein silver trifluoroacetate is added to the sample to promote ionization. Suitable instrument is a Bruker Daltonics ULTRAFLEX MALDI-TOF mass spectrometer equipped with a nitrogen laser (wavelength is 337nm).

[0049] Suitable organic solvents that can be used to prepare the present polymers are benzyl esters of (C2-C6) alkanecarboxylic acids, dibenzyl esters of (C2-C6) alkanedicarboxylic acids, tetrahydrofurfuryl esters of (C2-C6) alkanecarboxylic acids, ditetrahydrofurfuryl esters of (C2-C6) alkanedicarboxylic acids, phenethyl esters of (C2-C6) alkanecarboxylic acids, diphenethyl esters of (C2-C6) alkanedicarboxylic acids, aromatic ethers, N-methylpyrrolidone (NMP), and gamma-butyrolactone (GBL). Preferred aromatic ethers are diphenyl ether, dibenzyl ether, (C1-C6) alkoxy-substituted benzenes, benzyl (C1-C6) alkyl ethers, NMP, and GBL, and more preferably (C1-C4) alkoxy-substituted benzenes, benzyl (C1-C4) alkyl ethers, NMP, and GBL. Preferred organic solvents are benzyl esters of (C2-C4) alkanecarboxylic acids, dibenzyl esters of (C2-C4) alkanedicarboxylic acids, tetrahydrofurfuryl esters of (C2-C4) alkanecarboxylic acids, ditetrahydrofurfuryl esters of (C2-C4) alkanedicarboxylic acids, phenethyl esters of (C2-C4) alkanecarboxylic acids, diphenethyl esters of (C2-C4) alkanedicarboxylic acids, (C1-C6) alkoxy-substituted benzyls, benzyl (C1-C6) alkyl ethers, NMP and GBL, and more preferably (C2-C6) alkanedicarboxylic acids. )alkanecarboxylic acid phenyl ester, (C2-C6)alkanecarboxylic acid tetrahydrofurfuryl ester, (C2-C6)alkanecarboxylic acid phenethyl ester, (C1-C4)alkoxy-substituted benzene, benzyl (C1-C4)alkyl ether, dibenzyl ether, NMP and GBL, and still more preferably (C2-C6)alkanecarboxylic acid benzyl ester, (C2-C6)alkanecarboxylic acid tetrahydrofurfuryl ester, (C1-C4)alkoxy-substituted benzene, benzyl (C1-C4)alkyl ether, NMP and GBL. Exemplary organic solvents include, but are not limited to, benzyl acetate, benzyl propionate, tetrahydrofurfuryl acetate, tetrahydrofurfuryl propionate, tetrahydrofurfuryl butyrate, anisole, methyl anisole, dimethyl anisole, dimethoxybenzene, ethyl anisole, ethoxybenzene, benzyl methyl ether, and benzyl ethyl ether, and preferably benzyl acetate, benzyl propionate, tetrahydrofurfuryl acetate, tetrahydrofurfuryl propionate, tetrahydrofurfuryl butyrate, anisole, methyl anisole, dimethyl anisole, dimethoxybenzene, ethyl anisole, and ethoxybenzene.

[0050] According to an embodiment, poly(arylene ether) can be prepared by combining the first monomer, the second monomer, any optional end-capping monomer and an organic solvent, each as described above, in any order in a container and heating the mixture. Preferably, the present polymer is prepared by combining the first monomer, the second monomer and an organic solvent, each as described above, in any order in a container and heating the mixture. Alternatively, the first monomer and the organic solvent can be first combined in a container, and then the second monomer is added to the mixture. In an alternative embodiment, the first monomer and the organic solvent mixture are first heated to the desired reaction temperature, and then the second monomer is added. The second monomer can be added all at once, or alternatively, can be added over a period of time, such as 0.25 to 6 hours, to reduce exothermic formation. The first monomer and the organic solvent mixture can be first heated to the desired reaction temperature, and then the second monomer is added. The blocked poly(arylene ether) of the present invention can be prepared by the following method: first, the first monomer, the second monomer and the organic solvent are combined in any order in a container and heated to prepare the poly(arylene ether), followed by separating the poly(arylene ether), and then combining the separated poly(arylene ether) with the end-capping monomer in an organic solvent, and heating the mixture for a period of time. Alternatively, the capped poly(arylene ether) of the present invention can be prepared by the following method: by combining the first monomer, the second monomer and the organic solvent in any order in a container and heating the mixture for a period of time to provide the desired poly(arylene ether), then adding the capping monomer to the reaction mixture containing the poly(arylene ether), and heating the reaction mixture for a period of time. The reaction mixture is heated at a temperature of 100°C to 250°C. Preferably, the mixture is heated to a temperature of 150°C to 225°C, and more preferably to a temperature of 175°C to 215°C. Typically, the reaction is allowed to proceed for 2 to 20 hours, preferably 2 to 8 hours, and more preferably 2 to 6 hours, wherein the shorter the reaction time, the lower the molecular weight of the poly(arylene ether). The reaction can be carried out in an oxygen-containing atmosphere, but an inert atmosphere such as nitrogen is preferred. After the reaction, the resulting poly(arylene ether) can be separated from the reaction mixture or used as is to coat a substrate.

[0051] Without intending to be bound by theory, it is believed that the poly(arylene ether) of the present invention is formed by a Diels-Alder reaction of the cyclopentadienone moiety of the first monomer with the alkynyl moiety of the second monomer upon heating. During this Diels-Alder reaction, carbonyl-bridged species are formed. Those skilled in the art will appreciate that such carbonyl-bridged species may be present in the polymer. Upon further heating, the carbonyl-bridged species will be substantially completely converted to an aromatic ring system. Due to the molar ratios of the monomers used, the polymers of the present invention contain arylene rings within the poly(arylene ether) backbone.

[0052] Exemplary poly(arylene ether) compounds include the following:

[0053]

[0054] wherein Ph is phenyl and n is an integer from 1 to 100, preferably from 2 to 50, more preferably from 2 to 10.

[0055] In order to increase the solubility of the polymer, one or more first monomers and / or one or more second monomers may be substituted with a polar moiety, such as those disclosed in U.S. Published Patent Application No. 2017 / 0009006 (incorporated herein by reference in its entirety). Suitable solubility-enhancing polar moieties include, but are not limited to, hydroxyl, carboxyl, sulfhydryl, nitro, amino, amido, sulfonyl, sulfonamide moieties, ester moieties, quaternary amino moieties, and the like. Exemplary first monomers with one or more solubility-enhancing polar moieties are disclosed in U.S. Patent Application Serial No. 15 / 790606, filed October 27, 2017 (incorporated herein by reference in its entirety). Exemplary second monomers with one or more solubility-enhancing polar moieties are those disclosed in U.S. Published Patent Application No. 2017 / 0009006 (incorporated herein by reference in its entirety). Preferably, the one or more first monomers do not contain a solubility-enhancing polar moiety. Preferably, the one or more second monomers do not contain a solubility-enhancing polar moiety. More preferably, one or more of the first monomer and the second monomer do not contain a solubility-enhancing polar moiety.

[0056] The poly(arylene ether) typically has a weight average molecular weight (Mw) of 1,000 to 100,000 Daltons (Da), preferably 1,000 to 50,000 Da, more preferably 2,000 to 10,000 Da, still more preferably 2,500 to 5,000 Da, even more preferably 2,700 to 5,000 Da, and still more preferably 3,000 to 5,000 Da. w The poly(arylene ether) typically has a number average molecular weight (M) of 1,500 to 50,000 Da. n The poly(arylene ether) has a polydispersity index (PDI) of 1 to 5, preferably 1 to 3, more preferably 1 to 2, still more preferably 1 to 1.9, and still more preferably 1.25 to 1.75. n and M wThe molecular weight of the poly(arylene ether) is 1,000 to 5,000 Da. The molecular weight of the poly(arylene ether) is 1,000 to 5,000 Da. The molecular weight of the poly(arylene ether) is 1,000 to 5,000 Da. w , a PDI of 1.25 to 1.75, and a ratio of the total moles of the first monomer to the total moles of the second monomer of 1:1.2 to 1:1.3.

[0057] Examples of commercially available poly(arylene ether)s include SILK semiconductor dielectrics (from The Dow Chemical Company), FLARE dielectrics (from Allied Signal, Inc.), and VELOX (poly(arylene ether)) (from Air Products / Shumacher). One preferred class of poly(arylene ether) polymers are thermally curable mixtures or b-staged products of poly(cyclopentadienone) and poly(acetylene), such as those described in WO 98 / 11149 (the teachings of which are incorporated herein by reference). Examples of precursors that can be used to prepare the poly(arylene ether)s of the present invention include monomers such as aromatic compounds substituted on the aromatic ring with acetylene groups in ortho positions to each other, as shown in WO 97 / 10193 (incorporated herein by reference); cyclopentadienone-functional compounds in combination with aromatic acetylene compounds, as shown in WO 98 / 11149 (incorporated herein by reference); and the poly(arylene ethers) of U.S. Pat. Nos. 5,115,082; 5,155,175; 5,179,188; 5,874,516; 5,965,679; and PCT WO 91 / 09081; WO 97 / 01593 and EP 0755957-81, each of which is incorporated herein by reference.

[0058] When the poly(arylene ether) comprises a thermally curable mixture or b-staged product of a poly(cyclopentadienone) and a poly(acetylene), the precursor is preferably characterized so that branching occurs relatively early in the cure process. The formation of a branched matrix early in the cure process minimizes the decrease in the modulus of the matrix and helps minimize pore collapse during cure, and / or allows the use of porogens that decompose or degrade at lower temperatures. One method of achieving this is to use a ratio of cyclopentadienone functional groups to acetylene functional groups in the precursor composition that is greater than about 3:4 and preferably less than about 2:1, more preferably about 1:1. A poly(arylene ether) prepared from a curable mixture comprising 3 parts 3,3'-(oxydi-1,4-phenylene)bis(2,4,5-triphenylcyclopentadienone) (DPO-CPD) and 2 parts 1,3,5-tris(phenylethynyl)benzene (TRIS) (molar ratio) is an example of such a system. Alternatively, an additional agent capable of crosslinking the heat-curable mixture or b-staged product of the poly(cyclopentadienone) and poly(acetylene) can be added to minimize the loss of modulus of the poly(arylene ether) during curing. Examples of suitable agents include bis-o-diacetylenes, such as disclosed, for example, in WO 97 / 10193 (incorporated herein by reference); mono-o-diacetylenes; bis-triazenes; tetrazines, such as 1,3-diphenyltetrazine; bis-azides, such as bis-sulfonyl azide; and peroxides, such as bis-peroxides.

[0059] The poly(arylene ether) is typically present in the photoresist underlayer composition in an amount of 10 to 99.9 weight percent, typically 25 to 99 weight percent, and more typically 50 to 99 weight percent, based on the total solids of the photoresist underlayer composition.

[0060] The additive of formula (14) is a compound having the following structure:

[0061] D-(L 1 -Ar-[X] n ) m (14)

[0062] wherein each Ar is independently a monocyclic or polycyclic C 5-60 an aromatic group; m is an integer from 1 to 6; and each n is independently an integer from 0 to 5, provided that the sum of n is 2 or greater.

[0063] In an embodiment, the monocyclic or polycyclic C 5-60 Aromatic groups can be monocyclic or polycyclic C 6-60 Arylene, or monocyclic or polycyclic C 5-60 Heteroarylene. When C 5-60When the aromatic group is polycyclic, the ring or ring groups may be fused (such as naphthyl, etc.), directly connected (such as biaryl, biphenyl, etc.), and / or bridged by heteroatoms (such as triphenylamino or diphenylene ether). In an embodiment, the polycyclic aromatic group may include a combination of fused and directly connected rings (such as binaphthyl, etc.). For convenience, the monocyclic or polycyclic C 5-60 Aromatic groups may be referred to herein as "Ar groups."

[0064] In addition to the substituent X, each monocyclic or polycyclic C 5-60 The aromatic group may be further substituted. Exemplary substituents include, but are not limited to, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Haloalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 1-30 Heterocycloalkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 7-30 Alkylaryl, substituted or unsubstituted C 3-30 Heteroaryl, substituted or unsubstituted C 4-30 heteroarylalkyl, or halogen.

[0065] It should be understood that when "monocyclic or polycyclic C 6-60 When the "arylene group" is polycyclic, the number of carbon atoms is sufficient to make the group chemically feasible. For example, "monocyclic or polycyclic C 6-60 "Arylene" may refer to "monocyclic C 6-60 Arylene or polycyclic C 10-60 Arylene"; or for example "monocyclic C 6-30 Arylene or polycyclic C 12-60 Similarly, when "monocyclic or polycyclic C 5-60 When the "heteroarylene" is polycyclic, the number of carbon atoms is sufficient to make the group chemically feasible. For example, "monocyclic or polycyclic C 5-60 "Heteroarylene" may refer to "monocyclic C 5-60 Heteroarylene or polycyclic C 10-60 Heteroarylene"; or for example "monocyclic C 5-30 Heteroarylene or polycyclic C 12-60 "Heteroarylene".

[0066] In formula (1), D is substituted or unsubstituted C 1-60 The organic group and optionally substituted or unsubstituted C1-60 Typically, D can be a polyvalent C 1-30 Alkyl, polyvalent C 3-30 Cycloalkyl, polyvalent C 1-20 Heterocycloalkyl, polyvalent C 6-30 Aryl, polyvalent C 6-30 Heteroaryl, -NH2 or its organic acid salt, or -C(O)OR 22 , where R 22 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 Heterocycloalkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 7-30 Alkylaryl, substituted or unsubstituted C 3-30 Heteroaryl, substituted or unsubstituted C 4-30 More preferably, D can be a polyvalent C 1-30 Alkyl, polyvalent C 3-30 Cycloalkyl, polyvalent C 6-30 Aryl, or polyvalent C 6-30 Heteroaryl.

[0067] In formula (1), each L 1 is independently a single bond or a divalent linking group. 1 When it is a single bond, D can be a substituted or unsubstituted C optionally fused to Ar. 3-30 Cycloalkyl or substituted or unsubstituted C 1-20 Heterocycloalkyl. When D is a polyvalent C 6-30 Aryl or polyvalent C 6-30 When heteroaryl, and when L 1 When it is a single bond, D can form a condensed polycyclic system together with Ar.

[0068] Exemplary divalent linking groups include one or more of the following: substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 2-30 Alkenylene, substituted or unsubstituted C 4-30 Cycloalkenylene, substituted or unsubstituted C 2-30 Alkynylidene, substituted or unsubstituted C 1-30 Heterocycloalkylene, substituted or unsubstituted C 6-30Arylene, substituted or unsubstituted C 4-30 Heteroarylene, -O-, -C(O)-, -C(O)O-, -NR 23 -, -S-, -S(O)-, -S(O)2-, or -C(O)NR 23 -, where R 23 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 Heterocycloalkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 7-30 Alkylaryl, substituted or unsubstituted C 3-30 Heteroaryl, substituted or unsubstituted C 4-30 Heteroarylalkyl.

[0069] In some aspects, D can be a polyvalent C 6-30 Aryl or polyvalent C 6-30 When heteroaryl, and when L 1 When is a single bond, D can form a condensed polycyclic ring system together with Ar. In some aspects, D can be a fused, condensed or spirocyclic polyvalent cycloalkyl moiety, wherein the cycloalkyl and Ar can optionally form a fused ring.

[0070] In order to increase adhesion to the substrate, the additive includes at least one protected or free polar functional group X. As used herein, the term "polar functional group" refers to a functional group that includes at least one heteroatom. The additive may include an aromatic or heteroaromatic group having at least one protected or free functional group selected from hydroxyl, sulfhydryl and amino groups. As used herein, the term "free functional group" refers to an unprotected functional group. Thus, the term "free hydroxyl" refers to "-OH", the term "free sulfhydryl" refers to "-SH", and the term "free amino" refers to "-NH2". As used herein, the term "protected functional group" refers to a functional group terminated by a protecting group that reduces or eliminates the reactivity of the free functional group. Protecting groups may optionally include -O-, -NR- (wherein R is hydrogen or C 1-10 alkyl), -C(=O)-, or a combination thereof.

[0071] The protecting group may include formyl, substituted or unsubstituted straight or branched C 1-10 Alkyl, substituted or unsubstituted C 3-10 Cycloalkyl, substituted or unsubstituted C 2-10Alkenyl, substituted or unsubstituted C 2-10 Alkynyl or a combination thereof. On any portion of the protecting group, the protecting group may include -O-, -NR- (wherein R is hydrogen or C 1-10 alkyl), -C(=O)-, or a combination thereof.

[0072] In an embodiment, the functional group may be a hydroxyl group, which may be protected as an alkyl ether to form the structure OR 24 , where R 24 It is C 1-10 Straight-chain or branched alkyl groups. Preferred alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl.

[0073] In another embodiment, the protecting group can be formyl-C(=O)H or C 2-10 Alkanoyl-C(=O)R 25 ,in 25 It is C 1-10 Straight or branched chain alkyl. Preferably, C 2-10 Alkanoyl is acetyl -C(=O)CH3 or propionyl -C(=O)CH2CH3. The functional group can be a hydroxyl protected by acetyl or propionyl to form the ester -OC(=O)CH3 or -OC(=O)CH2CH3, respectively.

[0074] In another embodiment, the hydroxyl group can be protected as a carbonate to form the structure -OC(=O)OR 26 , where R 26 It is C 1-10 Straight or branched alkyl. Preferred carbonate groups include -OC(=O)OCH3, -OC(=O)OCH2CH3, -OC(=O)OCH2CH2CH3, -OC(=O)OCH(CH3)2 or -OC(=O)OC(CH3)3. In another embodiment, the hydroxyl group can be protected as a carbamate to form the structure -OC(=O)NR 27 R 28 , where R 27 and R 28 Each is independently C 1-10 Straight or branched chain alkyl groups. Preferred carbamate groups include -OC(=O)NHCH3, -OC(=O)NHCH2CH3, -OC(=O)NHCH2CH2CH3, -OC(=O)NHCH(CH3)2, -OC(=O)NHC(CH3)3, or -OC(=O)N(CH3)2.

[0075] In one embodiment, the protecting group can be a polymerizable group comprising a substituted or unsubstituted C 2-10 Alkenyl, substituted or unsubstituted C 2-10 alkynyl or a combination thereof.

[0076] In formula (14), each X is independently -OR 30 、-SR 31 , or -NR 32 R 33 , where R 30 to R 33 are each independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, 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, each of which, except hydrogen, optionally further comprises as part of its structure one or more of: substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 2-30 Alkenylene, substituted or unsubstituted C 4-30 Cycloalkenylene, substituted or unsubstituted C 2-30 Alkynylidene, substituted or unsubstituted C 1-30 Heterocycloalkylene, substituted or unsubstituted C 6-30 Arylene, substituted or unsubstituted C 4-30 heteroarylene, -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -S(O)2-, or -NR 34 -, where R 34 is substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 1-20 Heterocycloalkyl, 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 4-30 Heteroaryl, substituted or unsubstituted C 5-30 Heteroarylalkyl, or substituted or unsubstituted C 5-30 It is understood that the substituent X does not include structures containing unstable chemical moieties such as -OO-.

[0077] In one aspect, in formula (14), each X is independently -OR 30 or -NR 32 R 33 , m is an integer from 2 to 4, and the sum of n is 3 or greater. In another aspect, in formula (1), each X is independently -OR 30 , where each R 30 are independently hydrogen, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted -C(O)-C 1-6 Alkyl (substituted or unsubstituted C 2-8 Alkanoyl), substituted or unsubstituted C 3-10 Cycloalkyl, substituted or unsubstituted C 2-30 Alkynyl, 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.

[0078] In formula (14), when n is 2, optionally R of the first group X 30 to R 33 Any one of them is a divalent group, and R of the second group X 30 to R 33 Any one of the above is a divalent group, and the divalent group of the first group X and the divalent group of the second group X together form a ring, wherein the ring optionally further comprises a linking group, the linking group comprising one or more of the following: substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 2-30 Alkenylene, substituted or unsubstituted C 4-30 Cycloalkenylene, substituted or unsubstituted C 2-30 Alkynylidene, substituted or unsubstituted C 6-30 Arylene, -O-, -C(O)-, -C(O)O-, -NR 35 -, -S-, -S(O)-, or -S(O)2-, where R 35 is substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 1-20 Heterocycloalkyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C7-30 Alkylaryl, substituted or unsubstituted C 4-30 Heteroaryl, substituted or unsubstituted C 5-30 Heteroarylalkyl, or substituted or unsubstituted C 5-30 Alkylheteroaryl.

[0079] In some aspects, the additive can be a compound having formula (15):

[0080]

[0081] In formula (15), D is as defined above for formula (14), and each Ar 5 Is a monocyclic or polycyclic C 6-60 Arylene or monocyclic or polycyclic C 5-60 Heteroarylene, each X is independently -OR 30 、-SR 31 , or -NR 32 R 33 , m is an integer from 2 to 4, and each n is independently an integer from 1 to 5, with the proviso that the sum of n is 3 or greater.

[0082] In yet another aspect, in formula (14), D can be -(C(O)O - )(M + ) or -(NH3 + )(Z - ), where M + is an organic cation and Z - is an organic anion. In this regard, each L 1 is independently a divalent linking group comprising one or more of the following: substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 2-30 Alkenylene, substituted or unsubstituted C 4-30 Cycloalkenylene, substituted or unsubstituted C 2-30 Alkynylidene, substituted or unsubstituted C 6-30 Arylene, -O-, -C(O)-, -C(O)O-, -NR 36 -, -S-, -S(O)-, -S(O)2-, or -C(O)NR 36 -, m is 1, each Ar is independently a monocyclic or polycyclic C 5-60 Aromatic group, each X is independently -OR 30 、-SR 31 , or -NR 32 R 33 , n is an integer from 2 to 4, R 36 is hydrogen, substituted or unsubstituted C1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 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, and R 30 to R 33 As disclosed herein.

[0083] For example, the additive compound may have formula (16):

[0084]

[0085] Where Z is an organic anion, L 1 is a single bond or a divalent linking group comprising one or more of the following: substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 2-30 Alkenylene, substituted or unsubstituted C 4-30 Cycloalkenylene, substituted or unsubstituted C 2-30 Alkynylidene, -O-, -C(O)-, -C(O)O-, -NR 23 -, -S-, -S(O)-, or -S(O)2-, each R b are independently substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 1-30 Heterocycloalkyl, 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 4-30 Heteroaryl, substituted or unsubstituted C 5-30 Heteroarylalkyl, or substituted or unsubstituted C 5-30 Alkylheteroaryl, -OR 30 、-SR 31 , or -NR 32 R 33 , p is an integer from 0 to 3, and R 23 and R 30 to R 33 Same as defined in this article.

[0086] Exemplary additive compounds include the following:

[0087]

[0088] Where X is -OR c 、-SR c , or -NR d R e ; A is -O-, -S-, or -NR d -; and R c 、R d and R e are each independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, 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, each of which, except hydrogen, optionally further comprises as part of its structure one or more of: substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 2-30 Alkenylene, substituted or unsubstituted C 4-30 Cycloalkenylene, substituted or unsubstituted C 2-30 Alkynylidene, substituted or unsubstituted C 1-30 Heterocycloalkylene, substituted or unsubstituted C 6-30 Arylene, substituted or unsubstituted C 4-30 heteroarylene, -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -S(O)2-, or -NR 37 -, where R 37 is substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 1-20 Heterocycloalkyl, 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 4-30 Heteroaryl, substituted or unsubstituted C5-30 Heteroarylalkyl, or substituted or unsubstituted C 5-30 Alkylheteroaryl.

[0089] Other exemplary additive compounds include the following:

[0090]

[0091]

[0092] wherein X is as defined herein.

[0093] Still other exemplary additive compounds include the following:

[0094]

[0095]

[0096] wherein A and X are as defined herein.

[0097] Still other exemplary additive compounds include the following:

[0098]

[0099]

[0100] wherein A and X are as defined herein.

[0101] The additive having formula (14) is typically present in the photoresist underlayer composition in an amount of 0.1 to 20 wt % based on the total solids of the photoresist underlayer composition.

[0102] Various solvents can be used for photoresist bottom layer composition of the present invention, such as but not limited to alcohol, glycol ether, lactone, ester, ether, ketone, water and aromatic hydrocarbon. Preferably, relatively polar solvents are used, such as alcohol, glycol ether, lactone, ester, ether, ketone or water. A mixture 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), methyl 3-methoxypropionate (MMP), ethyl lactate, n-butyl acetate, anisole, N-methylpyrrolidone (NMP), gamma-butyrolactone (GBL), gamma-valerolactone, delta-valerolactone, ethyl lactate, 1,4-dioxane, cyclohexanone, cyclopentanone, methyl ethyl ketone, water, mesitylene, xylene, anisole, 4-methylanisole, ethoxybenzene, benzyl propionate, benzyl benzoate, cyclohexanone, cyclopentanone, propylene carbonate, xylene, mesitylene, cumene, limonene, and the like, and combinations thereof. The preferred solvent is methyl alcohol, ethanol, propyl alcohol, propylene glycol, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, gamma-butyrolactone, gamma-valerolactone, delta-valerolactone, ethyl lactate, 1,4-diox, pimelinketone and water.When using solvent mixture, the ratio of solvent is not critical usually, and can change from 99:1 to 1:99 weight / weight (w / w), and condition is that solvent mixture can dissolve the component of composition.It will be appreciated by those skilled in the art that, as can be according to hope, can regulate the concentration of component in organic solvent by removing a part of organic solvent or by adding more organic solvent.

[0103] The photoresist bottom layer composition may include optional additives, such as curing agent, cross-linking agent, surface leveling agent or any combination thereof. The selection of such optional additives and their amount are fully within the ability of those skilled in the art. Curing agent is typically present in an amount of 0 to 20 wt % based on total solids and preferably 0 to 3 wt %. Cross-linking agent is typically used in an amount of 0 to 30 wt % based on total solids and preferably 0 to 10 wt %. Surface leveling agent is typically used in an amount of 0 to 5 wt % based on total solids and preferably 0 to 1 wt %. The selection of such optional additives and their usage are within the ability of those skilled in the art.

[0104] Optionally, the base composition of the present invention may further include one or more curing agents to assist in the curing of the deposited polymer film. A curing agent is any component that cures the base composition on the substrate surface. A preferred curing agent is a thermal acid generator (TAG). A TAG is any compound that releases acid when exposed to heat. Thermal acid generators are well known in the art and are commercially available 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. It will also be understood by those skilled in the art that certain photoacid generators are capable of releasing acid when heated and can be used as thermal acid generators. The amount of such curing agents that can be used in the composition of the present invention can be, for example, greater than 0 to 10 wt % based on the total solids of the base composition, and typically greater than 0 to 3 wt %.

[0105] Preferred curing agents are acids, photoacid generators, and thermal acid generators. Suitable acids include, but are not limited to: arylsulfonic acids, such as p-toluenesulfonic acid; alkylsulfonic acids, such as methanesulfonic acid, ethanesulfonic acid, and propanesulfonic acid; perfluoroalkylsulfonic acids, such as trifluoromethanesulfonic acid; and perfluoroarylsulfonic acids. A photoacid generator is any compound that releases an acid when exposed to light. A thermal acid generator is any compound that releases an acid when exposed to heat. Thermal acid generators are well known in the art and are commercially available. For a discussion of the use of photoacid generators, see U.S. Patent No. 6,261,743 (which application is incorporated herein by reference in its entirety). 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, for example, amine-terminated dodecylbenzenesulfonic acid. Those skilled in the art will also appreciate that certain photoacid generators are capable of releasing acid upon heating and can function as thermal acid generators.

[0106] Examples of crosslinking agents can be amine-based crosslinking agents such as melamine materials, including melamine resins such as those manufactured by Cytec Industries and sold under the trade names CYMEL 300, 301, 303, 350, 370, 380, 1116, and 1130; glycolurils, including those available from Cytec Industries; and guanamine and urea-based materials, including resins such as guanamine resins available from Cytec Industries under the names CYMEL 1123 and 1125, and urea resins available from Cytec Industries under the names POWDERLINK 1174 and 1196. In addition to being commercially available, such amine-based resins can be prepared, for example, by the reaction of acrylamide or methacrylamide copolymers with formaldehyde in a solution containing an alcohol, or alternatively by copolymerization of N-alkoxymethylacrylamide or methacrylamide with other suitable monomers. Examples of the cross-linking agent may be epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, alicyclic epoxy resin, and glycidylamine epoxy resin.

[0107] The bottom composition of the present invention may optionally include one or more surface leveling agents (or surfactants) and antioxidants. Typical surfactants include those that exhibit amphiphilic properties, and amphiphilic properties mean that they can be hydrophilic and hydrophobic at the same time. 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 (oxyalkylene) surfactants, and fluorochemical 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 side-chain secondary alcohol ethoxylates, such as TERGITOL TMN-6 (Dow Chemical Company, Midland, Michigan, USA) and PF-656 (Omnova Solutions, Beachwood, Ohio, USA). Still other exemplary surfactants include alcohol (primary and secondary) 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, published in 2000 by Manufacturers Confectioners Publishing Co., Glen Rock, NJ. Nonionic surfactants that are derivatives of acetylenic diols may also be suitable. Such surfactants are commercially available from Air Products and Chemicals, Inc., Allentown, PA, and are sold under the trade names SURFYNOL and DYNOL. Additional suitable surfactants include other polymeric compounds such as the triblock EO-PO-EO copolymers PLURONIC 25R2, L121, L123, L31, L81, L101, and P123 (BASF, Inc.) If used, such surfactants can be present in the composition in small amounts, for example, greater than 0 to 1 wt % based on the total solids of the primer composition.

[0108] Antioxidants can be added to the bottom layer composition to prevent or minimize the oxidation of the organic materials in the composition. Suitable antioxidants include, for example, phenol-based antioxidants, antioxidants consisting of organic acid derivatives, sulfur-containing antioxidants, phosphorus-based antioxidants, amine-based antioxidants, antioxidants consisting of amine-aldehyde condensates, and antioxidants consisting of amine-ketone condensates. Examples of phenol-based antioxidants include substituted phenols such as 1-oxy-3-methyl-4-isopropylbenzene, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, butylated hydroxyanisole, 2-(1-methylcyclohexyl)-4,6-dimethylphenol, 2,4-dimethyl-6-tert-butylphenol, 2-methyl-4,6-dinonylphenol, 2,6-di-tert-butyl-α-dimethylamino-p-cresol, 6-(4-hydroxy-3,5-di-tert-butylanilino)-2,4-dioctyl-thio-1,3,5-triazine, n-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenyl) propionate, octylated phenols, arylalkyl-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-cross-linked polyvalent alkylphenols, 4,4'-butylenebis-(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 tetrakis-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane. Suitable antioxidants are commercially available, for example, Irganox TM Antioxidant (Ciba Specialty Chemicals Corp.) If used, the antioxidant can be present in the primer composition in an amount, for example, greater than 0 to 1 wt % based on the total solids of the primer composition.

[0109] Another aspect of the present invention provides a coated substrate comprising a layer of a photoresist base composition disposed on a substrate; and a photoresist layer disposed on the base composition layer. The coated substrate may further comprise a silicon-containing layer and / or an organic anti-reflective coating disposed above the base composition and below the photoresist layer.

[0110] The above compositions can be used to deposit a photoresist underlayer composition comprising an additive and a poly(arylene ether) as a coating on a patterned semiconductor device substrate, wherein the coating has a suitable thickness, such as 10 nm to 500 μm, preferably 25 nm to 250 μm, and more preferably 50 nm to 125 μm, although such coatings can be thicker or thinner than these ranges depending on the specific application. The compositions of the present invention substantially fill, preferably fill, and more preferably completely fill multiple gaps on a patterned semiconductor device substrate. The poly(arylene ether)s of the present invention are advantageous in that they planarize (form a planar layer on a patterned substrate) and fill gaps, wherein substantially no voids are formed, and preferably no voids are formed.

[0111] Preferably, after coating on the surface of the patterned semiconductor device substrate, the resist base composition is heated (soft baked) to remove the organic solvent present. Typical baking temperatures are 80°C to 240°C, although other suitable temperatures can be used. This baking to remove residual solvents is typically carried out for about 30 seconds to 10 minutes, although longer or shorter times can be used appropriately. After solvent removal, a layer, film or coating of the resist base on the substrate surface is obtained. Preferably, the resist base is then cured to form an insoluble film. Typically, this curing is achieved by heating, such as being heated to a temperature of ≥300°C, preferably ≥350°C and more preferably ≥400°C. Such a curing step can take 1 to 180 minutes, preferably 1 to 60 minutes and more preferably 1 to 10 minutes, although other suitable times can be used. This curing step can be carried out in an oxygen-containing atmosphere or in an inert atmosphere and is preferably carried out in an inert atmosphere.

[0112] Yet another aspect of the present invention provides a method for forming a pattern. The method comprises: (a) applying a layer of an underlying composition to a substrate; (b) curing the applied underlying composition to form an underlying layer; and (c) forming a photoresist layer on the underlying layer. The method may further comprise forming a silicon-containing layer and / or an organic anti-reflective coating on the underlying layer before forming the photoresist layer. The method may further comprise patterning the photoresist layer and transferring the pattern from the patterned photoresist layer to the underlying layer and a layer below the underlying layer.

[0113] As used herein, the term "underlayer" refers to all removable processing layers between the substrate and the photoresist layer, such as organic antireflective agent layers, silicon-containing interlayers, spin-on carbon layers, and photoresist underlayers.

[0114] A variety of substrates can be used in the patterning method, with electronic device substrates being typical. Suitable substrates include, for example, package 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; etc. Suitable substrates can be in the form of wafers, such as those used to manufacture integrated circuits, optical sensors, flat panel displays, integrated optical circuits, and LEDs. As used herein, the term "semiconductor wafer" is intended to encompass "electronic device substrates," "semiconductor substrates," "semiconductor devices," and various packages for various interconnect levels, including single-chip wafers, multi-chip wafers, packages for various levels, or other components requiring solder connections. Such substrates can be of any suitable size. Typical wafer substrate diameters are 200 mm to 300 mm, although wafers with smaller and larger diameters can be appropriately used according to the present 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 or is being mass-produced.

[0115] The substrate is typically composed of one or more of silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. The substrate may include one or more layers and patterned features. The layers may include, for example, one or more conductive layers, such as aluminum, copper, molybdenum, tantalum, titanium, tungsten, alloys of these metals, nitrides or silicides, 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 single crystal silicon; and combinations thereof. Different techniques can form the layers, 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.

[0116] Can be coated on substrate with bottom composition by any suitable means such as spin coating, slot die coating, blade coating, curtain coating, roller coating, spray coating, dip coating etc.In the situation of semiconductor wafer, spin coating is preferred.In typical spin coating method, bottom composition is applied to the substrate that rotates with the speed of 500 to 4000rpm and continues 15 to 90 seconds to obtain the layer of bottom composition of hope on substrate.Those skilled in the art will appreciate that the thickness of the bottom composition of coating can be regulated by changing the solid content of rotational speed and composition.The bottom formed by bottom composition typically has the dry layer thickness of 5nm to 50 μ m, typically 25nm to 3 μ m and more typically 50 to 500nm.Can apply bottom composition to fill basically, preferably fill and more preferably fill the multiple gaps on substrate fully.

[0117] The applied primer composition is optionally soft-baked at a relatively low temperature to remove any solvents and other relatively volatile components in the composition. Exemplary baking temperatures may be between 60°C and 240°C, although other suitable temperatures may be used. This baking to remove residual solvent may be performed for 10 seconds to 10 minutes, although longer or shorter times may be used as appropriate. When the substrate is a wafer, this baking step may be performed by heating the wafer on a hot plate.

[0118] Then the applied photoresist bottom layer composition is cured to form a bottom layer, for example a photoresist bottom layer. The photoresist bottom layer composition should be fully cured so that the bottom layer is not mixed with the layer applied subsequently (such as the photoresist or other organic or inorganic layer directly arranged on the bottom layer) or is mixed to the minimum extent. The photoresist bottom layer composition can be cured in an oxygen-containing atmosphere (such as air) or in an inert atmosphere (such as nitrogen) and under conditions (such as heating) sufficient to provide a cured coating. This curing step is preferably carried out on a hot plate type device, although an oven curing can be used to obtain equivalent results. The curing temperature should be enough to cure the entire layer, for example, enough to crosslink a curing agent such as a free acid, or to release an acid from a thermal acid generator and to crosslink the released acid, wherein the curing agent is TAG. Typically, curing is carried out 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, still 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 also more preferably 45 to 90 seconds.Optionally, ramp-up or multi-stage curing process can be used. The ramp-up baking typically starts at relatively low (for example, environment) temperature, and the temperature is increased to a higher target temperature with a constant or variable ramp-up rate. The multi-stage curing process relates to curing at two or more temperature platforms, typically carries out the first stage at a lower baking temperature, carries out one or more extra stages at a higher temperature. The condition of this type of ramp-up or multi-stage curing process is known to those skilled in the art, and can allow omitting previous soft baking process.

[0119] After the photoresist bottom layer composition is cured, one or more treatment layers such as photoresist layer, hard mask layer (such as metal hard mask layer), organic or inorganic bottom anti-reflective coating (BARC) etc. can be arranged on the cured bottom layer.The photoresist layer can be directly formed on the surface of the bottom layer, or alternatively, can be formed on one or more intermediate layers on the bottom layer.In this case, one or more intermediate treatment layers (as mentioned above) can be formed successively on the bottom layer, then form the photoresist layer.The determination of suitable layer, thickness and coating method is well known to those skilled in the art.

[0120] A wide variety of photoresists can be suitably used in the methods of the present invention and are typically positive-working materials. Suitable photoresists include, for example, materials within the EPIC series of photoresists available from DuPont Electronics & Imaging of Marlborough, Massachusetts. The photoresist can be applied to the substrate by known coating techniques (as described above with respect to the underlying composition, of which spin coating is typical). The typical thickness of the photoresist layer is 300 to 1000 angstroms. Next, the photoresist layer is typically soft-baked to minimize the solvent content in the layer, thereby forming a tack-free coating and improving the adhesion of the layer to the substrate. The soft bake can be performed on a hot plate or in an oven, with a hot plate being typical. A typical soft bake is performed at a temperature of 90°C to 150°C and for a time of 30 to 90 seconds.

[0121] Optionally, one or more barrier layers may be disposed over the photoresist layer. Suitable barrier layers include a top coat, a top antireflective coating (or TARC layer), and the like. Preferably, a top coat is used when the photoresist is patterned using immersion lithography. Such top coats are well known in the art and are commercially available, such as OC 2000 available from DuPont Electronics & Imaging. Those skilled in the art will recognize that a TARC layer is not required when an organic antireflective layer is used below the photoresist layer.

[0122] Next, the photoresist layer is exposed to activating radiation through a photomask to produce a solubility difference between the exposed area and the unexposed area. The exposure of the photoresist composition to the radiation that activates the composition mentioned herein shows that radiation can form a latent image in the photoresist composition. The photomask has optically transparent and optically opaque areas, corresponding to the areas to be exposed and unexposed by the activating radiation in the resist layer, respectively. The exposure wavelength is typically lower than 400nm, lower than 300nm, such as 248nm (KrF), 193nm (ArF) or extreme ultraviolet (EUV) wavelength (for example 13.5nm). In a preferred aspect, the exposure wavelength is 193nm. The exposure energy is typically 10 to 80mJ / cm 2 , which depends on, for example, the exposure tool and the components of the photosensitive composition.

[0123] After exposing the photoresist layer, a post-exposure bake (PEB) is typically performed. PEB can be performed, for example, on a hot plate or in an oven. PEB is typically performed at a temperature of 80°C to 150°C and for a time of 30 to 90 seconds. A latent image defined by the boundary between polarity-switched and unswitched areas (corresponding to exposed and unexposed areas, respectively) is thereby formed. The exposed photoresist layer is then developed using a suitable developer to provide a patterned photoresist layer.

[0124] The pattern of the photoresist layer can then be transferred to one or more underlying layers, including the bottom layer, and to the substrate by an appropriate etching technique, such as by plasma etching or wet etching. Plasma etching can use appropriate gas species for each layer being etched. Suitable wet chemical etching chemicals include, for example, a mixture comprising ammonium hydroxide, hydrogen peroxide, and water (e.g., SC-1 cleaning solution); a mixture comprising hydrochloric acid, hydrogen peroxide, and water (e.g., SC-2 cleaning solution); a mixture comprising sulfuric acid, hydrogen peroxide, and water (e.g., SPM cleaning solution); a mixture comprising phosphoric acid, hydrogen peroxide, and water; a mixture comprising hydrofluoric acid and water; a mixture comprising hydrofluoric acid, phosphoric acid, and water; a mixture comprising hydrofluoric acid, nitric acid, and water; a mixture comprising tetramethylammonium hydroxide and water; and the like.

[0125] Depending on the number of layers and materials involved, pattern transfer can involve multiple etching steps using different techniques. After the pattern is transferred to the substrate using conventional techniques, the patterned photoresist layer, the bottom layer, 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 the pattern is transferred to the underlying layer and before the pattern is transferred to the substrate. The substrate is then further processed according to known methods to form an electronic device.

[0126] The photoresist bottom layer composition can also be used for self-aligned double patterning process. In this process, a layer of the above-mentioned photoresist bottom layer composition is coated on a substrate, such as by spin coating. Any remaining organic solvent is removed and the coating is cured to form a photoresist bottom layer. A suitable intermediate layer such as a silicon-containing hard mask layer is optionally coated on the photoresist bottom layer. Then a suitable photoresist layer is coated on the intermediate layer as by spin coating. The photoresist layer is then imaged (exposed), and then the exposed photoresist layer is 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 bottom layer by a suitable etching technique to expose a part for the substrate. Typically, the photoresist is also removed during this etching step. Next, a conformal silicon-containing layer is arranged on the exposed portion of the patterned bottom layer and the substrate. This type of silicon-containing layer is typically an inorganic silicon layer, such as SiON or SiO , deposited conventionally by CVD. Such conformal coating produces a silicon-containing layer on the exposed portion of the substrate surface and above the underlying pattern, i.e., such silicon-containing layer substantially covers the sides and top of the underlying pattern. Next, the silicon-containing layer is partially etched (trimmed) to expose the top surface of the patterned underlying layer and a portion of the substrate. After this partial etching step, the pattern on the substrate comprises a plurality of features, each of which comprises a line or column of the underlying layer, wherein the silicon-containing layer is directly adjacent to the side of each underlying feature. Next, the exposed area of ​​the underlying layer is removed, such as by etching, to expose the substrate surface below the underlying pattern and provide a patterned silicon-containing layer on the substrate surface, wherein such patterned silicon-containing layer is double (i.e., twice as many lines and / or columns) compared to the patterned underlying layer.

[0127] The photoresist underlayer formed from the photoresist underlayer composition of the present invention exhibits excellent planarization, good solvent resistance, adjustable etching rate, and good resistance to wet chemical etchants. The preferred photoresist underlayer composition of the present invention can therefore be used in various semiconductor manufacturing processes.

[0128] The present invention is further illustrated by the following examples. All compounds and reagents used herein are commercially available, except for the procedures provided below.

[0129] Examples

[0130] Matrix polymer synthesis

[0131] Example 1: Poly(arylene ether) oligomer (I)

[0132] A mixture of 30.0 grams (g) of 3,3'-(oxydi-1,4-phenylene)bis(2,4,5-triphenylcyclopentadienone) (DPO-CPD), 18.1 g of 1,3,5-tris(phenylethynyl)benzene (TRIS) and 102.2 g of GBL was heated at 185°C for 14 hours. The reaction was then allowed to cool to room temperature and diluted with 21.5 g of GBL to form a crude product mixture. The crude product mixture was added to 1.7 liters (L) of a 1:1 mixture of isopropyl alcohol (IPA) / PGME and stirred for 30 minutes. The solid was collected by vacuum filtration and washed with IPA / PGME (1:1 v / v). 0.4 L of deionized water was added to the solid and the resulting slurry was heated to 50°C and then stirred at 50°C for another 30 minutes. The hot slurry was then filtered using vacuum filtration to obtain a wet solid, which was dried in a vacuum oven at 70°C for 2 days to provide 34.1 g of poly(arylene ether) oligomer 1 in 71% yield. Analysis provided an Mw of 3487 Da and a PDI of 1.42.

[0133]

[0134] Additive synthesis

[0135] Example 2: Dopamine salicylate (VIII)

[0136] Dopamine hydrochloride (2.02 g) and silver salicylate (2.69 g) were added to a solution of methanol (50 mL) and water (5 mL) at room temperature. The resulting mixture was then heated at 35° C. for 18 hours with stirring. After the reaction was complete, the crude product was filtered through celite and washed with methanol, and the collected crude product solution was then concentrated to dryness to provide a yellow oil. The crude product was dissolved in PGMEA and eluted on a silica gel plug, and then concentrated to dryness to give 3 g of product (VIII). Example 3: OH-TRIS (IX)

[0137] At room temperature, 1,3,5-tribromobenzene (2.36g), cuprous iodide (0.21g) and triethylamine (3.42g) are added to 20g1,4-dioxane. Nitrogen bubbling is used to purge the reaction mixture for 1 hour. Bis(triphenylphosphine)palladium chloride (II) (0.53g) is added to the reaction mixture, and the resulting mixture is heated to 70°C. Acetic acid 4-ethynylphenyl ester (4.81g) is dissolved in aliquots of nitrogen-degassed 1,4-dioxane (14g), and then the solution is slowly added to the mixture by addition funnel. After the addition is complete, the reaction contents are stirred at 70°C for 18 hours under nitrogen. After the reaction is complete, the reaction mixture is cooled to room temperature, and the obtained crude product is filtered, and the solvent is evaporated. The residue is purified by column chromatography to obtain a light yellow solid. Subsequently, under nitrogen, the semi-purified solid is dissolved in THF (35g). Lithium hydroxide monohydrate (0.94 g) and water (8 g) were then added thereto, and the resulting reaction mixture was stirred at 60 ° C for 1 hour. Afterwards, the reaction mixture was diluted with ethyl acetate and then the pH of the aqueous layer was adjusted with hydrochloric acid until a pH of 1 was obtained. The organic phase was then separated, and the aqueous phase was extracted with ethyl acetate again. The combined organic layer was washed with water, and the solvent was removed under vacuum to obtain 1,3,5-tris((4-hydroxyphenyl)ethynyl)benzene (2.6 g, 81% yield) as a light yellow solid.

[0138] Example 4: Propargyl OH-TRIS(X)

[0139] 1,3,5-tris((4-hydroxyphenyl)ethynyl)benzene in 46g of anhydrous dimethylformamide (DMF) was stirred at room temperature for 15 minutes. The mixture was heated to 3°C, and 10.34gK2CO3 was added thereto. The reaction was then heated to 50°C and 8.63g of propargyl bromide solution (80wt% in toluene) was added dropwise through an additional funnel. The reaction mixture was heated at 50°C for 24 hours. The reaction was then cooled to room temperature and filtered to remove K2CO3. The resulting organic solution was precipitated into 2L of deionized water and then stirred at room temperature for 30 minutes. The precipitated material was then collected by filtration and dried under vacuum at 35°C for 1 day to provide 17.8g of solid product.

[0140] Example 5: Acetoxy OH-TRIS(XI)

[0141] 1,3,5-tribromobenzene (2.36g), cuprous iodide (0.21g) and triethylamine (3.42g) are added to 20g1,4-dioxane at room temperature. The reaction mixture is purged using nitrogen bubbling for 1 hour. Then bis(triphenylphosphine)palladium chloride (II) (0.53g) is added to the reaction mixture, and the resulting reaction mixture is heated to 70 DEG C. 4-ethynylphenyl acetate (4.81g) is dissolved in nitrogen degassed 1,4-dioxane (14g), and then the solution is slowly added to the reaction mixture using an addition funnel. After the addition is complete, the reaction mixture is stirred at 70 DEG C under nitrogen for 18 hours. After the reaction is complete, the reaction mixture is cooled to room temperature, contents are filtered and the solvent is evaporated to provide a crude product. The crude product is purified by column chromatography to obtain 1,3,5-tris((4-acetoxyphenyl)ethynyl)benzene (3.5g, 84% yield) as a light yellow solid.

[0142] Example 6: Methoxy OH-TRIS (XII)

[0143] 1,3,5-tribromobenzene (3.12g), cuprous iodide (0.29g) and triethylamine (4.55g) are added to 22g1,4-dioxane at room temperature. The reaction mixture is purged using nitrogen bubbling for 1 hour. Then bis(triphenylphosphine)palladium chloride (II) (0.70g) is added to the reaction mixture, and the reaction mixture is heated to 70 DEG C. 1-ethynyl-4-methoxybenzene (5.28g) is dissolved in nitrogen degassed 1,4-dioxane (20g), and then the solution is slowly added to the reaction mixture using an addition funnel. After the addition is complete, the reaction mixture is stirred at 70 DEG C under nitrogen for 18 hours. After the reaction is complete, the reaction contents are cooled to room temperature, the product is filtered and the solvent is evaporated to provide a crude product. The crude product is purified by column chromatography to obtain 1,3,5-tris((4-methoxyphenyl)ethynyl)benzene (4.0g, 85% yield) as a light yellow solid.

[0144] Additive compounds having formula (II) to (VII) were purchased from commercially available sources and used without further preparation.

[0145] The structures of compounds having formulae (II) to (XII) are shown below:

[0146]

[0147] Evaluation Example

[0148] Preparations containing additives

[0149] The formulations of the present invention are prepared by dissolving the polymer and one or more adhesion-promoting additives at approximately 4 wt% solids in a mixture of PGMEA and benzyl benzoate (97:3, w / w). The amounts of the additives relative to the total solids are provided in Table 1 below. The resulting solution is filtered through a 0.2 μm poly(tetrafluoroethylene) (PTFE) syringe filter.

[0150] Preparations without additives

[0151] The formulation was prepared by dissolving the polymer at approximately 4 wt% solids in a mixture of PGMEA and benzyl benzoate (97:3, w / w).The resulting solution was filtered through a 0.2 μm poly(tetrafluoroethylene) (PTFE) syringe filter.

[0152] Standard coating and cleaning

[0153] The standard coating process of the above formulation was carried out on a 200 mm silicon wafer with a 10 nm TiN coating deposited by CVD. The above formulation was applied to the TiN coated wafer by spin coating, soft baking at 170°C for 60 seconds, and then hard baking at 450°C for 4 minutes.

[0154] A standard cleaning solution (SC1) was prepared by mixing 30% ammonium hydroxide, 30% hydrogen peroxide, and deionized water in a ratio of 1:5:40 (w / w / w). Both ammonium hydroxide and hydrogen peroxide were purchased from Fisher Scientific and used as received. Wafer specimens coated with a photoresist underlying film were immersed in a bath containing SC1 at 70°C with gentle stirring. The treated specimens were rinsed twice with deionized water and then air-dried. The time before significant film delamination (visual observation) was recorded to evaluate the resistance of the SOC coating to SC1 peeling. The film thickness before and after treatment with SC1 was measured in the non-delaminated area and showed no change, confirming that the photoresist underlying film was not etched under wet etching conditions.

[0155] Table 1

[0156]

[0157] The examples disclosed in Table 1 demonstrate that inventive Formulations 1 to 16 exhibit excellent resistance to wet chemical etching conditions of standard cleaning solutions. In particular, comparative Formulation C1 delaminated at 1 minute, while inventive Formulations 1 to 16 each took more than 1 minute to delaminate from the substrate.

[0158] While the disclosure has been described in connection with what are presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A photoresist base composition comprising: a poly(arylene ether) derived from a first compound comprising two or more cyclopentadienone moieties and a second compound comprising an aryl moiety and two or more alkyne groups; An additive having formula (15): as well as solvents, in, In formula (15), D is a polyvalent C 1-30 Alkyl, polyvalent C 3-30 Cycloalkyl, polyvalent C 6-30 Aryl, or polyvalent C 6-30 heteroaryl, Each Ar 5 Is a monocyclic or polycyclic C 6-60 Arylene or monocyclic or polycyclic C 5-60 Heteroarylene, Each X is independently -OR 30 、-SR 31 , or -NR 32 R 33 , m is an integer from 2 to 4, Each n is independently an integer from 1 to 5, provided that the sum of all n is 3 or greater, R 30 to R 33 are each independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, 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, each of which, except hydrogen, optionally further comprises as part of its structure one or more of: substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 2-30 Alkenylene, substituted or unsubstituted C 4-30 Cycloalkenylene, substituted or unsubstituted C 2-30 Alkynylidene, substituted or unsubstituted C 1-30 Heterocycloalkylene, substituted or unsubstituted C 6-30 Arylene, substituted or unsubstituted C 4-30 heteroarylene, -O-, -C(O)-, -C(O)O-, -S-, -S(O)-, -S(O)2-, or -NR 34 -, where R 34 is substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 1-20 Heterocycloalkyl, 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 4-30 Heteroaryl, substituted or unsubstituted C 5-30 Heteroarylalkyl, or substituted or unsubstituted C 5-30 Alkylheteroaryl.

2. The photoresist underlayer composition according to claim 1, wherein In formula (15), each X is independently -OR 30 , where each R 30 are independently hydrogen, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted -C(O)-C 1-6 Alkyl, substituted or unsubstituted C 3-10 Cycloalkyl, substituted or unsubstituted C 2-30 Alkynyl, 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.

3. The photoresist underlayer composition according to claim 1 or 2, wherein The additive is present in an amount of 0.1 to 20 wt % based on the total solids of the photoresist underlayer composition.

4. A method for forming a pattern, the method comprising: (a) applying a layer of the photoresist underlayer composition according to any one of claims 1 to 3 on a substrate; (b) curing the applied photoresist underlayer composition to form a photoresist underlayer; and (c) forming a photoresist layer on the photoresist underlayer. 5 . The method of claim 4 , further comprising forming a silicon-containing layer, an organic anti-reflective coating, or a combination thereof on the photoresist bottom layer before forming the photoresist layer.

6. The method of claim 4 or 5, further comprising patterning the photoresist layer and transferring a pattern from the patterned photoresist layer to the coating layer and a layer below the photoresist bottom layer.

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