Composition for photoresist underlayer

Abstract

A photoresist bottom layer composition comprises: a first polymer, the first polymer comprising a crosslinkable group; a second polymer, the second polymer comprising: a first repeating unit and a second repeating unit, the first repeating unit comprising a repeating unit comprising a photoacid generator, the second repeating unit comprising a hydroxyl-substituted C 1‑30 Alkyl, hydroxy substituted C 3‑30 Cycloalkyl or hydroxy substituted C 6‑30 an aryl group; an acid catalyst; and a solvent.

Description

Technical Field

[0001] The present invention relates generally to the field of manufacturing electronic devices, and more particularly to the field of materials used in semiconductor manufacturing. Background Art

[0002] 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.

[0003] When chemically amplified photoresist compositions for ArF or extreme ultraviolet (EUV) lithography are prepared using resins that may contain byproducts, the number of defects (surface defects) in the resist pattern after development may become problematic, even if characteristics such as sensitivity, resolution, and resist pattern shape are satisfactory. These surface defects refer to problems such as scum and bridging between resist patterns.

[0004] EUV lithography is a leading alternative to optical lithography for volume semiconductor manufacturing with feature sizes of a few nanometers. Currently, EUV lithography has become the preferred patterning technology for immersion processes beyond 193nm, used for high-volume manufacturing of product nodes below 10nm. In EUV lithography, fewer photons are exposed in the exposed areas than in ArF lithography. Due to the lack of photons and the shrinking pattern pitch, the impact of shot noise on the pattern profile becomes more significant. Scum and bridging defects between resist patterns, such as nanobridge defects at line-to-space patterns with a 3x nm pitch, can lead to fatal bridge defects after the entire pattern is transferred through the etching process.

[0005] Therefore, there remains a need for new photoresist underlayer materials that can mitigate scum and bridging defects in photoresists used for ArF and EUV lithography. Summary of the Invention

[0006] On the one hand, a photoresist bottom layer composition is provided, which comprises: a first polymer, the first polymer comprising a crosslinkable group; a second polymer, the second polymer comprising: a first repeating unit and a second repeating unit, the first repeating unit comprising a repeating unit comprising a photoacid generator, the second repeating unit comprising a hydroxyl-substituted C 1-30 Alkyl, hydroxy substituted C 3-30 Cycloalkyl or hydroxy substituted C 6-30 an aryl group; an acid catalyst; and a solvent.

[0007] Also provided is a coated substrate comprising: a cured layer of the photoresist base composition of the present invention disposed on the substrate; and a photoresist layer disposed on the cured layer of the photoresist base composition.

[0008] On the other hand, a method of forming a pattern is provided, the method comprising applying a layer of the photoresist base composition of the present invention to a substrate; curing the applied layer of the photoresist base composition to form an underlying film; applying a layer of the photoresist composition on the underlying film to form a photoresist layer; exposing the applied photoresist layer to activating radiation in a patterned manner; and developing the exposed photoresist layer to provide a resist relief image. DETAILED DESCRIPTION

[0009] 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 description described herein. Therefore, exemplary embodiments will be described below only with reference to the accompanying drawings to explain aspects of this specification. As used herein, the term "and / or" includes all combinations of one or more of the relevant listed items. When a statement such as "at least one of ... " precedes an element list, it modifies the entire element list and does not modify a single element in the list.

[0010] As used herein, the terms "a / an" and "the" do not represent a limit on 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 indicated, "or" means "and / or". 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 of its non-occurrence. The terms "first", "second" and similar terms do not represent order, quantity, or importance in this article, 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 is no intervening element. It will be appreciated that components, elements, limitations and / or features of the described aspects may be combined in any suitable manner among the various aspects.

[0011] 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.

[0012] 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 group" refers to a group having the formula "-C(=O)-OH"; " "Cycloalkyl" refers to a monovalent group having one or more saturated rings in which all ring members are carbon; "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 and S 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-".

[0013] The prefix "hetero" means that the compound or group includes at least one member (e.g., 1, 2, 3, or 4 or more heteroatoms) that is a heteroatom replacing a carbon atom, wherein the heteroatoms are each independently selected from N, O, S, Si, or P; "heteroatom-containing group" refers to a substituent that includes at least one heteroatom; "heteroalkyl" refers to an alkyl group having 1-4 heteroatoms replacing a carbon atom; "heterocycloalkyl" refers to a cycloalkyl group having one or more N, O, or S atoms replacing a carbon atom; "heterocycloalkylene" refers to a heterocycloalkyl group having a valence of at least 2; "heteroaryl" refers to an aryl group having from 1 to 3 ring members having one or more N, O, or S atoms replacing a carbon atom, either separate or fused; and "heteroarylene" refers to a heteroaryl group having a valence of at least 2.

[0014] 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.

[0015] The symbol "*" indicates the bonding site (ie, point of attachment) of the repeating unit.

[0016] "Substituted" means that at least one hydrogen atom on a 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, C 2-6 Alkyl esters (-C(=O)O-alkyl or -OC(=O)-alkyl), C 7-13 Aryl esters (-C(=O)O-aryl or -OC(=O)-aryl), amides (-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), thiocyanato (-SCN), C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Halogenated alkyl, C 1-9 Alkoxy, C1-6 Halogenated alkoxy, C 3-12 Cycloalkyl, C 5-18 Cycloalkenyl, C 6-12 Aryl (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.

[0017] As used herein, the term "polymer" refers to a polymeric compound containing one or more repeating units, wherein, when two or more repeating units are present, each repeating unit may be the same or different from each other. Thus, the disclosed polymers of the present invention may be referred to herein as "polymers" or "copolymers."

[0018] In positive tone development (PTD) processes using EUV or ArF lithography, scum and bridging defects of line and space (L / S) patterns are increasingly important factors for high energy latitude (EL) and wide depth of focus (DoF) margins. Scum and bridging defects may depend on the film properties of the EUV underlayer, including any bottom anti-reflective coating (BARC). As an acidic catalyst, a photoacid generator (PAG) in the EUV underlayer / BARC formulation can be used to control the acidity and improve scum and bridging defects in exposed areas. However, in addition to reduced film uniformity (i.e., poor film uniformity) due to the polarity mismatch with the EUV underlayer / BARC polymer, a significant disadvantage of this approach is the loss of material due to film stripping by solvents present during photoresist coating.

[0019] The present inventors have discovered that EUV underlayers and / or BARC formulations comprising polymer-bound PAGs can reduce the extent of film lift-off loss by forming cross-linked polymers through a cross-linking reaction with a cross-linkable polymer during a bake step. Furthermore, the amount of scum and bridging defects can be reduced by photoacid generated from the cross-linked polymer during subsequent photoresist exposure.

[0020] According to one aspect, the photoresist underlayer composition comprises a first polymer comprising a crosslinkable group; a second polymer comprising a first repeating unit and a second repeating unit, wherein the first repeating unit comprises a repeating unit comprising a photoacid generator, and the second repeating unit comprises a hydroxyl-substituted C 1-30 Alkyl, hydroxy substituted C 3-30 Cycloalkyl or hydroxy substituted C 6-30 an aryl group; an acid catalyst; and a solvent.

[0021] In an embodiment, the first polymer may be a crosslinkable polyester polymer comprising crosslinkable groups. For example, the first polymer may comprise isocyanurate repeating units and crosslinkable groups. In some aspects, the crosslinkable groups may be selected from hydroxyl, carboxyl, thiol, amino, epoxy, alkoxy, amide, vinyl, or combinations thereof.

[0022] Preferably, the first polymer comprises one or more isocyanurate repeat units derived from a monomer having formula (1):

[0023]

[0024] In formula (1), K, L and M are each independently a linear or branched C 1-10 Hydrocarbon, C 1-10 Alkoxycarbonyl, C 1-10 Alkanoyloxy, each of which is optionally substituted by a carboxylic acid group, or a linear or branched C 1-10 Hydroxyalkyl, which is optionally replaced by C 1-5 Alkoxycarbonyl or C 1-5 Substituted alkoxy substituted.

[0025] In formula (1), for K, L and M, C 1-10 Hydrocarbon, C 1-10 Alkoxycarbonyl, C 1-10 Alkanoyloxy and C 1-10 Each of the hydroxyalkyl groups may be optionally substituted with halogen, amino, mercapto, epoxy, amide, C 1-5 Alkyl, C 3-8 Cycloalkyl, C 3-20 Heterocycloalkyl, C 2-5 Alkenyl, C 1-5 Alkoxy, C 2-5 Alkenyloxy, C 6-12 Aryl, C 6-12 Aryloxy, C 7-13 Alkyl aryl, or C 7-13 At least one of the alkylaryloxy groups is substituted. 3-8 Cycloalkyl and C 3-20The heterocycloalkyl group may be optionally substituted with an oxo group (=O) on at least one ring carbon atom. At least one hydrogen atom of the first polymer derived from the monomer having formula (2) is substituted with a functional group independently selected from hydroxyl, carboxyl, thiol, amino, epoxy, alkoxy, amide, vinyl, and combinations thereof. Among them, hydroxyl, carboxyl, or alkoxy is preferred.

[0026] The first polymer can be formed by conventional polycondensation techniques, such as those described in Zeno W. Wicks, Jr., Frank N. Jones, S. Peter Pappas, "Organic Coatings, Science and Technology," pp. 246-257 (John Wiley & Sons, 1999, 2nd ed.), and references therein, or in Houben-Weyl, "Methoden der Organischen Chemie, Band E20, Makromolekulare Soffe, Polyester," pp. 1405-1429 (Georg Thieme Verlag, Stuttgart, 1987), and references therein. In one aspect, a diol or polyol and a dicarboxylic acid or polycarboxylic acid are charged to a conventional polymerization vessel and reacted at about 150° C. to 280° C. for several hours. Optionally, an esterification catalyst can be used to reduce the reaction time. It should also be understood that esterified derivatives of polycarboxylic acids (such as dimethyl esters or anhydrides of polycarboxylic acids) can be used to prepare polyesters. Exemplary polyols and polycarboxylic acids include isocyanurate polyols and isocyanurate polycarboxylic acids. The polyester polymer can be linear or branched.

[0027] Suitable diols and polyols include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol and higher polyethylene glycols, propylene glycol, dipropylene glycol, tripropylene glycol and higher polypropylene glycols, 1,3-propanediol, 1,4-butanediol and other butanediols, 1,5-pentanediol and other pentanediols, hexanediol, decanediol, and dodecanediol, glycerol, trimethylolpropane, trimethylolethane, neopentyl glycol, pentaerythritol, cyclohexanedimethanol, dipentaerythritol, 1,2- -dimethyl-1,3-propanediol, 1,4-benzyl dimethanol, 2,4-dimethyl-2-ethylhexane-1,3-diol, isopropylidenebis(p-phenylene-oxypropanol-2), 4,4'-dihydroxy-2,2'-diphenylpropane, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol (or a mixture of 1,3-cyclohexanedimethanol and 1,4-cyclohexanedimethanol, which may be cis or trans), sorbitol, etc., or a combination thereof.

[0028] The first polymer may optionally comprise one or more additional repeating units that are different from the repeating units comprising formula (1). The additional repeating units may comprise, for example, one or more additional units for the purpose of regulating the properties (such as etch rate and solubility) of the photoresist composition. Exemplary additional units may comprise one or more of (meth)acrylate, vinyl ether, vinyl ketone, and vinyl ester. The one or more additional repeating units in the polymer (if present) are typically used in an amount of up to 99 mol% and typically 3 to 80 mol% based on the total repeating units of the polymer.

[0029] Preferably, the first polymer of the present invention will have a weight average molecular weight (Mw) of 1,000 to 100,000 grams per mole (g / mol), more typically 2,000 to 30,000 g / mol, and a number average molecular weight (Mn) of 500 to 1,000,000 g / mol. w or M n ) is suitably determined by gel permeation chromatography (GPC).

[0030] The second polymer comprises a first repeating unit comprising a repeating unit comprising a photoacid generator; and a second repeating unit comprising a hydroxyl-substituted C 1-30 Alkyl, hydroxy substituted C 3-30 Cycloalkyl, or hydroxy substituted C 6-30 The second polymer may optionally comprise a third repeating unit comprising an unsubstituted C 1-30 Alkyl, fluorine-substituted C 1-30 Alkyl, C substituted by polymerizable groups 1-30 Alkyl, C substituted by polymerizable groups 3-30 Cycloalkyl, or C substituted by a polymerizable group 6-30 An aromatic group wherein the polymerizable group is reactive toward self-crosslinking a second polymer.

[0031] Preferably, the first repeat unit of the second polymer comprises a repeat unit derived from a monomer having formula (2):

[0032]

[0033] In formula (2), R a is hydrogen, fluorine, cyano, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted C 1-10 Preferably, R a is hydrogen, fluorine, or substituted or unsubstituted C 1-5 The alkyl group is typically a methyl group.

[0034] In formula (2), L 1 is a single bond or a divalent linking group. Typically, L 1 is a single bond or a divalent linking group selected from one or more of the following: a substituted or unsubstituted heteroatom, a substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 1-30 Heterocycloalkylene, substituted or unsubstituted C 6-30 Arylene, substituted or unsubstituted divalent C 7-30 Arylalkyl, substituted or unsubstituted C 1-30 Heteroarylene, or substituted or unsubstituted divalent C 3-30 Heteroarylalkyl, or a combination thereof. For example, substituted or unsubstituted heteroatoms may be selected from -O-, -C(O)-, -N(R)-, -S-, -S(O)2-, wherein R is hydrogen or C 1-6 Preferably, L 1 It is a single bond, -O- or -C(O)-.

[0035] In formula (2), A is a divalent linking group. Typically, A is a divalent linking group selected from one or more of the following: substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 1-30 Heterocycloalkylene, substituted or unsubstituted C 6-30 Arylene, substituted or unsubstituted divalent C 7-30 Arylalkyl, substituted or unsubstituted C 1-30 Heteroarylene, substituted or unsubstituted divalent C 3-30 Preferably, A is substituted or unsubstituted C 1-30 Alkylene or substituted or unsubstituted C 6-30 Arylene.

[0036] In formula (2), Z - It is an anion portion containing a sulfonate group, a sulfonamide anion, a sulfonimide anion, or a methide anion. + is an organic cation as described below.

[0037] In some embodiments, -L in formula (2) 1 -AZ - The structure represented may be a group represented by one of formulae (3) to (5):

[0038]

[0039] In formula (3), Q 1is a fluorine-substituted divalent linking group. Typically, Q 1 is a fluorine-substituted divalent linking group comprising a substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 1-30 Heterocycloalkylene, substituted or unsubstituted C 6-30 Arylene, substituted or unsubstituted divalent C 7-30 Arylalkyl, substituted or unsubstituted C 1-30 Heteroarylene, or substituted or unsubstituted divalent C 3-30 One or more of heteroarylalkyl, and optionally further comprising one or more of -O- or -C(O)-. Preferably, Q 1 is a fluorine-substituted divalent linking group comprising a substituted or unsubstituted C 1-30 alkylene and one or more of -O- or -C(O)-.

[0040] In formula (4), Q 2 is a fluorine-substituted divalent linking group. Typically, Q 2 is a fluorine-substituted divalent linking group comprising a substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 1-30 Heterocycloalkylene, substituted or unsubstituted C 6-30 Arylene, substituted or unsubstituted divalent C 7-30 Arylalkyl, substituted or unsubstituted C 1-30 Heteroarylene, or substituted or unsubstituted divalent C 3-30 One or more of heteroarylalkyl, and optionally further comprising one or more of -O- or -C(O)-. Preferably, Q 2 is a fluorine-substituted divalent linking group comprising a substituted or unsubstituted C 1-30 Alkylene.

[0041] In formula (5a), Q 3 is a divalent linking group. Typically, Q 3 is a divalent linking group comprising a substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 1-30 Heterocycloalkylene, substituted or unsubstituted C 6-30 Arylene, substituted or unsubstituted divalent C 7-30 Arylalkyl, substituted or unsubstituted C 1-30 Heteroarylene, or substituted or unsubstituted divalent C 3-30One or more of heteroarylalkyl, and optionally further comprising one or more of -O- or -C(O)-. Preferably, Q 3 is a divalent linking group comprising a substituted or unsubstituted C 1-30 Alkylene or substituted or unsubstituted C 6-30 Arylene.

[0042] In formula (5a), R f is fluorine-substituted C 1-30 Alkyl, fluorine-substituted C 3-30 Cycloalkyl, or with Q 3 Preferably, R f is fluorine-substituted C 1-10 alkyl.

[0043] In formula (5b), Q 4 is a single bond or a divalent linking group. Typically, Q 4 is a single bond or a divalent linking group comprising a substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 1-30 Heterocycloalkylene, substituted or unsubstituted C 6-30 Arylene, substituted or unsubstituted divalent C 7-30 Arylalkyl, substituted or unsubstituted C 1-30 Heteroarylene, or substituted or unsubstituted divalent C 3-30 One or more of heteroarylalkyl, and optionally further comprising one or more of -O- or -C(O)-. Preferably, Q 4 It is a single bond.

[0044] Exemplary monomers having formula (2) include the following:

[0045]

[0046] Among them G + is an organic cation. The organic cation includes, for example, an iodonium cation substituted with two alkyl groups, aryl groups, or a combination of an alkyl group and an aryl group; and a sulfonium cation substituted with three alkyl groups, aryl groups, or a combination of an alkyl group and an aryl group.

[0047] In an embodiment, the organic cation G + is represented by one of equations (6), (7) or (8):

[0048]

[0049] In formulae (6), (7) and (8), X is I or S.

[0050] In formulas (6), (7) and (8), R h 、R i 、R j and R k are each independently hydroxy, nitrile, halogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Fluoroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 1-30 Fluorinated cycloalkyl, substituted or unsubstituted C 1-30 Alkoxy, substituted or unsubstituted C 3-30 Alkoxycarbonylalkyl, substituted or unsubstituted C 3-30 Alkoxycarbonylalkoxy, substituted or unsubstituted C 3-30 Cycloalkoxy, substituted or unsubstituted C 5-30 Cycloalkoxycarbonylalkyl, substituted or unsubstituted C 5-30 Cycloalkoxycarbonylalkoxy, substituted or unsubstituted C 1-30 Fluoroalkoxy, substituted or unsubstituted C 3-30 Fluoroalkoxycarbonylalkyl, substituted or unsubstituted C 3-30 Fluoroalkoxycarbonylalkoxy, substituted or unsubstituted C 3-30 Fluorocycloalkoxy, substituted or unsubstituted C 5-30 Fluorocycloalkoxycarbonylalkyl, substituted or unsubstituted C 5-30 Fluorocycloalkoxycarbonylalkoxy, substituted or unsubstituted C 6-30 Aryl, C 6-30 Fluoroaryl, substituted or unsubstituted C 6-30 Aryloxy, substituted or unsubstituted C 6-30 Preferably, R h 、R i 、R j and R k One or more of them is hydroxy, halogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 Alkoxycarbonylalkoxy, substituted or unsubstituted C 5-30 cycloalkoxycarbonylalkoxy, or a combination thereof.

[0051] In formula (8), each R aa are independently substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Fluoroalkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C 3-20 Fluorinated cycloalkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 2-20Fluoroalkenyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 6-30 Fluoroaryl, substituted or unsubstituted C 6-30 Iodoaryl, substituted or unsubstituted C 4-30 Heteroaryl, substituted or unsubstituted C 7-20 Arylalkyl, substituted or unsubstituted C 7-20 Fluoroarylalkyl, substituted or unsubstituted C 5-30 Heteroarylalkyl, or substituted or unsubstituted C 5-30 Fluoroheteroarylalkyl, wherein each R aa is alone or connected to another group R via a single bond or a divalent linking group aa Form a ring. Each R aa Optionally, it may include as part of its structure one or more groups selected from the group consisting of: -O-, -C(O)-, -C(O)-O-, -C 1-12 Alkylidene-, -O-(C 1-12 alkylene)-、-C(O)-O-(C 1-12 alkylene)- and -C(O)-O-(C 1-12 Alkylene)-O-. Each R aa Independently, it may optionally contain an acid labile group selected from, for example, a tertiary alkyl ester group, a secondary or tertiary aryl ester group, a secondary or tertiary ester group having a combination of alkyl and aryl groups, a tertiary alkoxy group, an acetal group, or a ketal group. aa The divalent linking group of the group includes, for example, -O-, -S-, -Te-, -Se-, -C(O)-, -C(S)-, -C(Te)-, -S(O)-, S(O)2-, -N(R)- or -C(Se)-, substituted or unsubstituted C 1-5 Alkylene, and combinations thereof, wherein R is hydrogen, C 1-20 Alkyl, C 1-20 Heteroalkyl, C 6-30 Aryl or C 4-30 Heteroaryl, wherein each of the groups except hydrogen may be substituted or unsubstituted.

[0052] In formula (8), when X is 1, p is 2, and R 1 is a lone pair of electrons. In formula (8), when X is S, p is 3, and R 1 is substituted or unsubstituted C 6-20 Aryl.

[0053] In formulae (6), (7), and (8), q and r are each independently an integer from 0 to 5. In formulae (6), (7), and (8), s and t are each independently an integer from 0 to 4.

[0054] In formulas (6), (7) and (8), R h 、R i 、R j and R k One of the compounds may optionally further comprise an acid cleavable group as described herein.

[0055] Exemplary sulfonium cations include the following:

[0056]

[0057]

[0058] Exemplary iodonium cations include the following:

[0059]

[0060] The second repeat unit of the second polymer is preferably derivable from a monomer having formula (9):

[0061]

[0062] In formula (9), R a is hydrogen, halogen, cyano, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted C 1-10 Preferably, R a is hydrogen, fluorine, or substituted or unsubstituted C 1-5 The alkyl group is typically a methyl group.

[0063] In formula (9), L 2 is a single bond or a divalent linking group. Typically, L 2 is a single bond or a divalent linking group comprising a substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 1-30 Heterocycloalkylene, substituted or unsubstituted C 6-30 Arylene, substituted or unsubstituted divalent C 7-30 Arylalkyl, substituted or unsubstituted C 1-30 Heteroarylene, substituted or unsubstituted divalent C 3-30 Preferably, L 2 is a single bond, or substituted or unsubstituted C 1-30 Alkylene.

[0064] In formula (9), Y includes a hydroxy-substituted C 1-30 Alkyl, hydroxy substituted C 3-30 Cycloalkyl, hydroxy substituted C6-30 Aryl, hydroxy substituted C 5-30 heteroaryl, or a combination thereof, each of which is optionally further substituted. For example, each may be further substituted with one or more of the following (i.e., including further substituents in addition to the hydroxy moiety): substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 1-30 Heterocycloalkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 7-30 Alkylaryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl, -OR 9a , or -NR 9b R 9c , where R 9a to R 9c are each independently substituted or unsubstituted C 1-30 Alkyl, 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.

[0065] Exemplary monomers having formula (9) include the following:

[0066]

[0067] In some embodiments, the second polymer may optionally comprise a third repeating unit comprising an unsubstituted C 1-30 Alkyl, fluorine-substituted C 1-30 Alkyl, C substituted by polymerizable groups 1-30 Alkyl, C substituted by polymerizable groups 3-30 Cycloalkyl, or C substituted by a polymerizable group 6-30 An aromatic group wherein the polymerizable group is reactive toward self-crosslinking a second polymer. The third repeat unit may be selected to enhance solubility, hydrophobicity, and / or self-crosslinking capability.

[0068] Exemplary monomers that may be suitable for preparing the third repeating unit include the following:

[0069]

[0070] In an embodiment, the polymerizable group of the second polymer includes a hydroxyl group, a carboxyl group, a thiol group, an amino group, an epoxy group, an alkoxy group, an amide group, a vinyl group, or a combination thereof.

[0071] The second polymer can optionally comprise one or more other repeating units that are different from the first, second and third repeating units as herein described.This other repeating unit can comprise one or more other units such as for characteristic (such as etch rate and solubility) purpose for regulating photoresist composition.Exemplary other unit can comprise one or more in (methyl) acrylate, vinyl ether, vinyl ketone and vinyl ester.One or more other repeating units in the second polymer (if present) typically use with the amount of up to 99mol% and typically 3 to 80mol% based on the total repeating units of the second polymer.

[0072] The second polymer typically has an M of 1,000 to 100,000 Da, preferably 2,000 to 50,000 Da, more preferably 3,000 to 40,000 Da, and still more preferably 3,000 to 30,000 Da. w The PDI of the polymer is typically 1.1 to 4, and more typically 1.1 to 3. Molecular weight is determined by GPC using polystyrene standards.

[0073] The second polymer can be prepared using any suitable method known in the art. For example, one or more monomers corresponding to the repeating units described herein can be combined or fed separately using a suitable solvent or solvents and initiators and polymerized in a reactor. For example, the second polymer can be obtained by polymerizing the corresponding monomers under any suitable conditions, such as by heating at an effective temperature, irradiating with actinic radiation at an effective wavelength, or a combination thereof.

[0074] The photoresist bottom layer composition may further comprise any suitable solvent or solvent mixture. Suitable solvents include, for example, one or more oxyisobutyrates, particularly methyl 2-hydroxyisobutyrate, 2-hydroxyisobutyric acid, ethyl lactate, or glycol ethers, such as one or more of 2-methoxyethyl ether (diglyme), ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; solvents having both ether and hydroxyl moieties, such as methoxybutanol, ethoxybutanol, methoxypropanol, and ethoxypropanol; methyl 2-hydroxyisobutyrate; esters, such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and other solvents, such as dibasic esters, propylene carbonate, and gamma-butyrolactone.

[0075] The concentration of the dry components in the solvent will depend on several factors, such as the application method. Generally speaking, the total solid content of the photoresist base composition can be 0.05 to 20 wt % of the total weight of the photoresist base composition. Preferably, the total solid content of the photoresist base composition can be 0.1 to 5 wt % of the photoresist base composition.

[0076] In a preferred embodiment, the photoresist bottom layer composition comprises 20 to 95 wt % of the first polymer and 5 to 80 wt % of the second polymer, each based on the total weight of the first polymer and the second polymer combined. For example, the bottom layer composition may comprise 30 to 90 wt % of the first polymer and 10 to 70 wt % of the second polymer, each based on the total weight of the first polymer and the second polymer combined.

[0077] The photoresist bottom layer composition further comprises an acid catalyst. Acid catalysts that can be used for the present invention include free acids and acid generators. Any free acid that is compatible with the composition of the present invention and catalyzes the crosslinking of a crosslinkable polymer and a crosslinking agent is suitable for use in the present invention. Examples of free acids include, but are not limited to, sulfonic acids, such as methanesulfonic acid, ethanesulfonic acid, propylsulfonic acid, phenylsulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid, and trifluoromethylsulfonic acid. The photoresist bottom layer composition can comprise a catalyst or can comprise two or more different acid catalysts.

[0078] The acid catalyst can be a thermal acid generator (TAG), which is a compound that can generate an acidic portion when heated. The thermal acid generator can be nonionic or ionic. Suitable nonionic thermal acid generators include, for example, cyclohexyl p-toluenesulfonate, methyl p-toluenesulfonate, cyclohexyl 2,4,6-triisopropylbenzenesulfonate, nitrobenzyl ester, benzoin toluenesulfonate, 2-nitrobenzyl toluenesulfonate, tris (2,3-dibromopropyl) -1,3,5-triazine-2,4,6-trione, alkyl esters of organic sulfonic acids, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, oxalic acid, phthalic acid, phosphoric acid. , camphorsulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 5-sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorodecanoylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol-5-sulfonic acid, 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid and their salt, and combination thereof. Suitable ionic thermal acid generators include, for example, triethylamine dodecylbenzenesulfonic acid salt, triethylamine dodecylbenzenedisulfonic acid salt, ammonium p-toluenesulfonate, sulfonates, such as carbocyclic aromatics (such as phenyl, naphthyl, anthracenyl, etc.) and heteroaryl (such as thienyl) sulfonates, aliphatic sulfonates and benzenesulfonates. Compounds that produce sulfonic acid during activation are generally suitable. Preferred thermal acid generators include ammonium p-toluenesulfonate and fluorinated derivatives thereof. In an embodiment, the acid catalyst comprises N-benzyl-N,N-dimethylammonium trifluoromethanesulfonate. Typically, one or more thermal acid generators may be present in the photoresist bottom layer composition in an amount of 0.1 to 20 wt %, more preferably 0.5 to 15 wt % of the solid content of the photoresist bottom layer composition.

[0079] Preferably, the acid catalyst is not an additional PAG compound.It is understood that the term "additional PAG compound" refers to a PAG-containing polymeric or non-polymeric material that is different from the second polymer of the photoresist underlayer composition as described herein.

[0080] The photoresist bottom layer composition can further comprise one or more additives selected from cross-linking agent and surfactant. It will be appreciated by those skilled in the art that other additives may be applicable to compositions of the present invention. In some respects, the photoresist bottom layer composition does not comprise cross-linking agent, surfactant or cross-linking agent and surfactant.

[0081] For example, the photoresist bottom layer composition may further comprise a crosslinking agent. Any suitable crosslinking agent may be used in the composition of the present invention, provided that such crosslinking agent has at least 2, and preferably at least 3, moieties that can react with the polymer of the present invention under suitable conditions (e.g., under acidic conditions). Exemplary crosslinking agents include, but are not limited to, novolac resins, epoxy-containing compounds, melamine compounds, guanamine compounds, isocyanate-containing compounds, benzocyclobutene, benzoxazine, and the like, and typically have 2 or more, more typically 3 or more, selected from hydroxymethyl, C 1-10 Alkoxymethyl, and C 2-10 Any of the substituents of the acyloxymethyl group.

[0082] Examples of suitable cross-linking agents are those shown by formulas (10) and (11).

[0083]

[0084] Such crosslinking agents are well known in the art and are commercially available from a variety of sources. The amount of such crosslinking agents useful in the compositions of the present invention can be, for example, in the range of greater than 0 to 50 wt %, and typically greater than 0 to 30 wt %, based on the total solids of the photoresist bottom layer composition.

[0085] The photoresist bottom layer composition of the present invention may optionally include one or more surface leveling agents (or surfactants). 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 alcohol) ethoxylates, amine ethoxylates, glucosides, glucosamine, polyethylene glycol, poly (ethylene glycol-to-propylene glycol), or other surfactants disclosed in: McCutcheon's Emulsifiers and Detergents, 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 photoresist bottom layer composition.

[0086] Another aspect of the present invention provides a coated substrate comprising a cured layer of a photoresist base composition disposed on the substrate; and a photoresist layer disposed on the layer of the photoresist base composition. As used herein, the term "cured layer" refers to a layer derived from the photoresist base composition after the composition has been disposed on the substrate and subsequently cured to form a coating or film. In other words, curing the photoresist base composition forms a cured layer derived from the photoresist base composition.

[0087] Yet another aspect of the present invention provides a method for forming a pattern. The method comprises: applying a layer of the photoresist basecoat composition of the present invention to a substrate; curing the layer of the photoresist basecoat composition to form an underlying film; applying the layer of the photoresist composition to the underlying film to form a photoresist layer; exposing the photoresist layer to activating radiation in a patterned manner; and developing the exposed photoresist layer to provide a resist relief image.

[0088] A variety of substrates can be used in the patterning method, of which electronic device substrates are typical. Suitable substrates include, for example, packaging substrates such as multi-chip modules; flat panel display substrates; integrated circuit substrates; substrates for light-emitting diodes (LEDs) including organic light-emitting diodes (OLEDs); semiconductor wafers; polycrystalline silicon substrates; 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 manufactured in batches.

[0089] 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. The layers may be formed by various techniques, such as chemical vapor deposition (CVD), such as plasma-enhanced CVD (PECVD), low pressure CVD (LPCVD), or epitaxial growth, physical vapor deposition (PVD), such as sputtering or evaporation, or electroplating.

[0090] In certain patterning methods of the present invention, before forming the photoresist bottom layer of the present invention, it may be desirable to provide one or more photoresist layers on the upper surface of the substrate, such as a hard mask layer, for example, a spin-on carbon (SOC), an amorphous carbon or metal hard mask layer, a CVD layer, such as a silicon nitride (SiN) layer, a silicon oxide (SiO) layer or a silicon oxynitride (SiON) layer, an organic or inorganic BARC layer or a combination thereof. Such layers, together with the overcoat bottom layer and the photoresist layer of the present invention, form a photoresist material stack. Typical photoresist stacks that can be used in the patterning method of the present invention include, for example, the following: SOC layer / bottom layer / photoresist layer; SOC layer / SiON layer / bottom layer / photoresist layer; SOC layer / SiARC layer / bottom layer / photoresist layer; SOC layer / metal hard mask layer / bottom layer / photoresist layer; amorphous carbon layer / bottom layer / photoresist layer; and amorphous carbon layer / SiON layer / bottom layer / photoresist layer.

[0091] Can be coated on substrate with photoresist bottom layer composition by any suitable means such as spin coating, slot die coating, scraping, curtain coating, roller coating, spraying, dip coating etc.In the situation of semiconductor wafer, spin coating is preferred.In typical spin coating method, photoresist bottom layer composition is applied to the substrate that rotates with the speed of 500 to 4000rpm and continues 15 to 90 seconds time period to obtain the layer of the photoresist bottom layer composition of hope on substrate.Those skilled in the art will appreciate that the thickness of the photoresist bottom layer composition through applying can be regulated by changing the solids content of rotational speed and photoresist bottom layer composition.The photoresist bottom formed by the photoresist bottom layer composition typically has the dried layer thickness of 1 to 50nm, more typically 1 to 20nm.

[0092] Optionally, the applied photoresist bottom layer composition is soft-baked at a relatively low temperature to remove any solvent and other relatively volatile components from the photoresist bottom layer composition. Typically, the coated substrate is baked at a temperature of less than or equal to 150°C, preferably 60°C to 130°C and more preferably 90°C to 120°C. The baking time is typically 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes and more preferably 6 to 120 seconds. When the substrate is a wafer, this type of baking step can be carried out by heating the wafer on a hot plate. The soft baking step can be carried out as a part of the curing of the applied photoresist bottom layer composition, or can be omitted completely.

[0093] The applied photoresist bottom layer composition is then cured to form the photoresist bottom layer. The applied photoresist bottom layer composition should be fully cured so that the gained bottom layer does not mix with the layer applied subsequently (such as the photoresist layer or other organic or inorganic layer directly arranged on the photoresist bottom layer), or is minimally mixed with it. The applied 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 a condition (such as heating) that is enough to provide a cured coating. This curing step is preferably carried out on a hot plate type device, although oven curing can be used to obtain equivalent results. The curing temperature should be enough to make the acid catalyst cure in the whole layer, for example, be enough to make the free acid crosslinked, or make the hot acid generator release acid and make the released acid crosslinked. Typically, curing is carried out at a temperature of 150 ℃ or higher and preferably 150 ℃ to 450 ℃. More preferably, the curing temperature is 180 ℃ or higher, still more preferably 200 ℃ or higher and even more preferably 200 ℃ to 400 ℃.Curing time is typically 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes, more preferably 45 seconds to 2 minutes and still more preferably 45 to 90 seconds.Optionally, a ramp-up or multi-stage curing process can be used. Ramp-up baking typically starts at a relatively low (e.g., ambient) temperature, and the temperature is increased to a higher target temperature at a constant or variable ramp-up rate. A multi-stage curing process involves curing at two or more temperature platforms, typically carrying out the first stage at a lower baking temperature, and carrying out one or more other stages at a higher temperature. The conditions of such ramp-up or multi-stage curing processes are known to those skilled in the art and can allow for omitting a previous soft baking process.

[0094] After curing the applied photoresist bottom layer composition, one or more treatment layers (such as photoresist layers), hard mask layers (such as metal hard mask layers), organic or inorganic BARC layers etc. can be arranged on the cured photoresist bottom layer. The photoresist layer can be formed directly on the surface of the photoresist bottom layer, or alternatively, can be formed on the photoresist bottom layer on one or more intermediate layers. In this case, one or more intermediate treatment layers as described above can be formed sequentially on the photoresist bottom layer, and then form the photoresist layer. The determination of suitable layer, thickness and coating method is well known to those skilled in the art.

[0095] Various photoresists can be suitably used in the method of the present invention, and are typically positive materials. Suitable photoresists include, for example, materials in the photoresists of the EPIC series available from DuPont Electronics & Imaging in Marlborough, Massachusetts. Photoresists can be applied to substrates by known coating techniques (as described above about photoresist bottom compositions, where spin coating is typical). The typical thickness of the photoresist layer is 10 to 300 nm. Next, the photoresist layer is typically soft-baked to minimize the solvent content in the layer, thereby forming a non-stick coating and improving the adhesion of the layer to the substrate. Soft baking can be carried out on a hot plate or in an oven, where a hot plate is typical. Typical soft baking is carried out at a temperature of 70° C. to 150° C., and the time is 30 to 90 seconds.

[0096] 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 below 400nm and more typically below 300nm, such as 248nm (KrF), 193nm (ArF) or EUV wavelength (e.g., 13.5nm). In preferred aspects, the exposure wavelength is 193nm or EUV wavelength. The exposure energy is typically 10 to 150mJ / cm 2 , which depends on, for example, the exposure tool and the components of the photosensitive composition.

[0097] 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 70°C to 150°C and for a time of 30 to 90 seconds. This forms a latent image defined by the boundary between polarity-switched and unswitched regions (corresponding to exposed and unexposed regions, respectively). The exposed photoresist layer is then developed using a suitable developer to provide a patterned photoresist layer.

[0098] Then, the pattern of the photoresist layer can be transferred to one or more lower layers including the photoresist bottom layer and transferred to the substrate by appropriate etching techniques, as by using appropriate gas species to carry out plasma etching to each etched layer. Depending on the number of layers involved and materials, pattern transfer can involve multiple etching steps using different etching gases. After the substrate is patterned using conventional techniques, the patterned photoresist layer, the photoresist bottom layer and other optional layers in the photolithography stack can be removed. Optionally, one or more layers of the stack can be removed or consumed after the pattern is transferred to the lower 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.

[0099] The photoresist underlayer formed from the photoresist underlayer composition of the present invention shows excellent photospeed and improved pattern collapse. The preferred photoresist underlayer composition of the present invention can therefore be used in various semiconductor manufacturing processes.

[0100] The inventive concepts are further illustrated by the following examples, which are intended to be non-limiting. All compounds and reagents used herein are commercially available, except for the procedures provided below.

[0101] Examples

[0102] polymer synthesis

[0103] Synthesis Example 1

[0104] In round-bottomed flask, add 30.4 grams (g) of tris (2-hydroxyethyl) isocyanurate, 20.1g of tris (2-carboxyethyl) isocyanurate, 0.5g of p-toluenesulfonic acid, 20g of n-butyl alcohol and 34g of anisole.Reaction mixture is heated to 150 ℃ and stirred 3 hours (hrs.), and then diluted with 2-hydroxyisobutyric acid methyl ester (160g) to form mixed solutions.Subsequently, 1,3,4,6-tetrakis (methoxymethyl) tetrahydroimidazo [4,5-d] imidazole-2,5 (1H, 3H)-dione and the mixture of p-toluenesulfonic acid of 0.1g are added in the mixed solutions of 40g, and content is heated to 50 ℃ and stirred 4 hours.Reaction mixture is cooled to room temperature and quenched by adding triethylamine (0.4mL).From Virahol and heptane, be precipitated out product, filter, and then 40 ℃ of lower dryings 16 hours.

[0105] The structure of the polymer of Synthesis Example 1 is represented by formula (I):

[0106]

[0107] Synthesis Example 2

[0108] To the first round-bottom flask, 34.3 g of a solution containing ethyl lactate and γ-butyrolactone (1:1 by weight) was added, and the contents were heated to 80° C. In a second round-bottom flask, 13.9 g of (4-(tert-butyl)phenyl)diphenylsulfonium 1,1-difluoro-2-(methacryloyloxy)ethane-1-sulfonate, 3.3 g of 2-hydroxyethyl methacrylate, 12.8 g of 2,2,2-trifluoroethyl methacrylate, and 1.2 g of V601 initiator were dissolved in 150 g of a solution containing ethyl lactate and γ-butyrolactone (1:1 by weight), and this mixture was transferred to the first round-bottom flask over 4 hours. After the transfer was complete, the reaction mixture was held at 80° C. for an additional hour, and the contents were then cooled to room temperature. The product was precipitated from methyl tert-butyl ether, filtered, and then dried at 40° C. for 16 hours.

[0109] The structure of the polymer of Synthesis Example 2 is represented by Formula (II), wherein a is 19, b is 22, and c is 59.

[0110]

[0111] Synthesis Example 3

[0112] To the first round-bottom flask, 45.7 g of ethyl lactate and γ-butyrolactone (1:1 by weight) were added and the contents were heated to 80° C. In a second round-bottom flask, 15.2 g of 5-(4-(tert-butyl)phenyl)-5H-dibenzo[b,d]thiophen-5-ium 1,1-difluoro-2-(methacryloyloxy)ethane-1-sulfonate, 6.0 g of 2-hydroxyethyl methacrylate, 18.7 g of 2,2,2-trifluoroethyl methacrylate, and 1.7 g of V601 initiator were dissolved in 200 g of a solution containing ethyl lactate and γ-butyrolactone (1:1 by weight) and the mixture was transferred to the first round-bottom flask over 4 hours. After the transfer was complete, the reaction mixture was held at 80° C. for an additional hour, and the contents were then cooled to room temperature. The product was precipitated from methyl tert-butyl ether, filtered, and then dried at 40° C. for 16 hours.

[0113] The structure of the polymer of Synthesis Example 3 is represented by the above formula (II), wherein a is 17, b is 25, and c is 58.

[0114] Synthesis Example 4

[0115] To the first round-bottom flask was added 14.4 g of bis(4-(tert-butyl)phenyl)iodonium 1,1-difluoro-2-(methacryloyloxy)ethane-1-sulfonate, 5.0 g of 2-hydroxyethyl methacrylate, 15.6 g of 2,2,2-trifluoroethyl methacrylate, and 1.4 g of V601 initiator dissolved in 175 g of a solution containing ethyl lactate and gamma-butyrolactone (1:1 by weight), and the mixture was transferred to the first round-bottom flask over a period of 4 hours. After the transfer was complete, the reaction mixture was held at 80° C. for an additional hour, and the contents were then cooled to room temperature. The product was precipitated from methyl tert-butyl ether, filtered, and then dried at 40° C. for 16 hours.

[0116] The structure of the polymer of Synthesis Example 4 is represented by the above formula (II), wherein a is 17, b is 25, and c is 58.

[0117] Synthesis Example 5

[0118] To the first round-bottom flask was added 2.3 g of 5-(4-(2-((1-ethylcyclopentyl)oxy)-2-oxoethoxy)-3,5-dimethylphenyl)-5H-dibenzo[b,d]thiophen-5-ium((trifluoromethyl)sulfonyl)((4-vinylphenyl)sulfonyl)amide, 0.7 g of 2-hydroxyethyl methacrylate, 2.0 g of 2,2,2-trifluoroethyl methacrylate, and 0.2 g of V601 initiator dissolved in 25 g of a solution containing ethyl lactate and γ-butyrolactone (1:1 by weight), and the mixture was transferred to the first round-bottom flask over 4 hours. After the transfer was complete, the reaction mixture was held at 80° C. for an additional hour, and the contents were then cooled to room temperature. The product was precipitated from methyl tert-butyl ether, filtered, and then dried at 40° C. for 16 hours.

[0119] The structure of the polymer of Synthesis Example 5 is represented by Formula (III) wherein a is 19, b is 26, and c is 55.

[0120]

[0121] Composition

[0122] Example 1

[0123] 0.23 g of the polymer of Synthesis Example 1, 0.06 g of the polymer of Synthesis Example 2, and 0.01 g of 2,4,6-trimethylpyridin-1-ium 4-methylbenzenesulfonate were dissolved in 99.7 g of methyl 2-hydroxyisobutyrate, and the mixture was passed through a micro syringe filter having a pore size of 0.2 μm.

[0124] Example 2

[0125] 0.23 g of the polymer of Synthesis Example 1, 0.06 g of the polymer of Synthesis Example 3, and 0.01 g of 2,4,6-trimethylpyridin-1-ium 4-methylbenzenesulfonate were dissolved in 99.7 g of methyl 2-hydroxyisobutyrate, and the mixture was passed through a micro syringe filter having a pore size of 0.2 μm.

[0126] Example 3

[0127] 0.22 g of the polymer of Synthesis Example 1, 0.07 g of the polymer of Synthesis Example 3, and 0.01 g of 2,4,6-trimethylpyridin-1-ium 4-methylbenzenesulfonate were dissolved in 99.7 g of methyl 2-hydroxyisobutyrate, and the mixture was passed through a micro syringe filter having a pore size of 0.2 μm.

[0128] Example 4

[0129] 0.23 g of the polymer of Synthesis Example 1, 0.06 g of the polymer of Synthesis Example 4, and 0.01 g of 2,4,6-trimethylpyridin-1-ium 4-methylbenzenesulfonate were dissolved in 99.7 g of methyl 2-hydroxyisobutyrate, and the mixture was passed through a micro syringe filter having a pore size of 0.2 μm.

[0130] Example 5

[0131] 0.23 g of the polymer of Synthesis Example 1, 0.06 g of the polymer of Synthesis Example 5, and 0.01 g of 2,4,6-trimethylpyridin-1-ium 4-methylbenzenesulfonate were dissolved in 99.7 g of methyl 2-hydroxyisobutyrate, and the mixture was passed through a micro syringe filter having a pore size of 0.2 μm.

[0132] Example 6 (comparison)

[0133] 0.29 g of the polymer of Synthesis Example 1 and 0.01 g of 2,4,6-trimethylpyridin-1-ium 4-methylbenzenesulfonate were dissolved in 99.7 g of methyl 2-hydroxyisobutyrate, and the mixture was passed through a micro syringe filter having a pore size of 0.2 μm.

[0134] Photoresist composition

[0135] A mixture for making a photoresist composition was prepared by combining the following components: (1r,3r,5r,7r)-2-isopropyladamantan-2-yl methacrylate: 1-methylcyclopentyl methacrylate: 2-oxotetrahydrofuran-3-yl methacrylate: (3aS,4S,5R,7S,7aS)-1-oxooctahedral-4,7-epoxybenzofuran-5-yl methacrylate (26.40 g, 10 wt % in propylene glycol monomethyl ether acetate, the molar ratio of the units in the copolymer being 11:29:42:18), 2-(methacryloyloxy)propane-1,3-diylbis(2,2-difluoropropionate): 1-ethylcyclopentyl methacrylate (1.96 g, 5 wt % in propylene glycol monomethyl ether acetate, the molar ratio of the units in the copolymer being 11:29:42:18), The mixture was added with 1,2-difluoro-2-(((1r,3s,5R,7S)-3-hydroxyadamantan-1-yl)methoxy)-2-oxoethane-1-sulfonate (53.78 g, 0.8 wt% in methyl 2-hydroxyisobutyrate), tri-p-tolylsulfonium ((3s,5s,7s)-adamantan-1-yl)sulfamate (8.97 g, 2 wt% in methyl 2-hydroxyisobutyrate), tert-butyl (1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl)carbamate (0.29 g, 2 wt% in methyl 2-hydroxyisobutyrate), propylene glycol monomethyl ether acetate (14.05 g), and methyl 2-hydroxyisobutyrate (0.16 g). The mixture was passed through a filter having a pore size of 0.2 micrometers. The mixture was then added to a solution of propylene glycol methyl ether acetate and methyl 2-hydroxyisobutyrate (2:3 by weight) to form a photoresist composition having a solid content of 1.1 wt %.

[0136] Resist patterning evaluation

[0137] The compositions of Examples 1 to 6 were coated on an 8-inch bare silicon wafer and cured at 205° C. for 60 seconds (s) to form a A first layer of thickness of 100 nm was prepared. A photoresist composition was then coated on the first layer, and the resulting combination was soft baked at 110°C for 90 seconds to form a second layer having a thickness of 30 nm. The wafer was exposed on a JBX9300FS EB scanner at an energy of 100 keV to form a 70 nm 1:1 line / space (L / S) pattern. The wafer was post-exposed and baked at 100°C for 60 seconds, developed with a 0.26 NTMAH solution, and spin dried to form a photoresist pattern. The patterned wafer was inspected on a HITACHI S9380 CD-SEM tool. The optimal exposure dose E of the 70 nm 1:1 L / S patterned resist on the bottom layer example was evaluated by direct electron beam writing using electron beam lithography. op (μC / cm 2 The results are shown in Table 1.

[0138] Table 1

[0139] <![CDATA[E op (μC / cm 2 )]]> Patterning dose (μC) EL margin (%) Example 1 386 300 14.7 Example 2 306 240 17.3 Example 3 269 200 19.0 Example 4 298 240 16.9 Example 5 367 280 15.9 Example 6 (comparison) 457 320 12.8

[0140] The photoresist underlayer compositions of Examples 1 to 5, which can improve scum / bridging defects through effective acid generation, achieve 20%-41% faster photospeeds relative to Comparative Example 6 and show improved pattern collapse margins in low-dose areas.

[0141] 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 first polymer comprising isocyanurate repeating units and crosslinkable groups; a second polymer, said second polymer comprising: a first repeating unit comprising a repeating unit comprising a photoacid generator, and The second repeating unit comprises a hydroxyl-substituted C 1-30 Alkyl, hydroxy substituted C 3-30 Cycloalkyl, or hydroxy substituted C 6-30 aryl; acid catalysts; and solvent.

2. The photoresist underlayer composition according to claim 1, wherein The isocyanurate repeating units are derived from monomers having formula (1): In formula (1), K, L and M are each independently a linear or branched C 1-10 Hydrocarbon, C 1-10 Alkoxycarbonyl, C 1-10 Alkanoyloxy, each of which is optionally substituted by a carboxylic acid group, or a linear or branched C 1-10 Hydroxyalkyl, which is optionally replaced by C 1-5 Alkoxycarbonyl or C 1-5 substituted alkoxy substituted, and Wherein, at least one hydrogen atom of the first polymer is substituted by a functional group independently selected from hydroxyl, carboxyl, thiol, amino, epoxy, alkoxy, amide, vinyl and combinations thereof.

3. The photoresist underlayer composition according to any one of claims 1 or 2, wherein The first repeating unit of the second polymer comprises a repeating unit derived from a monomer having formula (2): In formula (2), R a is hydrogen, fluorine, cyano, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted C 1-10 Fluoroalkyl, L 1 is a single bond or a divalent linking group, A is a divalent linking group; Z - is an anion moiety comprising a sulfonate, a sulfonamide anion, a sulfonimide anion, or a methide anion; and G + It is an organic cation.

4. The photoresist underlayer composition according to claim 3, wherein -L 1 -AZ - It is expressed by one of equations (3) to (5b): Wherein, in formulas (3) to (5b), Q 1 and Q 2 are each independently a fluorine-substituted divalent linking group; Q 3 is a divalent linking group; Q 4 is a single bond or a divalent linking group; and R f is fluorine-substituted C 1-30 Alkyl, fluorine-substituted C 3-30 Cycloalkyl, or with Q 3 Single bonds forming a ring.

5. The photoresist underlayer composition according to claim 3, wherein G + is a cation represented by one of formulas (6), (7) or (8): Wherein, in equations (6), (7) and (8): X is I or S; R h 、R i 、R j and R k are each independently hydroxy, nitrile, halogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Fluoroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 1-30 Fluorinated cycloalkyl, substituted or unsubstituted C 1-30 Alkoxy, substituted or unsubstituted C 3-30 Alkoxycarbonylalkyl, substituted or unsubstituted C 3-30 Alkoxycarbonylalkoxy, substituted or unsubstituted C 3-30 Cycloalkoxy, substituted or unsubstituted C 5-30 Cycloalkoxycarbonylalkyl, substituted or unsubstituted C 5-30 Cycloalkoxycarbonylalkoxy, substituted or unsubstituted C 1-30 Fluoroalkoxy, substituted or unsubstituted C 3-30 Fluoroalkoxycarbonylalkyl, substituted or unsubstituted C 3-30 Fluoroalkoxycarbonylalkoxy, substituted or unsubstituted C 3-30 Fluorocycloalkoxy, substituted or unsubstituted C 5-30 Fluorocycloalkoxycarbonylalkyl, substituted or unsubstituted C 5-30 Fluorocycloalkoxycarbonylalkoxy, substituted or unsubstituted C 6-30 Aryl, C 6-30 Fluoroaryl, substituted or unsubstituted C 6-30 Aryloxy, substituted or unsubstituted C 6-30 fluoroaryloxy; Each R aa are independently substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Fluoroalkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted C 3-20 Fluorinated cycloalkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 2-20 Fluoroalkenyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 6-30 Fluoroaryl, substituted or unsubstituted C 6-30 Iodoaryl, substituted or unsubstituted C 4-30 Heteroaryl, substituted or unsubstituted C 7-20 Arylalkyl, substituted or unsubstituted C 7-20 Fluoroarylalkyl, substituted or unsubstituted C 5-30 Heteroarylalkyl, or substituted or unsubstituted C 5-30 Fluoroheteroarylalkyl, wherein each R aa is alone or connected to another group R via a single bond or a divalent linking group aa forming a ring; When X is 1, p is 2, and R l It is a lone pair of electrons; When X is S, p is 3, and R l is substituted or unsubstituted C 6-20 aryl; q and r are each independently an integer from 0 to 5; and s and t are each independently an integer from 0 to 4.

6. The photoresist underlayer composition according to any one of claims 1 or 2, wherein The second repeating unit of the second polymer is derived from a monomer of formula (9): Among them, in formula (9), R a is hydrogen, halogen, cyano, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted C 1-10 Fluoroalkyl; L 2 is a single bond or a divalent linking group; Y includes hydroxy substituted C 1-30 Alkyl, hydroxy substituted C 3-30 Cycloalkyl, hydroxy substituted C 6-30 Aryl, hydroxy substituted C 5-30 heteroaryl, or a combination thereof, each of which is optionally further substituted.

7. The photoresist base composition according to any one of claims 1 or 2, in, The crosslinkable groups of the first polymer include hydroxyl, carboxyl, thiol, amino, epoxy, alkoxy, amide, vinyl, or a combination thereof, and The polymerizable group of the second polymer includes a carboxyl group, a thiol group, an amino group, an epoxy group, an alkoxy group, an amide group, a vinyl group, or a combination thereof.

8. The photoresist underlayer composition according to any one of claims 1 or 2, wherein The second polymer further comprises a third repeating unit comprising an unsubstituted C 1-30 Alkyl, fluorine-substituted C 1-30 Alkyl, C substituted by polymerizable groups 1-30 Alkyl, C substituted by polymerizable groups 3-30 Cycloalkyl, or C substituted by a polymerizable group 6-30 An aryl group, wherein the polymerizable group is reactive toward self-crosslinking a second polymer.

9. A coated substrate comprising: A cured layer of the photoresist base composition according to any one of claims 1 to 8 disposed on a substrate; as well as A photoresist layer is disposed on the cured layer of the photoresist underlayer composition.

10. A method for forming a pattern, the method comprising: applying a layer of the photoresist base composition according to any one of claims 1 to 8 on a substrate; curing the applied layer of the photoresist base layer composition to form a base layer film; applying a layer of a photoresist composition on the underlying film to form a photoresist layer; pattern-wise exposing the applied photoresist layer to activating radiation; as well as The exposed photoresist layer is developed to provide a resist relief image.

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