Method for forming a pattern using an antireflective coating composition containing a photoacid generator

Abstract

An antireflective coating composition is disclosed, which comprises a polymer, a photoacid generator having a crosslinkable group, a compound capable of crosslinking the polymer and the photoacid generator, a thermal acid generator, and an organic solvent.

Description

Technical Field

[0001] The present disclosure generally relates to antireflective coating compositions for use with photoresist applications. Specifically, the present disclosure provides antireflective compositions for improving pattern collapse margin in negative tone development. Background Art

[0002] A photoresist is a photosensitive composition used to transfer an image onto a substrate. A coating of the photoresist is formed on a substrate and then exposed to actinic radiation through a photomask. The photomask has areas that are opaque and transparent to actinic radiation. When the photoresist coating is exposed to actinic radiation, light-induced chemical modifications occur on the photoresist coating. As a result, the pattern of the photomask is transferred to the photoresist coating. Thereafter, the photoresist coating is developed to form a patterned image that can be selectively processed on the substrate.

[0003] Typically, chemically amplified negative photoresists include resins and photoacid generators (PAGs) with acid-labile leaving groups. When such photoresists are exposed to chemical radiation, the photoacid generator forms an acid, and the acid formed in this way causes the acid-labile group to break away from the resin during the baking process after exposure. The removal of the acid-labile group produces different solubility characteristics between the exposed area and the non-exposed area to aqueous alkaline developers or developers based on hydrophobic organic solvents. The exposed area of ​​the resist makes it soluble in aqueous alkaline developers and insoluble in developers based on hydrophobic organic solvents. In the manufacturing process of semiconductor devices, the positive process uses aqueous alkaline developers and only leaves the non-exposed area of ​​the photoresist on the substrate; and the negative process uses a developer based on a hydrophobic organic solvent and only leaves the exposed area of ​​the photoresist on the substrate.

[0004] Typically, photoresists are used to print micron or nanometer-scale patterns on semiconductor substrates such as Si or GaAs, which are converted into a complex matrix of electronic conduction paths (preferably micron or submicron geometries) for performing circuit functions. To achieve such purposes, the details of photoresist treatment and processing conditions are very important. Several operations for processing photoresists work interdependently, but one of the most important operations for obtaining high-resolution photoresist images is the radiation exposure step.

[0005] In such light exposure operations, reflected radiation from the photoresist coating degrades the resolution of the patterned features. For example, when the exposure radiation is reflected at the interface between the substrate and the photoresist, the intensity of the radiation radiated to the photoresist coating varies spatially, and the radiation is scattered toward the photoresist areas that are intentionally not exposed. Therefore, the reflection of radiation during photoresist exposure leads to a lack of pattern uniformity during development, such as uneven line widths in printed line-space features. In addition, due to differences in the amount of scattered radiation or reflected radiation between regions, the resolution may become sensitive to the substrate topography.

[0006] In order to solve the above-described reflection-related problems, an additional light absorbing layer, ie, an antireflective coating, is coated between the substrate surface and the photoresist coating (see US Pat. Nos. 5,939,236, 5,886,102, 5,851,738, 5,851,730, etc.).

[0007] However, in the case of such conventional antireflective coatings, when the pattern has a small critical dimension (40nm or less), negative tone development (NTD) in the photolithography process often suffers from pattern collapse. This phenomenon has led to deterioration of product quality and low yield due to considerable difficulty in ensuring process margin.

[0008] Recently, pattern collapse margin (PCM) in NTD process has become the most critical issue for higher yield in ArF immersion lithography with reduced pattern scale. PCM in NTD depends significantly on the properties of bottom anti-reflective coating (BARC) film. In particular, acidic BARC surface can strongly enhance pattern collapse by further increasing the deprotection reaction of photoresist. As an acidic catalyst in BARC, photoacid generator can be one of the good acidity control units in BARC formulation because it can improve pattern collapse by acid generated only in exposed areas. However, the main disadvantage of this method is that the PAG concentration on the BARC surface is reduced during photoresist spin coating or reduced resist consumption (RRC) process due to dissolution by process solvents. There is still a need for new anti-reflective coating compositions that can improve pattern collapse margin in negative development. Summary of the invention

[0009] The embodiment provides an anti-reflective coating composition including a polymer, a photoacid generator having a crosslinkable group, a compound capable of crosslinking the polymer and the photoacid generator, a thermal acid generator, and an organic solvent.

[0010] Another embodiment provides a coated substrate comprising (a) a substrate; and (b) a layer of an antireflective coating composition disposed on the substrate.

[0011] Yet another embodiment provides a method of forming a pattern, comprising:

[0012] (a) applying a layer of the antireflective coating composition on a substrate;

[0013] (b) curing the applied antireflective coating composition to form an antireflective layer;

[0014] (c) forming a photoresist layer on the anti-reflective layer; and

[0015] (d) patterning the photoresist layer and transferring the pattern from the patterned photoresist layer to the antireflective layer. DETAILED DESCRIPTION

[0016] 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 set forth herein. Therefore, exemplary embodiments are described below only by reference to the accompanying drawings to explain aspects of this specification. As used herein, the term "and / or" includes any and all combinations of one or more related listed items. When a statement such as "at least one of..." follows a list of elements, it modifies the entire list of elements and does not modify the individual elements in the list.

[0017] It should be understood that when an element is referred to as being "on" another element, it can be in direct contact with the other element or intervening elements that may exist therebetween. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements.

[0018] It should be understood that although the terms first, second, third, etc. can be used to describe various elements, components, regions, layers and / or parts in this article, these elements, components, regions, layers and / or parts should not be limited by these terms. These terms are only used to distinguish an element, component, region, layer or part from another element, component, region, layer or part. Therefore, the first element, component, region, layer or part discussed below can be referred to as the second element, component, region, layer or part without departing from the teaching of the embodiments of the present invention.

[0019] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0020] It should be further understood that when used in this specification, the terms “comprises” and / or “comprising”, or “includes” and / or “including” specify the presence of specified features, regions, integers, steps, operations, elements and / or components, but do not exclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components and / or groups thereof.

[0021] As used herein, "about" includes the stated value and means within an acceptable range of deviation of the particular value as determined by one of ordinary skill in the art, taking into account the measurement in question and the errors associated with the measurement of the particular quantity (i.e., the limitations of the measurement system). For example, "about" can mean within one or more standard deviations, or within ±30%, 20%, 10%, 5% of the stated value.

[0022] 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 should 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 in an idealized or overly formal sense unless explicitly defined as such herein.

[0023] As used herein, when no definition is otherwise provided, the term "hydrocarbyl" refers to an organic compound having at least one carbon atom and at least one hydrogen atom, optionally substituted where indicated with one or more substituents.

[0024] As used herein, when no definition is otherwise provided, the term "alkyl" refers to a group derived from a straight or branched chain saturated aliphatic hydrocarbon having the specified number of carbon atoms and having a valence of at least one.

[0025] As used herein, when no definition is otherwise provided, the term "hydroxyalkyl" refers to an alkyl group substituted with at least one hydroxyl (-OH) group.

[0026] As used herein, when no definition is otherwise provided, the term "alkoxy" refers to "alkyl-O-," wherein the term "alkyl" has the same meaning as the "alkyl" described above.

[0027] As used herein, when no definition is otherwise provided, the term "carboxylic acid group" refers to a group having the formula "-C(=O)-OH".

[0028] As used herein, when a definition is not otherwise provided, the term "cycloalkyl" refers to a monovalent group having one or more saturated rings, wherein all ring members are carbon.

[0029] As used herein, when a definition is not otherwise provided, the term "alkenyl" refers to a straight or branched monovalent hydrocarbon group having at least one carbon-carbon double bond.

[0030] As used herein, when no definition is otherwise provided, the term "aryl" used alone or in combination refers to an aromatic or heteroaromatic hydrocarbon containing at least one ring and having a specified number of carbon atoms. The term "aryl" may be interpreted as a group containing an aromatic or heteroaromatic ring fused to at least one cycloalkyl or heterocycloalkyl ring. "Aryl" may contain one or more heteroatoms independently selected from nitrogen (N), oxygen (O), phosphorus (P) and sulfur (S).

[0031] As used herein, when no definition is otherwise provided, the term "aryloxy" refers to "aryl-O-", wherein the term "aryl" has the same meaning as the "aryl" described above.

[0032] As mentioned above, the pattern collapse margin (PCM) in negative tone development (NTD) depends significantly on the properties of the bottom anti-reflective coating (BARC) film. In particular, an acidic BARC surface can strongly enhance pattern collapse by the deprotection reaction of the photoresist. A photoacid generator as a precursor of an acidic catalyst can be one of the good acidity control units in a BARC formulation because it can improve pattern collapse by the acid generated in the exposed area. However, the PAG concentration on the BARC surface decreases during photoresist spin coating because a portion of the PAG is washed away by the process solvent.

[0033] The inventors of the present invention have discovered that the implementation of a cross-linkable PAG in an anti-reflective composition can provide reduced PAG loss on the BARC surface through a cross-linking reaction with the BARC polymer during the polymer baking step, and that the provided anti-reflective layer exhibits greatly improved pattern collapse through the strong acid efficiently generated from the cross-linked PAG in the exposed BARC area.

[0034] Therefore, an embodiment of the present invention provides an anti-reflective coating composition comprising a polymer, a photoacid generator having a crosslinkable group, a compound capable of crosslinking the polymer and the photoacid generator, a thermal acid generator, and an organic solvent.

[0035] The anti-reflective composition comprises a photoacid generator with a crosslinkable group. As used herein, the term "crosslinkable group" refers to any reactive group that can crosslink a photoacid generator with a polymer. The crosslinkable group can be an unsaturated functional group, such as a carbon-carbon double bond or a carbon-carbon triple bond that can react by a free radical mechanism. The crosslinkable group can also be a functional group containing heteroatoms such as nitrogen, oxygen, phosphorus, sulfur or halogen. For example, the crosslinkable group can be a hydroxyl, an alkoxyl, an amino (which can be unsubstituted or substituted by at least one alkyl or at least one aryl), a thiol group, a thioether group, a carbonyl group present in an aldehyde and a ketone, a carboxylic acid group or its salt, a phosphoric acid group or its salt, a sulfonic acid group or its salt, a carboxylate group, can be an amide group, a sulfonate group or a phosphate group that can be unsubstituted or substituted by at least one alkyl or at least one aryl, but is not limited thereto. In an embodiment, the crosslinkable group can be a hydroxyl.

[0036] The crosslinkable photoacid generator can be an onium photoacid generator, such as a sulfonium salt or an iodonium salt, each comprising a cationic portion and an anionic portion. The crosslinkable group can be contained in the cationic portion or the anionic portion of the onium salt. When the onium salt comprises an aromatic group, the crosslinkable group can be attached directly or indirectly to the aromatic group.

[0037] In an embodiment, the photoacid generator may be a + A - Onium salt, where G + It can have formula 1 and A - Can be non-polymerizable organic anions:

[0038] Formula 1

[0039]

[0040] In Formula 1, z can be 2 or 3, wherein when Y is I, z is 2, or when Y is S, z is 3.

[0041] Each R in Formula 1 1 may be independently substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted polycyclic or monocyclic C 3-30 Cycloalkyl, substituted or unsubstituted polycyclic or monocyclic C 6-30 Aryl, wherein when X is S, the R 1 One of them may optionally be attached to an adjacent R via a single bond or a linking group. 1 At least one R in Formula 1 1 It is a polycyclic or monocyclic C 6-30 The hydroxyl group is directly (via a single bond) or indirectly (via an unsubstituted or substituted C1-C ... 30A linking group) is attached thereto.

[0042] In this example, G + It can be expressed by formula 2:

[0043] Formula 2

[0044]

[0045] In formula 2,

[0046] Each R a may independently be hydrogen, halogen, cyano, nitro, amino, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C3-C 30 Cycloalkyl, substituted or unsubstituted C3-C 30 Cycloalkenyl, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C6-C 30 Aryloxy, substituted or unsubstituted C6-C 30 Thioaryl, substituted or unsubstituted C7-C 30 Arylalkyl,

[0047] Each R b may be independently substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted polycyclic or monocyclic C 3-30 Cycloalkyl, substituted or unsubstituted polycyclic or monocyclic C 6-30 Aryl, where the group R b may optionally be attached to each other via a single bond or a linking group,

[0048] Each L can be a single bond, a substituted or unsubstituted C1-C 30 Alkylene, substituted or unsubstituted C2-C 30 Alkenylene, substituted or unsubstituted C2-C 30 Alkyne, substituted or unsubstituted C3-C 30 Cycloalkenylene, substituted or unsubstituted C3-C 30 Cycloalkynylene, substituted or unsubstituted C6-C 30 Arylene, or substituted or unsubstituted C6-C 30Heteroarylene, in each of which at least one non-adjacent -CH2- group is optionally replaced by -SO2-, -C(=O)-, -O-, -S-, -SO-, -C(=O)O-, -OC(=O)-, -C(=O)NR-, or -NRC(=O)-, wherein R is hydrogen or C1-C 10 Alkyl or combinations thereof;

[0049] n1 is an integer from 1 to 5, and

[0050] n2 is an integer from 0 to 4,

[0051] The condition is that the sum of n1 and n2 does not exceed 5.

[0052] In another example, G + It can be expressed by formula 3:

[0053] Formula 3

[0054]

[0055] In formula 3,

[0056] Each R a may independently be hydrogen, halogen, cyano, nitro, amino, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C3-C 30 Cycloalkyl, substituted or unsubstituted C3-C 30 Cycloalkenyl, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C6-C 30 Aryloxy, substituted or unsubstituted C6-C 30 Thioaryl, substituted or unsubstituted C7-C 30 Arylalkyl, where the group R a optionally attached to each other via a single bond or a linking group,

[0057] R b It may be substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted polycyclic or monocyclic C 3-30 Cycloalkyl, substituted or unsubstituted polycyclic or monocyclic C 6-30 Aryl,

[0058] Each L can be a single bond, a substituted or unsubstituted C1-C 30 Alkylene, substituted or unsubstituted C2-C30 Alkenylene, substituted or unsubstituted C2-C 30 Alkyne, substituted or unsubstituted C3-C 30 Cycloalkenylene, substituted or unsubstituted C3-C 30 Cycloalkynylene, substituted or unsubstituted C6-C 30 Arylene, or substituted or unsubstituted C6-C 30 Heteroarylene, in each of which at least one non-adjacent -CH2- group is optionally replaced by -SO2-, -C(=O)-, -O-, -S-, -SO-, -C(=O)O-, -OC(=O)-, -C(=O)NR-, or -NRC(=O)-, wherein R is hydrogen or C1-C 10 Alkyl or combinations thereof;

[0059] Each n1 can be an integer from 1 to 5, and

[0060] n2 can be an integer from 0 to 4,

[0061] The condition is that the sum of each n1 and n2 does not exceed 5.

[0062] In yet another example, G + It can be expressed by formula 4:

[0063] Formula 4

[0064]

[0065] In formula 4,

[0066] Each R a It can be hydrogen, halogen, cyano, nitro, amino, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C3-C 30 Cycloalkyl, substituted or unsubstituted C3-C 30 Cycloalkenyl, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C6-C 30 Aryloxy, substituted or unsubstituted C6-C 30 Thioaryl, substituted or unsubstituted C7-C 30 Arylalkyl,

[0067] Each L can be a single bond, a substituted or unsubstituted C1-C 30 Alkylene, substituted or unsubstituted C2-C30 Alkenylene, substituted or unsubstituted C2-C 30 Alkyne, substituted or unsubstituted C3-C 30 Cycloalkenylene, substituted or unsubstituted C3-C 30 Cycloalkynylene, substituted or unsubstituted C6-C 30 Arylene, or substituted or unsubstituted C6-C 30 Heteroarylene, in each of which at least one non-adjacent -CH2- group is optionally replaced by -SO2-, -C(=O)-, -O-, -S-, -SO-, -C(=O)O-, -OC(=O)-, -C(=O)NR-, or -NRC(=O)-, wherein R is hydrogen or C1-C 10 Alkyl or combinations thereof;

[0068] Each n1 can be an integer from 1 to 5, and

[0069] n2 can be an integer from 0 to 4,

[0070] The condition is that the sum of each n1 and n2 does not exceed 5.

[0071] Non-polymerizable organic anion A - It can be a sulfonate anion. For example, A - Can be non-fluorinated sulfonate anion, partially fluorinated sulfonate anion, or fully fluorinated sulfonate anion. In an embodiment, A - It can be represented by the formula R-SO3 - It represents, wherein R is a linear or branched C1-C30 alkyl group or a linear or branched C1-C30 heteroalkyl group, each of which may optionally contain at least one fluorine atom.

[0072] In another embodiment, A - It can be expressed by formula 8:

[0073] Formula 8

[0074] [A-(CHR 1 ) p ] k –(L)-(CH2) m -(C(R 2 )2) n -SO3 -

[0075] In formula 8,

[0076] A is a substituted or unsubstituted, monocyclic, polycyclic, or fused polycyclic C5 or larger alicyclic group, which optionally contains O, S, N, F, or a combination comprising at least one of the foregoing,

[0077] R 1 is H, a single bond, or substituted or unsubstituted C 1-30 Alkyl, where R 1 When it is a single bond, R 1 Covalently bonded to the carbon atom of A,

[0078] Each R 2 are independently H, F, or C 1-4 A fluoroalkyl group, wherein at least one R 2 Not hydrogen,

[0079] L is a linking group, wherein the linking group comprises a sulfonate group, a sulfonamide group, or a C 1-30 a sulfonate or sulfonamide group, and

[0080] p is an integer of 0 to 10, k is 1 or 2, m is an integer of 0 or more, and n is an integer of 1 or more.

[0081] In some embodiments, the cross-linkable photoacid generator may be represented by one of the following formulas (PA-1) to (PA-32):

[0082]

[0083]

[0084] The amount of the crosslinkable photoacid generator in the antireflective composition may be 1 wt % to 15 wt % based on the total solids of the antireflective composition. For example, the amount of the crosslinkable photoacid generator in the antireflective composition may be 1 wt % to 10 wt % based on the total solids of the antireflective composition or 1 wt % to 5 wt % based on the total solids of the antireflective composition, but is not limited thereto.

[0085] The antireflective composition further comprises a polymer capable of crosslinking with a photoacid generator. The polymer may comprise a cyanurate structural unit comprising a cyanurate structural unit comprising a cyanurate structural unit having a unique (different) carboxyl group (e.g., -COOH) and / or a carboxyl ester (e.g., -COOR, wherein R is not hydrogen, such as C1-C 12 The cyanurate structural unit can be derived from a compound represented by the free formula 5:

[0086] Formula 5

[0087]

[0088] In Formula 5, R 3 OOC(CX2) m1 -、R 2 - and R 4 OOC(CX2)m1 - may represent different acid or ester groups. 3 OOC(CX2) m1 -、R 2 - and R 3 OOC(CX2) m1 The statement that at least two of the groups R are different acid or ester groups means that at least two groups will have at least one atom difference. For example, if the values ​​of m1 are not equal, then the groups will be different acid or ester groups. 3 and R 4 Not the same (for example, R 3 is -CH3 and R 4 If R is -H), the groups will be different acid or ester groups. 2 is acid and R 3 is not hydrogen, then the groups are different. In many cases, the groups will differ by two or more atoms.

[0089] In formula 5,

[0090] R 2 , R 3 , R 4 , and each X may independently be a hydrogen or non-hydrogen substituent, such as a substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 2-30 alkenyl (such as optionally substituted allyl), substituted or unsubstituted C 2-30 alkynyl (such as optionally substituted propargyl), substituted or unsubstituted C 2-30 Alkanoyl (such as optionally substituted acetyl), substituted or unsubstituted C1-C 30 Alkoxy (such as optionally substituted methoxy, propoxy, butoxy), substituted or unsubstituted C1-C 30 Sulfanyl, substituted or unsubstituted C1-C 30 Alkylsulfinyl, substituted or unsubstituted C1-C 30 Alkylsulfonyl, -COOH, substituted or unsubstituted C2-C 30 Alkoxycarbonyl (including esters which are substantially unreactive with photoacids); substituted or unsubstituted C7-C 30 alkylaryl (such as optionally substituted benzyl), substituted or unsubstituted C6-C 30 Aryl (such as optionally substituted phenyl, naphthyl, acenaphthenyl), or substituted or unsubstituted C3-C 30 Heteroalicyclic or substituted or unsubstituted C3-C 30heteroaromatic groups (such as optionally substituted methylphthalimide, N-methyl-1,8-phthalimide), and

[0091] Each m1 may be the same or different and may independently be an integer from 1 to 10.

[0092] In an embodiment, the cyanurate structural unit can be derived from a compound represented by Formula 5a:

[0093] Formula 5a

[0094]

[0095] In Formula 5a, R 2 , R 3 and R 4 The same groups as those described with respect to Formula 5 above.

[0096] In Formulas 5 and 5a, R 2 It can be used to introduce various functional groups into the polymer, including those that impart desired imprinting properties, such as optical properties, etching rate, thermal properties, solubility in coating solvents, and coating properties on different substrate surfaces. 2 It may also affect the polymerization process used to obtain more linear and higher molecular weight coating polymer compositions.

[0097] The polymer may further include a cyanurate structural unit derived from the compound represented by Formula 6.

[0098] Formula 6

[0099]

[0100] In formula 6,

[0101] Each X', each X", and each R 5 may independently be hydrogen or non-hydrogen substituents, such as substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 2-30 alkenyl (such as optionally substituted allyl), substituted or unsubstituted C 2-30 alkynyl (such as optionally substituted propargyl), substituted or unsubstituted C 2-30 Alkanoyl (such as optionally substituted acetyl), substituted or unsubstituted C1-C 30 Alkoxy (such as optionally substituted methoxy, propoxy, butoxy), substituted or unsubstituted C1-C 30 Sulfanyl, substituted or unsubstituted C1-C 30 Alkylsulfinyl, substituted or unsubstituted C1-C30 Alkylsulfonyl, substituted or unsubstituted C1-C 30 (Alkyl)carboxyl (which includes groups such as: wherein R' is H or C1-C 30 -COOR' of alkyl, including esters that are substantially unreactive with photoacids); substituted or unsubstituted C7-C 30 alkylaryl (such as optionally substituted benzyl), substituted or unsubstituted C6-C 30 Aryl (such as optionally substituted phenyl, naphthyl, acenaphthenyl), or substituted or unsubstituted C3-C 30 Heteroalicyclic or substituted or unsubstituted C3-C 30 heteroaromatic groups (such as optionally substituted methylphthalimide, N-methyl-1,8-phthalimide), and

[0102] Each m2 may be the same or different and each may be an integer, such as 0, 1, 2, 3 or 4, with m2 being equal to a positive integer such as 1 or 2 being generally preferred.

[0103] The amount of the polymer in the anti-reflective composition may be 75 wt % to 99 wt % based on the total solids of the anti-reflective composition. For example, the amount of the polymer in the anti-reflective composition may be 85 wt % to 95 wt % based on the total solids of the anti-reflective composition, but is not limited thereto.

[0104] The composition further comprises a crosslinkable compound, which is not particularly limited and can be any crosslinking substance that can initiate a crosslinking reaction by light and / or heat. For example, the crosslinkable compound can be a molecule that can initiate a crosslinking reaction by heat. When the photoacid generator releases an acid after exposure to activating radiation, the crosslinkable compound is cured, crosslinked or hardened.

[0105] In an embodiment, the cross-linkable compound may be represented by Formula 7

[0106] Formula 7

[0107]

[0108] In formula 7,

[0109] Each X', each X", each R 5 , R 6 and R 7 may independently be hydrogen, halogen, hydroxyl, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C3-C 30 Cycloalkyl, substituted or unsubstituted C7-C 30arylalkyl, and

[0110] Each m2 and each m3 may independently be an integer from 1 to 10.

[0111] The amount of the crosslinkable compound in the anti-reflective composition may be 0 wt % to 15 wt % by weight based on the total solids of the anti-reflective composition. For example, the amount of the crosslinkable compound in the anti-reflective composition may be 0 wt % to 10 wt % based on the total solids of the anti-reflective composition or 0 wt % to 5 wt % based on the total solids of the anti-reflective composition, but is not limited thereto.

[0112] When the polymer reacts with the crosslinkable compound, a crosslinked polymer is formed. In an embodiment, the crosslinked polymer may include a structural unit derived from a compound represented by Formula 5 and a structural unit derived from a compound represented by Formula 6. In another embodiment, the crosslinked polymer may include a structural unit derived from a compound represented by Formula 5 and a structural unit derived from a compound represented by Formula 7. In yet another embodiment, the crosslinked polymer may include a structural unit derived from a compound represented by Formula 5, a structural unit derived from a compound represented by Formula 6, and a structural unit derived from a compound represented by Formula 7.

[0113] The crosslinked polymer may be represented by one of the following formulae (PA) to (PR):

[0114]

[0115]

[0116] Examples of polymers comprising cross-linked cyanurate structural units are also provided in U.S. Patent Publication No. 2011 / 0033801A1 and U.S. Patent Publication No. 2019 / 0129305A1, the contents of which are incorporated herein by reference in their entirety.

[0117] The antireflective composition further comprises a thermal acid generator. During the curing process of the antireflective coating composition layer, the thermal acid generator promotes or improves the crosslinking reaction. The thermal acid generator can be an ionic or substantially neutral thermal acid generator.

[0118] In an embodiment, the thermal acid generator may be an aromatic sulfonic acid generator, for example, a benzene sulfonic acid generator represented by Formula 9:

[0119] Formula 9

[0120]

[0121] In formula 9,

[0122] Each R 2are independently non-hydrogen substituents such as hydroxy, cyano, halogen (F, Cl, Br or I), amino, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted carbocycle or optionally substituted heteroaryl; and

[0123] M + It is a cation.

[0124] In another embodiment, the thermal acid generator may be a pyridinium acid generator represented by Formula 10:

[0125] Formula 10

[0126]

[0127] In formula 10,

[0128] R 1 is a non-hydrogen substituent such as optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted carbocycle, or optionally substituted heteroaryl;

[0129] Each R 2 are independently non-hydrogen substituents such as hydroxy, cyano, halogen (F, Cl, Br or I), amino, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted carbocycle or optionally substituted heteroaryl; and

[0130] n is 0 (no R 2 groups, the pyridyl ring is substituted), 1, 2, 3, 4 or 5, and more typically n is 0, 1, 2 or 3.

[0131] The amount of one or more thermal acid generators in the antireflective composition can be 0.1 to 10 weight percent based on the total solids of the antireflective composition. For example, the amount of one or more thermal acid generators in the antireflective composition can be about 0.5 weight % to 2 weight % based on the total solids of the antireflective composition.

[0132] The antireflective composition may further comprise a solvent. The solvent may be an organic solvent typically used in the electronics industry, such as propylene glycol methyl ether (PGME), 2-hydroxyisobutyric acid methyl ester (HBM), propylene glycol methyl ether acetate (PGMEA), 3-methoxy methyl propionate (MMP), ethyl lactate, n-butyl acetate, anisole, N-methylpyrrolidone, γ-butyrolactone, ethoxybenzene, benzyl propionate, benzyl benzoate, propylene carbonate, xylene, mesitylene, cumene, limonene, and mixtures thereof. Can use the mixture of organic solvent, such as comprising one or more in anisole, ethoxybenzene, PGME, HBM, PGMEA, GBL, MMP, n-butyl acetate, benzyl propionate and benzyl benzoate and the mixture of one or more other organic solvents, for example comprising two or more mixtures in anisole, ethoxybenzene, PGME, HBM, PGMEA, GBL, MMP, n-butyl acetate, benzyl propionate, dimethylbenzene, mesitylene, cumene, limonene and benzyl benzoate.When using solvent mixture, the ratio of solvent is usually not critical, and can be from 99:1 to 1:99 weight / weight (w / w) change, condition is that solvent mixture can dissolve the component of composition.Those skilled in the art will recognize that, as can be desired, can regulate the concentration of component in organic solvent by removing a part of organic solvent or by adding more organic solvent.

[0133] The solvent component of the composition is typically present in an amount of 50 to 99.9 wt %, e.g., 55 to 99.9 wt %, 60 to 99.9 wt %, 65 to 99.9 wt %, 70 to 99.9 wt %, 75 to 99.9 wt %, 80 to 99.9 wt %, 85 to 99.9 wt %, 90 to 99.9 wt %, or 95 to 99 wt %, based on the total solids of the antireflective composition.

[0134] The antireflective composition may include one or more optional additives, including, for example, surfactants and antioxidants. Typical surfactants include those that exhibit amphiphilic properties, meaning that they can be both hydrophilic and hydrophobic at the same time. Amphiphilic surfactants have one or more hydrophilic head groups (which have a strong affinity for water) and long hydrophobic tails that are organophilic and repel water. Suitable surfactants can be ionic (i.e., anionic, cationic) or nonionic. Further 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 X-114, X-100, X-45, X-15, and branched secondary alcohol ethoxylates such as TERGITOL TMTMN-6 (The Dow Chemical Company, Midland, Michigan, USA) and PF-656 (Omnova Solutions, Beachwood, Ohio, USA). Still further exemplary surfactants include alcohol (primary and secondary) ethoxylates, amine ethoxylates, glucosides, glucosamines, polyethylene glycols, poly(ethylene glycol-co-propylene glycol), or other surfactants disclosed in the 2000 North American edition of McCutcheon's Emulsifiers and Detergents published 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. of Allentown, Pennsylvania and are marketed under the trade name and Other suitable surfactants include other polymer compounds, such as triblock EO-PO-EO copolymers 25R2, L121, L123, L31, L81, L101 and P123 (BASF, Inc.). If used, such surfactants and other optional additives are typically present in the antireflective composition in small amounts, such as 0.01 wt % to 10 wt % based on the total solids of the antireflective composition.

[0135] Antioxidants can be added to the antireflective composition to prevent or minimize the oxidation of organic materials in the antireflective 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, butylhydroxyanisole, 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 phenol, aralkyl-substituted phenol, alkylated p-cresol and hindered phenol; bisphenols, triphenols and polyphenols such as 4,4'-dihydroxydiphenyl, methylenebis(dimethyl-4,6-phenol), 2,2' -methylene-bis-(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis-(4-ethyl-6-tert-butylphenol), 4,4'-methylene-bis-(2,6-di-tert-butylphenol), 2,2'-methylene-bis-(6-α-methyl-benzyl-p-cresol), methylene-crosslinked 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, antioxidants are typically present in the antireflective composition in an amount of 0.01 wt % to 10 wt % based on the total solids of the antireflective composition.

[0136] The anti-reflective coating composition disclosed herein can be used to form a film comprising the anti-reflective coating composition, wherein the film on the substrate constitutes a coated substrate. Such a coated substrate may include: (a) a substrate having one or more layers to be patterned on its surface; (b) a layer of the anti-reflective coating composition arranged on the substrate. The coated substrate may further include: (c) a layer of the photoresist composition arranged on the layer of the anti-reflective coating composition or on one or more layers to be patterned. For example, ultraviolet radiation with a wavelength of less than 248nm and in particular 193nm or patterning can be used or by using EUV. The patternable film may therefore include a photoacid generator.

[0137] The method for forming a pattern by negative development may include the following steps: (a) applying a layer of the antireflective coating composition on a substrate; (b) curing the applied antireflective coating composition to form an antireflective layer; (c) forming a photoresist layer on the antireflective layer; and (d) patterning the photoresist layer and transferring the pattern from the patterned photoresist layer to the antireflective layer. Patterning the photoresist layer and transferring the pattern from the patterned photoresist layer to the antireflective layer may include: (d)(1) exposing the photoresist layer and the antireflective layer to activating radiation, and (d)(2) developing the exposed photoresist layer and antireflective layer with an organic solvent developer.

[0138] According to the method, a layer of an antireflective coating composition is first formed on a substrate. The content of the antireflective coating composition is the same as described above, and the antireflective coating composition can be prepared by mixing appropriate amounts of source materials including organic polymers, photoacid generators, crosslinking agents, etc.

[0139] The antireflective coating composition may be applied by any conventional means such as spin coating, etc. The antireflective coating composition may be applied to a substrate with a dry layer thickness of 2.0 nm to 300.0 nm, for example, 5.0 nm to 30.0 nm.

[0140] The applied anti-reflective coating composition layer can be cured. Curing conditions will vary with the components of the anti-reflective coating composition. Curing conditions can be, for example, 80° C. to 250° C. for 0.1 to 40 minutes. Curing conditions can make the anti-reflective coating composition coating substantially insoluble in photoresist solvents and alkaline aqueous developer solutions.

[0141] The anti-reflective coating composition layer can be formed in the form of a single layer or multiple layers. For example, before forming the anti-reflective coating composition layer, a second anti-reflective coating composition layer different from the anti-reflective coating composition layer is formed on a substrate, and the anti-reflective coating composition layer is formed on the second anti-reflective coating composition layer.

[0142] The formation of the anti-reflective coating composition layer can prevent the degradation of the pattern quality of the photoresist composition layer caused by the substrate due to the reflection of the incident rays when the photoresist composition layer is exposed to radiation, and the formation particularly improves the line width (CD) in the pattern and prevents the pattern collapse caused by the thorough activation of the de-blocking of the photoresist composition layer during the exposure process. In addition, such coatings can also improve the depth of focus, exposure latitude and line width uniformity.

[0143] The substrate may include one or more layers. The layers contained in the substrate may be one or more conductive layers of aluminum, copper, molybdenum, tantalum, titanium, tungsten or alloys thereof; nitride or silicide layers; doped amorphous silicon or doped polysilicon; dielectric layers, such as layers of silicon oxide, silicon nitride, silicon oxynitride or metal oxide; semiconductor layers, such as single crystal silicon; glass layers; quartz layers; and combinations or mixtures thereof, but are not limited thereto.

[0144] In addition, the layers contained in the substrate can be etched to form a pattern by various techniques, such as chemical vapor deposition (CVD), such as plasma-enhanced CVD, low-pressure CVD or epitaxial growth; physical vapor deposition (PVD), such as sputtering or evaporation; electroplating, etc.

[0145] The substrate may include a hard mask layer. It may be desirable to use a hard mask layer, for example, in the case of very thin resist layers, where the layer to be etched requires a significant etch depth or where a particular etchant has poor resist selectivity. Where a hard mask layer is used, the resist pattern to be formed may be transferred to the hard mask layer and may be used as a mask for etching the underlying layer.

[0146] Typical materials for hard masks include, for example, tungsten, titanium, titanium nitride, titanium oxide, zirconium oxide, aluminum oxide, aluminum oxynitride, hafnium oxide, amorphous carbon, organic polymers, silicon oxynitride, silicon nitride, and silicon organic hybrid materials, but are not limited thereto. The hard mask layer can be formed by, for example, CVD, PVD, or spin coating techniques. The hard mask layer can include a single layer or multiple layers of different materials.

[0147] A photoresist composition layer is then formed on the antireflective coating composition layer. The photoresist composition may include a matrix polymer, a photoacid generator, and a solvent.

[0148] The matrix polymer may include at least one unit having an acid cleavable protecting group. The acid cleavable protecting group may be, for example, an acetal group or an ester group containing a tertiary non-cyclic alkyl carbon (e.g., tert-butyl) or a tertiary alicyclic carbon (e.g., methyladamantyl) covalently attached to the carboxyl oxygen of the ester of the matrix polymer.

[0149] Suitable units that may be included in the matrix polymer may be, for example, units derived from (alkyl) acrylates, such as units derived from acid-cleavable (alkyl) acrylates. Specific examples thereof include units derived from tert-butyl acrylate, tert-butyl methacrylate, methyladamantyl acrylate, methyladamantyl methacrylate, ethyladamantyl acrylate, ethylfenchyl methacrylate, and the like.

[0150] Another example of suitable units that can be included in the matrix polymer may be units derived from non-aromatic cyclic olefins (intracyclic double bonds) such as optionally substituted norbornene. Still another example of suitable units that can be included in the matrix polymer may be units derived from anhydrides, such as maleic anhydride, itaconic anhydride, and the like.

[0151] In addition, the matrix polymer may include units containing heteroatoms such as oxygen and sulfur, and for example, the heterocyclic unit may be fused to the main chain of the matrix polymer. The matrix polymer may be used in the form of a mixture of two or more. The matrix polymer may be commercially available or prepared by those skilled in the art.

[0152] The matrix polymer of the photoresist composition is used in an amount sufficient to make the exposed coating of the photoresist developable with a suitable solution, for example, 50% to 95% by weight based on the total solids of the antireflective composition. The weight average molecular weight (M) of the matrix polymer is w ) may be less than 100,000 Daltons, such as 5,000 to 100,000 Daltons, such as 5,000 to 15,000 Daltons.

[0153] The photoresist composition may further comprise a photoactive material used in an amount sufficient to generate a latent image in a coating layer of the composition upon exposure to activating radiation, and may comprise a photoacid generator. Suitable photoacid generators may be the same types of photoacid generators as described in the antireflective coating composition.

[0154] The photoresist composition may include a solvent, for example, glycol ethers such as 2-methoxyethyl ether, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; propylene glycol monomethyl ether acetate; lactates such as ethyl lactate and methyl lactate; propionates such as methyl propionate, ethyl propionate, ethylethoxypropionate, and methyl-2-hydroxyisobutyrate; methyl cellosolve acetate; aromatic hydrocarbons such as toluene and xylene; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and 2-heptanone. Such solvents may be used alone or in combination of two or more solvents.

[0155] The photoresist composition can be applied to the anti-reflective coating composition layer by spin coating, dipping, roller coating or other conventional coating techniques. For example, spin coating can be used. For spin coating, the solid content of the coating solution can be adjusted to provide a desired film thickness based on the specific coating equipment used, the viscosity of the solution, the speed of the coating tool and the amount of time allowed for the rotation.

[0156] The thickness of the photoresist composition layer may be, for example, 50 nm to 300 nm.

[0157] Next, the photoresist composition layer can be soft baked to minimize the solvent content in the layer, thereby forming a non-sticky 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. The temperature and time of the soft bake will depend on the specific material and thickness of the photoresist. For example, a typical soft bake is performed at a temperature of 90° C. to 150° C. for about 30 seconds to 90 seconds.

[0158] In addition, an overcoating layer can be formed on the photoresist composition layer. An overcoating layer can be formed to provide uniform resist patterns, to reduce reflectivity, improved depth of focus and exposure tolerance and defect reduction during the exposure process of the resist. An overcoating layer can be formed by a spin coating technique using an overcoating composition. The solid content of the coating solution can be adjusted to provide a desired film thickness based on the specific coating equipment used, the viscosity of the solution, the speed of the coating tool and the time allowed for rotation. The thickness of the overcoating layer can be, for example, 200 angstroms. to

[0159] The overcoat layer may be soft baked to minimize the solvent content in the layer. The soft bake may be performed on a hot plate or in an oven. A typical soft bake is performed at a temperature of 80°C to 120°C for about 30 seconds to 90 seconds.

[0160] The photoresist composition layer is then exposed to activating radiation through a photomask to create a solubility difference between exposed and non-exposed areas. The photomask has optically transparent areas and optically opaque areas.

[0161] The exposure wavelength can be, for example, 400 nm or less, 300 nm or less, 200 nm or less, such as 248 nm (e.g., KrF excimer laser) or 193 nm (e.g., ArF excimer laser). The exposure energy is typically about 10 to 80 mJ / cm2. 2 ), depending on the exposure device and the components of the photosensitive composition.

[0162] After the exposure step of the photoresist composition layer, a post-exposure bake (PEB) is performed. PEB can be performed on a hot plate or in an oven. PEB conditions can vary with the composition and thickness of the photoresist composition layer. For example, a typical PEB is performed at a temperature of 80° C. to 150° C. for about 30 seconds to 90 seconds. Therefore, due to the solubility difference between the light-exposed area and the non-exposed area, a latent image is generated in the photoresist composition layer.

[0163] The overcoat layer and the exposed photoresist composition layer are then developed to remove the non-exposed areas, thereby forming a resist pattern. The developer is typically an organic developer, for example, selected from a solvent of ketones, esters, ethers, amides, hydrocarbons and mixtures thereof. The example of suitable ketones comprises acetone, 2-hexanone, 5-methyl-2-hexanone, 2-heptanone, 4-heptanone, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, diisobutyl ketone, hexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone and methyl isobutyl ketone. The example of suitable ester comprises methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxy propionate, 3-methoxy butyl acetate, 3-methyl-3-methoxy butyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate and propyl lactate. The example of suitable ether comprises dioxane, tetrahydrofuran and glycol ether (for example, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether and methoxymethyl butanol). The example of suitable amide comprises N-methyl-2-pyrrolidone, N,N-dimethylacetamide and N,N-dimethylformamide. Examples of suitable hydrocarbons include aromatic hydrocarbon solvents (eg, toluene and xylene).

[0164] The developer may contain a solvent useful in a photoresist composition, such as 2-heptanone, butyl acetate (e.g., n-butyl acetate). The developer may contain a mixture of these solvents, or one or more of the solvents listed above mixed with solvents different from those described above or mixed with water. For example, the developer may contain a mixture of a first organic solvent and a second organic solvent. Specific examples of the first organic solvent are C4-C9 ketones; hydroxyalkyl esters, such as methyl 2-hydroxyisobutyrate, ethyl lactate; and straight or branched C5-C6 alkoxyalkyl acetates, such as propylene glycol monomethyl ether acetate, for example 2-heptanone or 5-methyl-2-hexanone. The example of the second organic solvent is a straight or branched C6-C8 alkyl ester, such as n-butyl acetate, n-pentyl acetate, n-butyl propionate, n-hexyl acetate, n-butyl butyrate and isobutyl butyrate;With a straight or branched C8-C9 ketone, such as 4-octanone, 2,5-dimethyl-4-hexanone, 2,6-dimethyl-4-heptanone, for example n-butyl acetate, n-butyl propionate or 2,6-dimethyl-4-heptanone. The example of the combination of the first organic solvent and the second organic solvent includes 2-heptanone / n-butyl propionate, cyclohexanone / n-butyl propionate, PGMEA / n-butyl propionate, 5-methyl-2-hexanone / n-butyl propionate, 2-heptanone / 2,6-dimethyl-4-heptanone, 2-heptanone / n-butyl acetate. In these combinations, 2-heptanone / n-butyl acetate or 2-heptanone / n-butyl propionate can be preferred.

[0165] The solvent may be present in the developer in an amount of 90 to 100 weight percent, such as greater than 95 weight percent, greater than 98 weight percent, greater than 99 weight percent, or 100 weight percent.

[0166] The developer may also contain optional additives, such as surfactants, etc. Such optional additives will typically be present in minor concentrations (eg, about 0.01 to 5 weight percent).

[0167] The developer can be applied to the photoresist composition layer by known techniques, such as spin coating or puddle coating. The developing time is a period of time effective to remove the non-exposed areas of the photoresist. For example, the developing is performed at room temperature for 5 to 30 seconds.

[0168] The developed photoresist composition layer may be further cured by an additional bake at a temperature of 100°C to 150°C for several minutes.

[0169] The developed substrate can have a substrate region from which the photoresist has been removed, and the substrate region can be treated in a selective manner. For example, the substrate region from which the photoresist has been removed can be chemically etched or plated using methods well known in the relevant art. Hydrofluoric acid etching solutions and plasma gas etchants such as oxygen plasma etchants can be used as etchants. For example, the anti-reflective coating composition layer can be removed and a plasma gas etchant can be used to etch the substrate.

[0170] Hereinafter, the present disclosure is described in more detail with reference to examples. However, these examples are exemplary, and the present disclosure is not limited thereto.

[0171] Examples

[0172] Polymer synthesis

[0173] Example 1

[0174] A 3-neck 100 mL round bottom flask was equipped with a thermocouple, a Dean-Stark water trap, a condenser and a heating oil bath. Tris (2-hydroxyethyl) isocyanurate (30.4 g, 116.5 mmol), tris (2-carboxyethyl) isocyanurate (20.1 g, 58.2 mmol), n-butyl alcohol (20.0 g, 270.0 mmol), p-toluenesulfonic acid (0.5 g, 2.8 mmol) and anisole (34 g) were weighed into the flask. The reaction mixture was heated to 150 ° C for 3 h under stirring, cooled to room temperature, and diluted with HBM (160 g). The mixed solution (40 g), p-toluenesulfonic acid (0.07 g, 0.35 mmol) and 1,3,4,6-tetrakis (methoxymethyl) tetrahydroimidazo [4,5-d] imidazole-2,5 (1H, 3H) -dione (3.6 g, 7.4 mmol) were weighed and heated to 50 ° C for 4 h under stirring. The solution was quenched with triethylamine (0.4 mL) and cooled to room temperature. The mixture solution was precipitated with IPA / heptane, filtered, and dried under vacuum at 40 ° C for 24 h.

[0175] Synthesis of cross-linkable photoacid generators

[0176] Example 2. (4-Hydroxyphenyl)diphenylsulfonium trifluoromethanesulfonate.

[0177] Sodium trifluoromethanesulfonate (25.0 g, 1.0 equivalent) and (4-hydroxyphenyl) diphenylsulfonium iodide (47.2 g, 0.8 equivalent) were dissolved in dichloromethane (360 g) and deionized water (360 g), and stirred overnight at room temperature. The organic layer was washed with deionized water (360 g x 5), and the solvent was evaporated. The crude product was precipitated from iso-propanol / heptane and dried under vacuum.

[0178] Example 3. (4-Hydroxyphenyl)diphenylsulfonium 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate.

[0179] 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonic acid lithium (10.0 g, 1.0 equivalent) and (4-hydroxyphenyl) diphenylsulfonium iodide (10.6 g, 0.8 equivalent) were dissolved in dichloromethane (85 g) and deionized water (85 g), and stirred overnight at room temperature. The organic layer was washed with deionized water (85 g x 5), and the solvent was evaporated. The crude product was precipitated from isopropanol / heptane and dried under vacuum.

[0180] Example 4. (4-(2-Hydroxyethoxy)phenyl)diphenylsulfonium trifluoromethanesulfonate.

[0181] (1) (4-Hydroxyphenyl)diphenylsulfonium iodide (4.0 g, 1.0 eq.), potassium carbonate (1.6 g, 1.1 eq.) and potassium iodide (0.4 g, 0.25 eq.) were dissolved in DMF (103 g) and 2-(2-chloroethoxy)tetrahydro-2H-pyran (1.8 g, 1.1 eq.) was added. The mixture was stirred at 100° C. for 16 h. The organic layer was washed with deionized water. The mixture was precipitated from heptane / dichloromethane and dried under vacuum to obtain 4.8 g (91%) of solid.

[0182] (2) Potassium trifluoromethanesulfonate (2.00 g, 1.8 equivalents) and diphenyl(4-(2-((tetrahydro-2H-pyran-2-yl)oxy)ethoxy)phenyl)sulfonium iodide (3.06 g, 1 equivalent) were dissolved in chloroform (100 g) and deionized water (30 g), and stirred at room temperature overnight. The organic layer was washed with deionized water (30 g×2), and the solvent was evaporated under reduced pressure. 3.0 g (94%) of a viscous liquid product was obtained.

[0183] (3) Diphenyl(4-(2-((tetrahydro-2H-pyran-2-yl)oxy)ethoxy)phenyl)sulfonium trifluoromethanesulfonate (3.1 g, 1.0 eq.) was dissolved in methanol (65 g) and 4N hydrogen chloride solution (3 mL) was added. The mixture was stirred at room temperature for 16 h. The solvent was evaporated under reduced pressure. 2.3 g (88%) of a viscous liquid product was obtained.

[0184] Example 5. (4-(2-Hydroxyethoxy)phenyl)diphenylsulfonium 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate.

[0185] (1) 2-(3-chloroethoxy)tetrahydro-2H-pyran (4.5 g, 1.0 equivalent), potassium carbonate (4.4 g, 1.3 equivalent) and potassium iodide (1.0 g, 0.3 equivalent) were added to a solution of (4-hydroxyphenyl)diphenylsulfonium iodide (10.0 g, 1.0 equivalent) in 114 g of DMF under heating at 100° C. The solution was cooled to room temperature and filtered to obtain a solution. The crude product was recrystallized from dichloromethane / heptane and dried under vacuum to obtain 13 g of a sticky light brown powder (99%).

[0186] (2) Lithium nonafluoro-1-butanesulfonate (4.0 g, 1.4 equivalents) and diphenyl(4-(2-((tetrahydro-2H-pyran-2-yl)oxy)ethoxy)phenyl)sulfonium iodide (5.0 g, 1.0 equivalents) were dissolved in dichloromethane (133 g) and deionized water (50 g), and the mixture was stirred at room temperature overnight. The organic layer was washed with deionized water (40 g×4), and the solvent was evaporated to obtain 6.4 g (97%) of a brown solid.

[0187] (3) Diphenyl(4-(2-((tetrahydro-2H-pyran-2-yl)oxy)ethoxy)phenyl)sulfonium nonafluorobutanesulfonate (6.4 g) and 4N hydrochloric acid in dioxane (1.5 mL) were dissolved in methanol (51 g), and the reaction mixture was stirred at room temperature overnight. The mixture was evaporated, and the solution was diluted with dichloromethane (66 g). The organic layer was washed with saturated sodium bicarbonate solution (66 g×1) and deionized water (40 g×3). The crude product was precipitated from dichloromethane / heptane and dried under vacuum to obtain 4.4 g (78%) of a viscous liquid.

[0188] Example 6. (4-(3-Hydroxypropoxy)phenyl)diphenylsulfonium trifluoromethanesulfonate.

[0189] (1) (4-Hydroxyphenyl)diphenylsulfonium iodide (10.2 g, 1.0 eq.), potassium carbonate (4.5 g, 1.3 eq.) and potassium iodide (2.1 g, 0.5 eq.) were dissolved in DMF (103 g), and 2-(2-chloroethoxy)tetrahydro-2H-pyran (4.9 g, 1.1 eq.) was added. The mixture was stirred at 100° C. for 16 h. The mixture was cooled to room temperature and filtered through celite, and the solvent was evaporated under reduced pressure. The mixture was precipitated from heptane / dichloromethane and dried under vacuum to obtain 12.9 g (94%) as a solid.

[0190] (2) Potassium trifluoromethanesulfonate (2.8 g, 1.4 equivalents) and diphenyl(4-(3-((tetrahydro-2H-pyran-2-yl)oxy)propoxy)phenyl)sulfonium trifluoromethanesulfonate (6.1 g, 1.0 equivalents) were dissolved in chloroform (100 g) and deionized water (30 g), and stirred at room temperature overnight. The organic layer was washed with deionized water (30 g×2), and the solvent was evaporated under reduced pressure. 6.1 g (97%) of a viscous liquid product was obtained.

[0191] (3) Diphenyl(4-(3-((tetrahydro-2H-pyran-2-yl)oxy)propoxy)phenyl)sulfonium trifluoromethanesulfonate (5.8 g, 1.0 eq.) was dissolved in methanol (60 g) and 4N hydrogen chloride solution (3 mL) was added. The mixture was stirred at 24° C. for 16 h. The mixture was evaporated under reduced pressure and dried under vacuum to obtain 4.2 g (84%) of the product.

[0192] Example 7. (4-(3-Hydroxypropoxy)phenyl)diphenylsulfonium 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate.

[0193] (1) (4-Hydroxyphenyl) diphenylsulfonium iodide (10.2 g, 1.0 eq.), potassium carbonate (4.5 g, 1.3 eq.) and potassium iodide (2.1 g, 0.5 eq.) were dissolved in DMF (103 g), and 2-(2-chloroethoxy) tetrahydro-2H-pyran (4.9 g, 1.1 eq.) was added. The mixture was stirred at 100° C. for 16 h. After the reaction was complete, the mixture was cooled to room temperature, filtered through celite, and the solvent was evaporated under reduced pressure. The mixture was precipitated from heptane / dichloromethane and dried under vacuum to obtain 12.9 g (94%) of solid.

[0194] (2) Lithium nonafluorobutane-1-sulfonate (3.6 g, 1.3 equivalents) and diphenyl(4-(3-((tetrahydro-2H-pyran-2-yl)oxy)propoxy)phenyl)sulfonium trifluoromethanesulfonate (5.0 g, 1 equivalent) were dissolved in dichloromethane (100 g) and deionized water (50 g), and the reaction mixture was stirred at room temperature overnight. After the reaction, the organic layer was washed with deionized water (30 g×2), and the solvent was evaporated under reduced pressure. 6.1 g (94%) of a viscous liquid product was obtained.

[0195] (3) Diphenyl(4-(3-((tetrahydro-2H-pyran-2-yl)oxy)propoxy)phenyl)sulfonium nonafluorobutane-1-sulfonate (6.2 g, 1.0 equivalent) was dissolved in methanol (60 g), and 4N hydrogen chloride solution (3 mL) was added. The mixture was stirred at 24° C. for 16 h. After the reaction was completed, the solvent was evaporated under reduced pressure. 4.5 g (84%) of the product was obtained.

[0196] Preparation of antireflective compositions

[0197] Example 8

[0198] 0.65 g of the polymer prepared according to Example 1, 0.10 g of tetramethoxymethyl glycoluril, 0.01 g of 2,4,6-trimethylpyridinium p-toluenesulfonate, and 0.02 g of the cross-linkable PAG prepared according to Example 2 were dissolved in 99.22 g of HBM solvent.

[0199] Example 9

[0200] 0.65 g of the polymer prepared according to Example 1, 0.10 g of tetramethoxymethyl glycoluril, 0.01 g of 2,4,6-trimethylpyridinium p-toluenesulfonate, and 0.02 g of the cross-linkable PAG prepared according to Example 3 were dissolved in 99.22 g of HBM solvent.

[0201] Example 10

[0202] 0.73 g of the polymer prepared according to Example 1, 0.02 g of tetramethoxymethyl glycoluril, 0.01 g of 2,4,6-trimethylpyridinium p-toluenesulfonate, and 0.02 g of the cross-linkable PAG prepared according to Example 4 were dissolved in 99.22 g of HBM solvent.

[0203] Example 11

[0204] 0.72 g of the polymer prepared according to Example 1, 0.02 g of tetramethoxymethyl glycoluril, 0.01 g of 2,4,6-trimethylpyridinium p-toluenesulfonate, and 0.02 g of the cross-linkable PAG prepared according to Example 5 were dissolved in 99.22 g of HBM solvent.

[0205] Example 12

[0206] 0.73 g of the polymer prepared according to Example 1, 0.02 g of tetramethoxymethyl glycoluril, 0.01 g of 2,4,6-trimethylpyridinium p-toluenesulfonate, and 0.02 g of the cross-linkable PAG prepared according to Example 6 were dissolved in 99.22 g of HBM solvent.

[0207] Example 13

[0208] 0.72 g of the polymer prepared according to Example 1, 0.02 g of tetramethoxymethyl glycoluril, 0.01 g of 2,4,6-trimethylpyridinium p-toluenesulfonate, and 0.02 g of the cross-linkable PAG prepared according to Example 7 were dissolved in 99.22 g of HBM solvent.

[0209] Comparative Example 1

[0210] 0.73 g of the polymer prepared according to Example 1, 0.02 g of tetramethoxymethyl glycoluril, 0.01 g of 2,4,6-trimethylpyridinium p-toluenesulfonate, and 0.02 g of triphenylsulfonium 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate were dissolved in 99.22 g of HBM solvent.

[0211] Imprint evaluation of antireflective compositions

[0212] 1. Thickness measurement

[0213] 200 mm bare silicon wafers were coated with BARC material on a TEL MARK track, where coating was done at 1500 RPM and curing was done for 60 seconds at 205° C. The coated wafers were inspected by thickness measurement on an Opti-Probe tool.

[0214] 2. Membrane peeling test

[0215] The BARC material was spin coated on an 8 inch silicon wafer and baked at 205°C for 60 seconds by MARK track (step 1). The coated wafer was exposed to 30 mL PGMEA:HBM (ratio 50wt%:50wt%) for 90 seconds, spin dried to form a thin film and cured at 110°C for 60 seconds (step 2). Film thickness measurements were performed by Opti-probe on the initial coated film (step 1) and the baked film (step 2). The amount of stripping was determined as the difference between the step 1 thickness and the step 2 thickness.

[0216] 3. Contact angle measurement

[0217] The BARC material was formed by spin coating at a spin rate of 1,500 rpm on an 8-inch silicon wafer. The film was cured on a hot plate at 205° C. for 60 seconds to remove residual solvent. The water contact angle was determined using a JDSA-100 dynamic contact angle goniometer, and a drop of water (3 ul) was placed directly on the BARC substrate to measure 9 points.

[0218] 4. Start the test

[0219] 200mm bare silicon wafers were coated with BARC material on a TEL MARK track, where coating was performed at 1,500RPM and cured for 60 seconds at each temperature of 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C. Each coated wafer was exposed to 30mL PGMEA:HBM (ratio 50wt%:50wt%) for 90 seconds, spin dried to form a film and cured for 60 seconds at 110°C. The film thickness was measured on the film after baking by Opti-probe. The starting temperature was determined by the increased film thickness representing the starting point of the cross-linking reaction.

[0220] 5.Marking evaluation

[0221] Using AR on TEL Lithius 300mm wafer track TM 46 (Dupont) coated a 300 mm bare silicon wafer and cured at 205° C. for 60 seconds to form The BARC material for imprint evaluation was coated on the first BARC layer and cured at 205° C. for 60 seconds to form Second BARC layer. DuPont ArF-i NTD photoresist was coated on the BARC layer stack and soft-baked at 100°C for 60 seconds to form The wafer was exposed to form a 46 / 94nm line / space pattern through a photomask on a NIKON 610C immersion scanner with 1.3 NA, 0.80 / 0.64 inner / outer σ, annular illumination. The wafer was subjected to post-exposure baking (PEB) at 90°C for 60 seconds. The wafer was developed with n-butyl acetate (NBA) developer and spin dried to form a photoresist pattern. The patterned wafer was inspected on a CD-SEM tool, and the imprint analysis results are provided in Table 2.

[0222] The newly formulated cross-linkable PAGs (Examples 8-13) showed improved solvent strip loss via the cross-linking reaction with the BARC polymer compared to Comparative Example 1 with comparable initial and contact angle performance (Table 1).

[0223] Table 1.

[0224]

[0225] Compared to Comparative Example 1, the new BARC formulations containing cross-linkable PAGs (Examples 8-13) showed improved EL and wider FL margin performance through efficient acid generation and cross-linking reactions (Table 2).

[0226] Table 2.

[0227]

[0228] *EoP: Optimum Exposure, EL: Exposure Latitude, FL: Focus Latitude, PCM: Pattern Collapse Margin

[0229] 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. An antireflective coating composition comprising: A polymer comprising cyanurate structural units, a photoacid generator comprising a crosslinkable group, a compound capable of cross-linking the polymer and the photoacid generator, Thermal acid generators, and Organic solvents, in, The photoacid generator is a compound having the formula G + A - Onium salt, where G + With formula 1 and A - It is a non-polymerizable organic anion: Formula 1 In formula 1, Each R 1 is independently substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted polycyclic or monocyclic C 3-30 Cycloalkyl, substituted or unsubstituted polycyclic or monocyclic C 6-30 Aryl, wherein when Y is S, the R 1 One is optionally attached to an adjacent R via a single bond or a linking group 1 , The condition is that at least one R 1 It is a polycyclic or monocyclic C 6-30 an aryl group, the hydroxyl group being connected by a single bond or an unsubstituted or substituted C1-C ... 30 A linking group is attached thereto, and z is 2 or 3, wherein z is 2 when Y is I, or z is 3 when Y is S.

2. The antireflective coating composition according to claim 1, wherein G + It is expressed by formula 2: Formula 2 In Formula 2, Each R a are independently hydrogen, halogen, cyano, nitro, amino, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C3-C 30 Cycloalkyl, substituted or unsubstituted C3-C 30 Cycloalkenyl, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C6-C 30 Aryloxy, substituted or unsubstituted C6-C 30 Thioaryl, substituted or unsubstituted C7-C 30 Arylalkyl, Each R b is substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted polycyclic or monocyclic C 3-30 Cycloalkyl, substituted or unsubstituted polycyclic or monocyclic C 6-30 Aryl, where the group R b optionally attached to each other via a single bond or a linking group, Each L is a single bond, a substituted or unsubstituted C1-C 30 Alkylene, substituted or unsubstituted C2-C 30 Alkenylene, substituted or unsubstituted C2-C 30 Alkyne, substituted or unsubstituted C3-C 30 Cycloalkenylene, substituted or unsubstituted C3-C 30 Cycloalkynylene, substituted or unsubstituted C6-C 30 Arylene, or substituted or unsubstituted C6-C 30 Heteroarylene, in each of which at least one non-adjacent -CH2- group is optionally replaced by -SO2-, -C(=O)-, -O-, -S-, -SO-, -C(=O)O-, -OC(=O)-, -C(=O)NR-, or -NRC(=O)-, wherein R is hydrogen or C1-C 10 Alkyl or combinations thereof; n1 is an integer from 1 to 5, and n2 is an integer from 0 to 4, The condition is that the sum of n1 and n2 does not exceed 5.

3. The anti-reflective coating composition according to claim 1, wherein G + It is expressed by formula 3: Formula 3 In formula 3, Each R a is hydrogen, halogen, cyano, nitro, amino, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C3-C 30 Cycloalkyl, substituted or unsubstituted C3-C 30 Cycloalkenyl, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C6-C 30 Aryloxy, substituted or unsubstituted C6-C 30 Thioaryl, substituted or unsubstituted C7-C 30 Arylalkyl, where the group R a optionally attached to each other via a single bond or a linking group, R b is independently substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted polycyclic or monocyclic C 3-30 Cycloalkyl, substituted or unsubstituted polycyclic or monocyclic C 6-30 Aryl, Each L is a single bond, a substituted or unsubstituted C1-C 30 Alkylene, substituted or unsubstituted C2-C 30 Alkenylene, substituted or unsubstituted C2-C 30 Alkyne, substituted or unsubstituted C3-C 30 Cycloalkenylene, substituted or unsubstituted C3-C 30 Cycloalkynylene, substituted or unsubstituted C6-C 30 Arylene, or substituted or unsubstituted C6-C 30 Heteroarylene, in each of which at least one non-adjacent -CH2- group is optionally replaced by -SO2-, -C(=O)-, -O-, -S-, -SO-, -C(=O)O-, -OC(=O)-, -C(=O)NR-, or -NRC(=O)-, wherein R is hydrogen or C1-C 10 Alkyl or combinations thereof; Each n1 is an integer from 1 to 5, Each n2 is an integer from 0 to 4, and The condition is that the sum of each n1 and n2 does not exceed 5.

4. The antireflective coating composition according to claim 1, wherein G + It is expressed by formula 4: Formula 4 In formula 4, Each R a is hydrogen, halogen, cyano, nitro, amino, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C3-C 30 Cycloalkyl, substituted or unsubstituted C3-C 30 Cycloalkenyl, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C6-C 30 Aryloxy, substituted or unsubstituted C6-C 30 Thioaryl, substituted or unsubstituted C7-C 30 Arylalkyl, Each L is a single bond, a substituted or unsubstituted C1-C 30 Alkylene, substituted or unsubstituted C2-C 30 Alkenylene, substituted or unsubstituted C2-C 30 Alkyne, substituted or unsubstituted C3-C 30 Cycloalkenylene, substituted or unsubstituted C3-C 30 Cycloalkynylene, substituted or unsubstituted C6-C 30 Arylene, or substituted or unsubstituted C6-C 30 Heteroarylene, in each of which at least one non-adjacent -CH2- group is optionally replaced by -SO2-, -C(=O)-, -O-, -S-, -SO-, -C(=O)O-, -OC(=O)-, -C(=O)NR-, or -NRC(=O)-, wherein R is hydrogen or C1-C 10 Alkyl or combinations thereof; Each n1 is an integer from 1 to 5, Each n2 is an integer from 0 to 4, and The condition is that the sum of each n1 and n2 does not exceed 5.

5. The anti-reflective coating composition according to claim 1, wherein The polymer comprises a structural unit derived from a compound represented by Formula 5: Formula 5 In Formula 5, R 2 , R 3 , R 4 , and each X is independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C 2-30 Alkanoyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C1-C 30 Sulfanyl, substituted or unsubstituted C1-C 30 Alkylsulfinyl, substituted or unsubstituted C1-C 30 Alkylsulfonyl, -COOH, substituted or unsubstituted C2-C 30 Alkoxycarbonyl, substituted or unsubstituted C7-C 30 Alkyl aryl, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C3-C 30 Heteroalicyclic, or substituted or unsubstituted C3-C 30 a heteroaromatic group, and Each m1 is independently an integer from 1 to 10.

6. The antireflective coating composition according to claim 1, wherein The cyanurate structural unit is derived from the compound represented by formula 6: Formula 6 In Formula 6, Each X' is independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C 2-30 Alkanoyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C1-C 30 Sulfanyl, substituted or unsubstituted C1-C 30 Alkylsulfinyl, substituted or unsubstituted C1-C 30 Alkylsulfonyl, -COOH, substituted or unsubstituted C2-C 30 Alkoxycarbonyl, substituted or unsubstituted C7-C 30 Alkyl aryl, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C3-C 30 Heteroalicyclic, or substituted or unsubstituted C3-C 30 a heteroaromatic group, and Each m2 is independently an integer from 1 to 10.

7. The anti-reflective coating composition according to claim 1, wherein The compound capable of cross-linking the photoacid generator and the polymer is represented by Formula 7: Formula 7 In Formula 7, Each X", each R 5 , R 6 and R 7 are independently hydrogen, halogen, hydroxy, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C1-C 30 Alkoxy, substituted or unsubstituted C3-C 30 Cycloalkyl, substituted or unsubstituted C7-C 30 arylalkyl, and Each m3 is independently an integer from 2 to 10.

8. A coated substrate comprising (a) a substrate; and (b) a layer of the antireflective coating composition of claim 1 disposed on the substrate.

9. A method for forming a pattern, comprising: (a) applying a layer of the antireflective coating composition as claimed in claim 1 on a substrate; (b) curing the applied antireflective coating composition to form an antireflective layer; (c) forming a photoresist layer on the antireflective layer; and (d) patterning the photoresist layer and transferring the pattern from the patterned photoresist layer to the antireflective layer.

10. The method of claim 9, wherein: Patterning the photoresist layer and transferring the pattern from the patterned photoresist layer to the antireflective layer includes: (d)(1) exposing the photoresist layer and the antireflective layer to activating radiation, and (d)(2) developing the exposed photoresist layer and antireflective layer with an organic solvent developer.

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