Coating composition and method of forming electronic device

Abstract

The coating composition comprises: a curable compound, the curable compound comprising: a core; and three or more substituents having formula (1); a polymer; and one or more solvents, wherein the total solvent content is 50 to 99 wt % based on the coating composition. A coated substrate formed with the coating composition and a method for forming an electronic device using the composition are also provided. The composition, the coated substrate and the method are particularly suitable for manufacturing semiconductor devices.

Description

Background Art

[0001] The present invention relates generally to the field of electronic device fabrication, and more particularly to the field of coating compositions used in the fabrication of electronic devices such as semiconductor devices.

[0002] It is well known in photolithography that if the resist pattern is relatively high (high aspect ratio) relative to its width, the resist pattern may collapse due to the surface tension from the developer used. Multilayer resist processes (such as three-layer and four-layer processes) have been designed, which can solve this problem of pattern collapse when high aspect ratio is desired. Such multilayer processes use a resist top layer, one or more intermediate layers and a bottom layer (or bottom layer) (or underlayer). In such multilayer resist processes, the top photoresist layer is imaged and developed in a typical manner to provide the resist pattern. The pattern is then typically transferred to one or more intermediate layers by etching. Each intermediate layer is selected so that different etching processes, such as different plasma etchings, are used. Finally, the pattern is typically transferred to the bottom layer by etching. Such intermediate layer can be made of a variety of materials, but the bottom material is typically made of a high carbon content material. The bottom material is selected to provide desired anti-reflection properties, planarization properties and etching selectivity.

[0003] Existing technologies for bottom layer formation include chemical vapor deposition (CVD) carbon and solution-processed high carbon content polymers. CVD materials have several significant limitations, including high cost of ownership, inability to form a planarization layer on the topography on the substrate, and high absorbance at 633nm for pattern alignment. For these reasons, the industry has turned to solution-processed high carbon content materials as bottom layers. The bottom layer material should ideally meet the following characteristics: be able to be cast onto the substrate by a spin coating process; heat set when heated, with low degassing and sublimation; be soluble in common processing solvents with good equipment compatibility; have appropriate n and k values ​​to work in conjunction with the currently used silicon hard mask and bottom anti-reflection (BARC) layer to give the low reflectivity necessary for photoresist imaging; be thermally stable until >400°C so as not to be damaged during subsequent processes (e.g., CVD such as silicon oxynitride (SiON) CVD processes); and resist stripping by common solvents used in the overcoated photoresist or other layers.

[0004] It is well known that materials with relatively low molecular weight have relatively low viscosity and can flow into features such as vias and trenches in a substrate to provide a planarizing layer. The base material must be capable of planarization at relatively low outgassing conditions up to 400°C. For use as a high carbon content base, it is desirable that any composition be heat set when heated. U.S. Pat. No. 9,581,905 B2 discloses a compound having the formula

[0005]

[0006] Wherein R1, R2 and R3 are each independently represented by the formula R A -C≡CR B -, where R A In particular, it may be an aryl group substituted with at least one of a hydroxyl group and an aryl group, and R B is a single bond or an aromatic group, wherein such compounds can be used to form a bottom layer in the manufacture of semiconductor devices. However, such compounds cure at relatively high temperatures.

[0007] There is a need in the art for coating compositions useful in forming electronic devices, and methods of using such compositions, which address one or more problems associated with the prior art. Summary of the invention

[0008] According to a first aspect of the present invention, a coating composition is provided. The coating composition comprises: a first curable compound, wherein the first curable compound comprises: an aromatic core, wherein the aromatic core is selected from a C6 carbocyclic aromatic ring, a C 2-5 Heterocyclic aromatic ring, C 9-30 Fused carbocyclic aromatic ring system, and C 4-30 A fused heterocyclic aromatic ring system; and three or more substituents having the formula (1)

[0009]

[0010] wherein at least two substituents having formula (1) are attached to the aromatic core; and wherein: Ar 1 Selected from C6 carbocyclic aromatic ring, C 2-5 Heterocyclic aromatic ring, C 9-30 Fused carbocyclic aromatic ring system, and C 4-30 A fused heterocyclic aromatic ring system; Z is a substituent independently selected from the following: OR 1 , protected hydroxyl, carboxyl, protected carboxyl, SR 1 , protected thiol, -OC(=O)-C 1-6 Alkyl, Halogen, and NHR 2 ; wherein each R1 is independently selected from H, C 1-10 Alkyl, C 2-10 Unsaturated hydrocarbon groups, and C 5-30 Aryl; each R 2 Independently selected from H, C 1-10 Alkyl, C 2-10 Unsaturated hydrocarbon group, C 5-30 Aryl, C(=O)-R 1 , and S(=O)2-R1 ; x is 1 to Ar 1 An integer representing the total number of available aromatic ring atoms in the core; and * indicating the point of attachment to the core; provided that the substituents having formula (1) on the same aromatic ring of the core are not in ortho positions to each other; a polymer; and one or more solvents, wherein the total solvent content is 50 to 99 wt % based on the coating composition.

[0011] According to another aspect of the present invention, a coated substrate is provided. The coated substrate comprises: an electronic device substrate; and a layer formed from a coating composition as described herein on a surface of the electronic device substrate. The layer can function in one or more capacities, for example, as a photoresist primer, a planarization layer, a gap fill layer, a protective layer, or a combination thereof.

[0012] According to another aspect of the present invention, a method for forming an electronic device is provided. The method comprises: (a) providing an electronic device substrate; (b) coating a layer of a coating composition as described herein on a surface of the electronic device substrate; and (c) curing the layer of the curable compound to form a cured layer. In another aspect of the method, the cured layer is a photoresist bottom layer that can be used in a patterning process. The method further comprises: (d) forming a photoresist layer on the bottom layer; (e) exposing the photoresist layer to activating radiation in a pattern manner; (f) developing the exposed photoresist layer to form a pattern in the photoresist layer; and (g) transferring the pattern to the bottom layer. In another aspect of the method, one or more of a silicon-containing layer, an organic anti-reflective coating, or a combination thereof may be coated on the bottom layer before step (d). In another aspect, after step (f) and before step (g), the pattern may be transferred to one or more of the silicon-containing layer, the organic anti-reflective coating, or a combination thereof. In yet another aspect, the method can further include: (h) transferring the pattern to a layer of the electronic device substrate beneath the patterned bottom layer; and (i) removing the patterned bottom layer.

[0013] It will be understood that when an element is referred to as being "on or over" another element, it can be directly adjacent to the other element or intervening elements may be present therebetween. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0014] It will also be understood that, although the terms first, second, third, etc. can be used to describe different 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 content of the present invention.

[0015] As used throughout this specification, unless the context clearly indicates otherwise, the following abbreviations shall have the following meanings: °C = degrees Celsius; g = gram; mg = milligram; L = liter; mL = milliliter; nm = nanometer; μm = micron = micrometer; mm = millimeter; sec. = second; min. = minute; hr. = hour; DI = deionized; and Da = Dalton. Unless otherwise indicated, "wt %" refers to weight percent based on the total weight of the reference composition.

[0016] Unless otherwise indicated, "aliphatic," "aromatic," "alkyl," and "aryl" include heteroaliphatic, heteroaromatic, heteroalkyl, and heteroaryl, respectively. The terms "heteroaliphatic," "heteroaromatic," "heteroalkyl," "heteroaryl," and the like refer to aliphatic, aromatic, alkyl, and aryl groups, respectively, in which one or more carbon atoms within the group are replaced with one or more heteroatoms (e.g., nitrogen, oxygen, sulfur, phosphorus, or silicon), for example, as in an ether or thioether.

[0017] Unless otherwise indicated, "aliphatic" refers to open chain (straight or branched) and cyclic aliphatic. Aliphatic structures can be saturated (e.g., alkanes) or unsaturated (e.g., alkenes or alkynes). Aliphatic refers to aliphatic groups, and includes aliphatic monovalent groups, divalent groups, and higher valent groups. Unless otherwise indicated, "aliphatic" includes "heteroaliphatic". In preferred aspects, aliphatic groups do not contain heteroatoms.

[0018] Unless otherwise indicated, "alkyl" refers to straight chain, branched and cyclic alkyl. As used herein, "alkyl" refers to an alkane group, and includes alkane monovalent groups, divalent groups (alkylene), and higher valent groups. Unless otherwise indicated, "alkyl" includes "heteroalkyl". In preferred aspects, alkyl groups do not contain heteroatoms. If the number of carbons is not indicated for any alkyl or heteroalkyl, 1-12 carbons are expected.

[0019] "Aromatic" and "aryl" include aromatic carbocycles and aromatic heterocycles. The terms "aromatic" and "aryl" refer to aromatic groups, and include monovalent groups, divalent groups (arylene groups), and higher valent groups. In preferred aspects, the aromatic or aryl group is an aromatic carbocycle.

[0020] Unless otherwise indicated, "substituted" refers to a moiety in which one or more hydrogen atoms are replaced by one or more substituents selected from the group consisting of halogen, C 1-6 Alkyl, halo-C 1-6 Alkyl, C 1-6 Alkoxy, halo-C 1-6 Alkoxy, phenyl, and phenoxy, preferably selected from halogen, C 1-6 Alkyl, halo-C 1-4 Alkyl, C 1-6 Alkoxy, halo-C 14 Alkoxy, and phenyl, and is more preferably selected from halogen, C 1-6 Alkyl, C 1-6 Alkoxy, phenyl, and phenoxy. Unless otherwise specified, substituted moieties preferably have 1 to 3 substituents, and more preferably 1 or 2 substituents. "Halo" refers to fluorine, chlorine, bromine, and iodine.

[0021] The term "B-stage" refers to a partially cured reaction product of a particular compound or compounds. As used herein, "partially cured" refers to a reaction product that is in oligomeric form and can be further polymerized or cured to form a higher molecular weight material, such as a reaction product that is useful when a coating composition is applied to a substrate and cured to form a layer or film of the composition. When such a coating composition is applied to a substrate to form a film, such a partially cured reaction product can undergo further curing during subsequent processing steps.

[0022] "Oligomer" and "oligomeric" refer to low molecular weight polymers that include a small number (e.g., 2 to 10) of total units and are capable of further curing. As used herein, the term "polymer" includes oligomers. The term "curing" means any process, such as polymerization or condensation, that increases the total molecular weight of a material, removes groups that enhance solubility, or both increases the total molecular weight and removes groups that enhance solubility. "Curable" refers to any material that can be cured under certain conditions. As used herein, "gap" refers to any hole on a semiconductor substrate that is intended to be filled with a gap-filling composition.

[0023] The articles "a" and "an" refer to the singular and the plural. Unless otherwise indicated, all amounts are weight percentages and all ratios are by weight. All numerical ranges are inclusive and combinable in any order, except where it is apparent that such numerical ranges are limited to add up to 100%. DETAILED DESCRIPTION

[0024] The coating composition of the present invention comprises a curable compound, wherein the curable compound comprises: a core, wherein the core is selected from a C6 carbocyclic aromatic ring, a C 2-5 Heterocyclic aromatic ring, C 9-30 Fused carbocyclic aromatic ring system, C 4-30 Fused heterocyclic aromatic ring system, C 1-20 Aliphatic, and C 3-20 alicyclic; and three or more substituents having the formula (1)

[0025]

[0026] wherein at least two substituents having formula (1) are attached to the core; and wherein: Ar 1 Selected from C6 carbocyclic aromatic ring, C 2-5 Heterocyclic aromatic ring, C 9-30 Fused carbocyclic aromatic ring system, and C 4-30 A fused heterocyclic aromatic ring system; Z is a substituent independently selected from the following: OR 1 , protected hydroxyl, carboxyl, protected carboxyl, SR 1 , protected thiol, -OC(=O)-C 1-6 Alkyl, Halogen, and NHR 2 ; where each R 1 Independently selected from H, C 1-10 Alkyl, C 2-10 Unsaturated hydrocarbon groups, and C 5-30 Aryl; each R 2 Independently selected from H, C 1-10 Alkyl, C 2-10 Unsaturated hydrocarbon group, C 5-30 Aryl, C(=O)-R 1 , and S(=O)2-R 1 ; x is 1 to Ar 1 The integer of the total number of available aromatic ring atoms in the nucleus; and * indicates the point of attachment to the nucleus; provided that the substituents of formula (1) on the same aromatic ring of the nucleus are not in ortho positions to each other. Thus, the substituents of formula (1) bonded to the same aromatic ring of the nucleus will not be bonded to the immediately adjacent carbon atoms of the aromatic ring, such as at positions 1 and 2 of the benzene nucleus.

[0027] Preferably, each Z is independently selected from OR 1 , protected hydroxyl, carboxyl, protected carboxyl, SH, -OC(=O)-C 1-6 Alkyl, and NHR 2 More preferably, each Z is independently selected from hydroxy, protected hydroxy, OCH2C≡CH, carboxyl, protected carboxyl, and NHR 2 , more preferably selected from hydroxyl, protected hydroxyl, OCH2C≡CH, carboxyl, and protected carboxyl, still more preferably selected from hydroxyl and protected hydroxyl, and most preferably selected from hydroxyl. Each R 1 Independently selected from H, C 1-10 Alkyl, C 2-10 Unsaturated hydrocarbon groups, and C 5-30 Aryl, and more preferably selected from H, C 1-10 Alkyl, C 2-10 Alkenyl, C 2-10 Alkynyl, and C 5-30 In a preferred embodiment, R 1 is H. Each R 2 Independently selected from H, C 1-10 Alkyl, C 2-10 Unsaturated hydrocarbon group, C 5-30 Aryl, C(=O)-R 1 , and S(=O)2-R 1 Preferably, R 2 Selected from H, C 1-10 -alkyl, C 2-10 -unsaturated hydrocarbon group, and C 5-30 Aryl, and more preferably selected from H, C 1-10 -alkyl, C 2-10 -Alkenyl and C 2-10 -alkynyl.

[0028] As used herein, the term "core" refers to a C6 carbocyclic aromatic ring, ... 2-5 Heterocyclic aromatic ring, C 9-30 Fused carbocyclic aromatic ring system, C 4-30 Fused heterocyclic aromatic ring system, C 1-20 Aliphatic, and C 3-20 Alicyclic. It is understood that in the compounds from which the curable compound is formed, the core described below (e.g., pyridine, benzene, ...) is substituted with substituents having formula (1) and optional additional substituents as described above. For example, the following compound is understood to have a benzene core and 3 substituents having formula (1):

[0029]

[0030] The core is preferably a C6 carbocyclic aromatic ring, C 2-5 Heterocyclic aromatic ring, C 9-30 A fused carbocyclic aromatic ring system, or C 4-30 Fused heterocyclic aromatic ring systems. Suitable aromatic nuclei include, for example, those selected from the group consisting of pyridine, benzene, naphthalene, quinoline, isoquinoline, carbazole, anthracene, phenanthrene, pyrene, coronene, triphenylene, , phenanthene, benz[a]anthracene, dibenzo[a,h]anthracene, oxazole, isoxazole, thiazole, isothiazole, triazole, and benzo[a]pyrene, more preferably selected from benzene, naphthalene, carbazole, anthracene, phenanthrene, pyrene, coronene, triphenylene, , phenanthene, benz[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene, and more preferably selected from benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenylene, The aliphatic nucleus may be substituted or unsubstituted, linear, branched or cyclic, and saturated or unsaturated (alkanes, alkenes or alkynes). Suitable aliphatic and heteroaliphatic cores include, for example, those selected from the group consisting of methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, methylmethane, dimethylmethane, dimethyl ether, butene, butyne, dimethyl sulfide, trimethylamine and tetramethylsilane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, norbornene, adamantane, tetrahydropyran, tetrahydrothiophene, pyrrolidine, tetrahydro-2H-pyran, tetrahydro-2H-thiopyran, piperidine and dioxane.

[0031] In formula (1), preferably, each Ar 1 independently selected from pyridine, benzene, naphthalene, quinoline, isoquinoline, anthracene, phenanthrene, pyrene, coronene, triphenylene, , phenanthene, benz[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene, more preferably selected from benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenylene, , phenanthene, benz[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene, and even more preferably selected from benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenylene, Preferably, x=1 or 2, and more preferably x=1.

[0032] The curable compound has three or more substituents of formula (1), wherein two or more substituents of formula (1) are directly attached to the core. It is further preferred that the curable compound has 2 to 4 substituents of formula (1) attached to the core, and more preferably 3 moieties of formula (1) attached to the core. One or more substituents of formula (1) may also be present in the curable compound, but not directly attached to the core. The curable compound may have any suitable number of moieties of formula (1), such as 2 to 10, preferably 2 to 8, more preferably 2 to 6, and even more preferably 3 or 4. When the core contains an aromatic ring, the substituents of formula (1) on the same aromatic ring of the core are not in adjacent positions to each other.

[0033] The curable compounds useful in the coating compositions of the present invention preferably have the formula (2)

[0034]

[0035] Where: R 0 is a nucleus as described above and is selected from C6 carbocyclic aromatic rings, C 2-5 Heterocyclic aromatic ring, C 9-30 Fused carbocyclic aromatic ring system, C 4-30 Fused heterocyclic aromatic ring system, C 1-20 Aliphatic, and C 3-20 Alicyclic; Ar 1 ,Ar 2 , and Ar 3 Each is independently an aromatic group, which is independently selected from C6 carbocyclic aromatic ring, C 2-5 Heterocyclic aromatic ring, C 9-30 Fused carbocyclic aromatic ring system, and C 4-30 A fused heterocyclic aromatic ring system; Y is a covalent chemical single bond, a divalent linking group, or a trivalent linking group; Z 1 and Z 2 Independently selected from OR 1 , protected hydroxyl, carboxyl, protected carboxyl, SR 1 , protected thiol, -OC(=O)-C 1-6 -Alkyl, halogen, and NHR 2 ; Each R 1 Selected from H, C 1-10 Alkyl, C 2-10 Unsaturated hydrocarbon groups, and C 5-30 Aryl; each R 2 Selected from H, C 1-10 Alkyl, C 2-10 Unsaturated hydrocarbon group, C 5-30 Aryl, C(=O)-R1 , and S(=O)2-R 1 ; x1=1 to 4; x2=1 to 4; y1=2 to 4; each y2=0 to 4; y1+each y2≥2; w=0 to 2; and z equals 0 to 2; wherein when Y is a covalent chemical single bond or a divalent linking group, z=1; and when Y is a trivalent linking group, z=2.

[0036] Preferably, R 0 is an aromatic nucleus having 5 to 30 carbon atoms, and more preferably 5 to 20 carbon atoms. 0 Suitable aromatic nuclei include, but are not limited to, pyridine, benzene, naphthalene, quinoline, isoquinoline, carbazole, anthracene, phenanthrene, pyrene, coronene, triphenylene, , phenanthene, benz[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene, preferably benzene, naphthalene, carbazole, anthracene, phenanthrene, pyrene, coronene, triphenylene, , phenanthene, benz[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene, and more preferably benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenylene, , and phenazone. Suitable aliphatic cores include, for example, those selected from the following: methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, methyl methane, dimethyl methane, dimethyl ether, butylene, butyne, dimethyl sulfide, trimethylamine, and tetramethylsilane. Suitable alicyclic cores include, for example, those selected from the following: cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, adamantane, tetrahydropyran, tetrahydrothiophene, pyrrolidine, tetrahydro-2H-pyran, tetrahydro-2H-thiopyran, piperidine and dioxane.

[0037] Ar 1 ,Ar 2 , and Ar 3 Preferably, each is independently selected from pyridine, benzene, naphthalene, quinoline, isoquinoline, anthracene, phenanthrene, pyrene, coronene, triphenylene, , phenanthene, benz[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene, more preferably selected from benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenylene, , phenanthene, benz[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene, and more preferably selected from benzene, naphthalene, anthracene, phenanthrene, pyrene, coronene, triphenylene, , and phenazone. Further preferably, R 0 Selected from pyridine, benzene, naphthalene, quinoline, isoquinoline, anthracene, phenanthrene, pyrene, coronene, triphenylene, , phenanthracene, benz[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene, and Ar1 ,Ar 2 , and Ar 3 Each independently selected from pyridine, benzene, naphthalene, quinoline, isoquinoline, anthracene, phenanthrene, pyrene, coronene, triphenylene, , phenanthene, benz[a]anthracene, dibenzo[a,h]anthracene, and benzo[a]pyrene. Preferably, Z 1 and Z 2 Each independently selected from OR 1 , protected hydroxyl, carboxyl (C(=O)OH), protected carboxyl, SH, fluorine, and NHR 2 , more preferably selected from hydroxyl (OH), protected hydroxyl, OCH2C≡CH, C(=O)OH, protected carboxyl, and NHR 2 , and more preferably selected from OH, protected hydroxyl, OCH2C≡CH, carboxyl, and protected carboxyl, and still more preferably selected from OH and protected hydroxyl. Each R 1 Independently selected from H, C 1-10 Alkyl, C 2-10 Unsaturated hydrocarbon groups, and C 5-30 Aryl, and more preferably selected from H, C 1-10 -alkyl, C 2-10 -Alkenyl, C 2-10 -alkynyl, and C 5-30 In a preferred embodiment, R 1 is H. Preferably, R 2 Selected from H, C 1-10 -alkyl, C 2-10 -unsaturated hydrocarbon group, and C 5-30 -aryl, and more preferably selected from H, C 1-10 -alkyl, C 2-10 -Alkenyl and C 2-10 Preferably, each Z 1 It is also preferred that each Z 2 are the same. It is further preferred that Z 1 =Z 2 Preferably, x1 and x2 are each independently selected from 1 to 3, more preferably independently 1 or 2, and even more preferably each 1. Preferably, each y2=0 to 2. Preferably, y1+each y2=3 to 8, more preferably 3 to 6, and even more preferably 3 or 4. Preferably, w=0 to 1. In a preferred embodiment, when w=0, R 0 and each Ar 1 In one preferred embodiment, Y is a covalent single bond. In another preferred embodiment, Y is a divalent or trivalent linking group. Exemplary linking groups of Y include, but are not limited to, O, S, N(R 3) r 、S(=O)2、CR 4 R 5 , bis-imide moiety, bis-etherimide moiety, bis-ketoimide moiety, bis-benzoxazole moiety, bis-benzimidazole moiety, and bis-benzothiazole moiety, wherein r = 0 or 1, and preferably the linking group of Y is O, N (R 3 ) w , and CR 4 R 5 . R 3 It is **-C(=O)-C 5-30 -aryl or **-S(=O)2-C 5-30 -aryl, where ** is the point of attachment to N. R 4 and R 5 Independently selected from H, C 1-10 -alkyl and C 5-10 -aryl, and R 4 and R 4 Together with the carbon to which they are attached, they may form a 5- or 6-membered ring, which may be fused to one or more aromatic rings.

[0038] When Y=CR 4 R 5 When a suitable linking group is a fluorenyl moiety having the following formula (A)

[0039]

[0040] Where * indicates 0 and Ar 2 Suitable bis-imide moiety linking groups of Y are shown by formula (B) and formula (C), wherein Y 1 Is a covalent single bond or C 5-30 -arylene, where * indicates the 0 and Ar 2 Suitable bis-etherimide moieties and bis-ketimide moieties are those of formula (C), wherein, respectively, Y 1 =O or -C(=O)-, and wherein * indicates the same 0 and Ar 2 Suitable bis-benzoxazole, bis-benzimidazole, and bis-benzothiazole moieties are those of formula (D) wherein G = O, NH, and S, respectively, and wherein Y 2 Is a covalent single bond or C 5-30 -arylene, and wherein * indicates 0 and Ar 2 attachment point.

[0041]

[0042]

[0043] For Z, Z in equations (1) and (2), 1 and Z 2 , a protected carboxyl group is any group that can be cleaved (deprotected) under certain conditions to produce a carboxyl group. Such protected carboxyl groups can be deprotected by heat, acid, base or a combination thereof, preferably by heat, acid or a combination thereof, and more preferably by heat. Exemplary protected carboxyl groups include esters, such as benzyl esters and esters having a quaternary carbon directly bonded to the alkoxy oxygen of the ester group. Preferably, the protected carboxyl group is an ester having a quaternary carbon directly bonded to the alkoxy oxygen of the ester group, and more preferably the ester has the formula YC(O)-O-CR'R"R"', wherein Y is an organic residue, and R', R" and R"' are each independently selected from C 1-10 Preferred protected carboxyl groups include: tert-butyl esters; 1-alkylcyclopentyl esters such as 1-methylcyclopentyl ester and 1-ethylcyclopentyl ester; 2,3-dimethyl-2-butyl ester; 3-methyl-3-pentyl ester; 2,3,3-trimethyl-3-butyl ester; 1,2-dimethylcyclopentyl ester; 2,3,4-trimethyl-3-pentyl ester; 2,2,3,4,4-pentamethyl-3-pentyl ester; and adamantyl esters such as hydroxyadamantyl ester and C 1-12 Alkyl adamantyl ester. Each of the above-mentioned protected carboxyl groups can be deprotected by one or more of heat, acid or base. Preferably, heat, acid or a combination of heat and acid are used, and more preferably the protected carboxyl group is deprotected by heat. For example, these protected carboxyl groups can be deprotected at a pH of ≤4 and preferably ≤1. At this pH, the protected carboxyl group is typically heated to a temperature of, for example, 90°C to 110°C, and preferably about 100°C to facilitate deprotection. Alternatively, when the protected carboxyl group is an ester with a tertiary carbon directly bonded to the alkoxy oxygen of the ester group, the protected carboxyl group can be deprotected by heating to a suitable temperature, such as ≥125°C, preferably 125°C to 250°C, and more preferably 150°C to 250°C. Such protected carboxyl groups and their conditions of use are well known in the art. For example, U.S. Patent No. 6,136,501 discloses various ester groups with quaternary carbons directly bonded to the alkoxy oxygen of the ester group.

[0044] For Z, Z in equations (1) and (2), 1 and Z 2, a suitable protected hydroxyl group is any group that can be cleaved (deprotected) under certain conditions to produce a hydroxyl group. Such protected hydroxyls can be deprotected by heat, acid, base, or a combination thereof. Exemplary protected hydroxyls include: ethers, such as methoxymethyl ether, ethoxyethyl ether, 2-methoxypropyl ether, tetrahydropyranyl ether, tert-butyl ether, allyl ether, benzyl ether, tert-butyldimethylsilyl ether, tert-butyldiphenylsilyl ether, acetone compounds, and benzylidene acetals; esters, such as pivalate and benzoate; and carbonates, such as tert-butyl carbonate. Each of the above-mentioned protected hydroxyls can be deprotected under acidic or alkaline conditions, and preferably under acidic conditions. More preferably, the protected hydroxyl group is deprotected using an acid or a combination of acid and heat. For example, these protected hydroxyls can be deprotected at a pH of ≤4 and preferably ≤1. At this pH, the protected hydroxyl group is typically heated to a temperature of, for example, 90°C to 110°C, and preferably about 100°C to facilitate deprotection. Such protected hydroxyl groups and conditions for their use are well known in the art.

[0045] For Z, Z in equations (1) and (2), 1 and Z 2 , a suitable protected thiol group is any group that can be cleaved (deprotected) under certain conditions to produce a thiol group. Such protected thiol groups can be cleaved by heat, acid, base or a combination thereof. Exemplary protected thiol groups include: ethers, such as methoxymethyl thioether, tetrahydropyranyl thioether, tert-butyl thioether, allyl thioether, benzyl thioether, tert-butyldimethylsilyl thioether, tert-butyldiphenylsilyl thioether, thioacetone compounds, and benzylidene thioacetals; thioesters, such as pivalic acid thioesters and benzoic acid thioesters; and thiocarbonates, such as tert-butyl thiocarbonate. Each of the above-mentioned protected thiol groups can be deprotected under acidic or alkaline conditions, and preferably under acidic conditions. More preferably, the protected thiol groups are deprotected using an acid or a combination of an acid and heat. For example, these protected thiol groups can be deprotected at room temperature, for example, when exposed to a pH of ≤1. At this pH, the protected thiol group is typically heated to a temperature of, for example, 90° C. to 110° C., and preferably about 100° C. to facilitate deprotection. Such protected thiol groups and conditions for their use are well known in the art.

[0046] The curable compound may be present in the coating composition in a wide range of, for example, 1 to 99 wt%, 10 to 99 wt%, or 50 to 90 wt% based on the total solids of the coating composition. It may be desirable that the curable compound is present in a relatively small amount, for example, 1 to 50 wt% or 1 to 30 wt%, relative to the total solids of the composition.

[0047] Curable compounds as described above can be easily manufactured by those skilled in the art using known synthesis techniques. For example, the compound can be prepared by mixing reactants (such as aryl halides or alkyl halides) with aromatic alkynes and one or more suitable catalysts (such as copper and palladium catalysts), alkalis and solvents. The solvent is typically an organic solvent, which is for example selected from toluene, benzene, tetrahydrofuran, dioxane and combinations thereof. The reaction is carried out at a temperature and time that effectively causes the reactants in the reaction mixture to react to form a curable compound. The reaction temperature is typically 0°C to 200°C, preferably 25°C to 100°C. The reaction time is typically 5 minutes to 96 hours, preferably 2 to 24 hours. The product compound can be purified by technology known in the art (such as column chromatography).

[0048] The coating composition further comprises one or more polymers. Including a polymer in the coating composition can allow one or more characteristics of the composition or the layer formed therefrom to be adjusted or improved, for example, planarization performance, stripping resistance, etching rate or coating quality. Such characteristics can be adjusted by selecting a suitable polymer and adjusting the relative amount of curable compounds and polymers in the composition. Suitable polymers include, for example, those selected from the following: acrylates, vinyl aromatic polymers, novolacs, polyphenylenes, polyarylene ethers, polyimides, polybenzoxazoles, polybenzimidazoles, polybenzothiazoles, polyquinoxalines, polyethersulfones, B-stage reaction products of the above-mentioned curable compounds, and combinations thereof. The polymer preferably comprises one or more functional groups, which are selected from, for example, hydroxyl, alkoxy, epoxy, alkenyl, alkynyl, carboxylic acid, acetal, ketal, tertiary alkyl esters and amines. Among these functional groups, epoxy is preferred. Suitable such polymers are known and can be easily manufactured by those skilled in the art using known synthesis techniques. Suitable polymers are described, for example, in U.S. Pat. Nos. 5,349,111 A, 5,965,679 A, ​​7,303,855 B2, 7,749,681 B2, 8,674,052 B2, 9,244,353 B2, and 9,540,476 B2; U.S. Patent Application Publication Nos. 2008 / 0160460 A1, 2013 / 0171569 A1, 2013 / 0280913 A1, and 2019 / 0146346 A1; D. W. Smith et al., Polyarylene Networks via Bergman Cyclopolymerization of Bis-ortho-diynyl Arenes, Adv. Funct. Mater. 2007, 17, 1237-1246; G. Maier, Polymers for Microelectronics [Polymers for Microelectronics], Materials Today [Materials Today], Vol. 4, No. 5, September-October 2001, 22-33; and PM Hergenrother, The Use, Design, Synthesis, and Properties of High Performance / High Temperature Polymers: an Overview [The Use, Design, Synthesis, and Properties of High Performance / High Temperature Polymers: an Overview], High Performance Polymers [High Performance Polymers], 15: 3-45, 2003, Sage Publications [Sage Publications].Suitable polymers include, for example, homopolymers or copolymers comprising polymerized units of one or more of the following monomers, and may include polymerized units of other monomers:.

[0049]

[0050]

[0051] Suitable B-stage polymers include reaction products of curable compounds as described above. Thus, in addition to the curable compounds described above, the coating composition may include the B-stage reaction product of the same curable compound present in the composition or a different such curable compound as described above. For example, the B-stage reaction product may be a curable compound comprising a core selected from the group consisting of a C6 carbocyclic aromatic ring, a C 2-5 Heterocyclic aromatic ring, C 9-30 Fused carbocyclic aromatic ring system, C 4-30 Fused heterocyclic aromatic ring system, C 1-20 Aliphatic, and C 3-20 alicyclic; and two or more substituents having formula (B-1) attached to the core:

[0052]

[0053] In formula (B-1), Ar 1, Z, x and * are as defined above with respect to formula (1), and the premise is that the substituents having formula (B-1) on the same aromatic ring of the core are not in ortho positions to each other. The B-stage reaction product of the curable compound can be prepared by methods known to those skilled in the art. For example, the B-stage of the compound can be carried out by dissolving the compound in a suitable solvent having a boiling point higher than the B-stage temperature. Suitable solvents include, for example, those described below with respect to the solvent component of the coating composition. It may be desirable to use the same solvent for B-stage as will be used later for the coating composition. The B-stage solvent is preferably selected from propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, γ-butyrolactone, methyl hydroxyisobutyrate, cyclohexanone, and combinations thereof. The solution is heated to a temperature for a time effective to cause partial polymerization or condensation of the compound until the target molecular weight (Mw) is reached. The B-staged reaction product of the above compounds typically has a weight average molecular weight (Mw) of 400 to 50,000 Da, more preferably 400 to 5,000 Da. The B-stage temperature is typically 50° C. to 250° C., preferably 100° C. to 200° C. The B-stage time is typically 5 minutes to 96 hours, preferably 2 to 24 hours. Known methods for forming B-staged polymers are described, for example, in U.S. Pat. No. 5,854,302 and So, Y.-H et al., Benzocyclobutene-based polymers for microelectronics, Chemical Innovation, Vol. 31, No. 12, pp. 40-47 (2001).

[0054] One or more polymers are typically present alone or in combination in an amount of, for example, 1 to 99 wt %, more typically 5 to 90 wt %, based on the total solids of the coating composition.

[0055] The coating composition comprises one or more solvents for dissolving the components of the composition and promoting its coating on the substrate. Preferably, one or more solvents are selected from organic solvents conventionally used in the manufacture of electronic devices. Suitable organic solvents include, but are not limited to; hydrocarbons, such as xylene, mesitylene, cumene, and limonene; ketones, such as cyclopentanone, cyclohexanone (CHO), methyl ethyl ketone, and methyl-2-n-pentyl ketone; alcohols, such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers, such as propylene glycol methyl ether (PGME), propylene glycol ethyl ether (PGEE), ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, anisole, and ethoxybenzene; esters such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate (EL), methyl hydroxyisobutyrate (HBM), ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol monotert-butyl ether acetate, benzyl propionate, cyclic or non-cyclic carbonates (such as propylene carbonate, dimethyl carbonate, ethylene carbonate and diphenyl carbonate); lactones such as γ-butyrolactone (GBL); lactams such as N-methylpyrrolidone; and any combination of the foregoing. Among these, preferred solvents are PGME, PGEE, PGMEA, EL, HBM, CHO, GBL, and combinations thereof. The total solvent content in the coating composition (i.e., the cumulative solvent content of all solvents) is based on 50 to 99 wt %, typically 80 to 99 wt %, and more typically 90 to 99 wt % of the coating composition. The desired solvent content will depend, for example, on the desired thickness of the applied primer layer and the coating conditions.

[0056] The coating composition of the present invention may optionally include one or more monomers, such as one or more vinyl-containing monomers selected from (meth)acrylate monomers and vinyl aromatic monomers. One or more monomers may include one or more functional groups selected from, for example, hydroxyl, alkoxy, epoxy, alkenyl, alkynyl, carboxylic acid, acetal, ketal, tertiary alkyl ester and amine. Among these functional groups, epoxy is particularly preferred. If present, such additive monomers may be present in the composition in a wide range of 1 to 90 wt % based on the total solids of the coating composition.

[0057] The coating composition of the present invention may also include one or more coating additives typically used for such coatings, such as curing agents, crosslinking agents, surface leveling agents, flow additives, etc. The selection of such optional additives and their amounts are completely within the capabilities of those skilled in the art. If used in the composition, the curing agent is typically present in an amount of 1 to 20wt% based on total solids, and preferably 1 to 3wt%. If used, the crosslinking agent is typically present in an amount of 1 to 30wt% based on total solids, and preferably 3 to 10wt%. If used, the surface leveling agent is typically used in an amount of 0.01 to 5wt% based on total solids, and preferably 0.01 to 1wt%. If used, the flow additive is typically used in an amount of 0.01 to 5wt% based on total solids, and preferably 0.01 to 3wt%. The selection of such optional additives and their usage amounts are within the capabilities of those skilled in the art.

[0058] A curing agent may optionally be used in the coating composition to aid in the curing of the composition after coating. A curing agent is any component that causes the composition to cure on the surface of the substrate. Preferred curing agents are acids and thermal acid generators. Suitable acids include, but are not limited to: aryl sulfonic acids, such as p-toluenesulfonic acid; alkyl sulfonic acids, such as methanesulfonic acid, ethanesulfonic acid, and propanesulfonic acid; perfluoroalkyl sulfonic acids, such as trifluoromethanesulfonic acid; and perfluoroaryl sulfonic acids. A thermal acid generator is any compound that releases an acid when exposed to heat. Thermal acid generators are well known in the art and are typically commercially available as from King Industries, Norwalk, Connecticut. Exemplary thermal acid generators include, but are not limited to, amine-terminated strong acids, such as amine-terminated dodecylbenzenesulfonic acid. It will also be appreciated by those skilled in the art that certain photoacid generators are capable of releasing an acid when heated and can be used as thermal acid generators.

[0059] 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 are capable of reacting with the aromatic resin reaction product 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, and the like, and preferably the foregoing has 2 or more, preferably 3 or more, and more preferably 4 selected from epoxy, hydroxymethyl, C1-C 10 Alkoxymethyl, and C2-C 10 Any of the substituents of the acyloxymethyl group. Suitable cross-linking agents are well known in the art and are commercially available from a variety of sources. Examples of suitable cross-linking agents include those having formula (3), (4), (5) and (6):

[0060]

[0061] The coating compositions of the present invention may optionally include one or more surface leveling agents (or surfactants). Although any suitable surfactant may be used, such surfactants are typically nonionic. Exemplary nonionic surfactants are those containing alkyleneoxy linkages (such as ethyleneoxy, propyleneoxy, or a combination of ethyleneoxy and propyleneoxy linkages).

[0062] The coating compositions of the present invention and films formed therefrom can exhibit good gap filling, surface planarization, solvent stripping resistance, and film quality characteristics. The compositions of the present invention preferably substantially fill, and more preferably completely fill, multiple gaps in a semiconductor substrate. Preferably, the gaps are substantially or completely void-free.

[0063] In the manufacture of electronic devices, an aromatic layer formed from the coating composition described herein can be formed according to a method comprising: (a) providing an electronic device substrate; (b) coating a layer of the coating composition as described herein on the surface of the electronic device substrate; and (c) curing the layer of the curable compound to form a cured layer. The composition can be used in the manufacture of electronic devices as one or more of a photoresist bottom layer, a planarization layer, a gap fill layer, or a protective layer.

[0064] In an illustrative aspect of the present invention, a method for patterning a photoresist bottom layer using a coating composition of the present invention will be described. The method includes: (a) providing an electronic device substrate; (b) coating a layer of a coating composition as described herein on a surface of the electronic device substrate; (c) curing the layer of the curable compound to form a bottom layer; (d) forming a photoresist layer on the bottom layer; (e) exposing the photoresist layer to activating radiation in a patterned manner; (f) developing the exposed photoresist layer to form a pattern in the photoresist layer; and (g) transferring the pattern to the bottom layer.

[0065] Suitable substrates on which the coating composition can be applied include electronic device substrates. A wide variety of electronic device substrates can be used in the present invention, such as: 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., wherein semiconductor wafers are preferred. Such substrates are typically composed of one or more of silicon, polycrystalline silicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper and gold. 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 cover "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. The preferred wafer substrate diameter is 200mm to 300mm, 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 layers or structures, which may optionally include active or operable portions of a semiconductor device. A semiconductor device refers to a semiconductor substrate on which at least one microelectronic device has been or is being mass-produced.

[0066] Optionally, before coating composition of the present invention is applied, an adhesion promoter layer is applied to the substrate surface. If adhesion promoter is desired, any suitable adhesion promoter for polymer film can be used, such as silane, preferably organosilane such as trimethoxyvinylsilane, triethoxyvinylsilane, hexamethyldisilazane, or aminosilane coupling agent such as γ-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those sold under the names of AP 3000, AP 8000 and AP 9000S available from DuPont Electronics & Imaging (Marlborough, Massachusetts).

[0067] The coating composition of the present invention can be applied to the electronic device substrate by any suitable means such as spin coating, slot die coating, scraping, curtain coating, roller coating, spray coating, dip coating, etc. Among these, spin coating is preferred. In a typical spin coating method, the composition of the present invention is applied to a substrate rotating at a speed of 500 to 4000 rpm for a period of 15 to 90 seconds to obtain a desired coating composition layer on the electronic device substrate. It will be appreciated by those skilled in the art that the height of the coating composition layer can be regulated by changing the rotation speed.

[0068] After the coating composition layer is applied to the substrate, it is optionally baked at a relatively low temperature to remove any organic solvents and other relatively volatile components from the layer. Typically, the substrate is baked at a temperature of 80° C. to 150° C., although other suitable temperatures can be used. The baking time is typically 10 seconds to 10 minutes and preferably 30 seconds to 5 minutes, although longer or shorter times can be used. When the substrate is a wafer, this baking step can be carried out by heating the wafer on a hot plate. After the solvent is removed, a layer, film or coating of the curable compound on the substrate surface is obtained.

[0069] The curable compound layer is then fully cured under the following conditions to form an aromatic bottom layer, the conditions making the film not intermixed with the subsequently applied coating (e.g., a photoresist layer or other layer directly coated on the aromatic bottom layer), while still maintaining the desired anti-reflection properties (n and k values) and etching selectivity of the bottom layer film. The bottom layer can be cured in an oxygen-containing atmosphere (e.g., air) or in an inert atmosphere (e.g., nitrogen), and preferably in an oxygen-containing atmosphere. This curing step is preferably performed on a hot plate device, although oven curing can be used. Typically, this curing is performed by heating the bottom layer at a curing temperature of ≥150°C, preferably ≥170°C, and more preferably ≥200°C. The selected curing temperature and time should be sufficient to cure the aromatic bottom layer. Suitable temperature ranges for curing the aromatic bottom layer are 150°C to 400°C, preferably 170°C to 350°C, and more preferably 200°C to 250°C. This curing step can take 10 seconds to 10 minutes, preferably 1 to 3 minutes, and more preferably 1 to 2 minutes, although other suitable times can be used.

[0070] If the curing step is performed in a manner such that the rapid release of solvents and curing byproducts does not allow the quality of the underlying film to be compromised, an initial baking step may not be necessary. For example, a ramp-up bake that starts at a relatively low temperature and then gradually increases to a temperature of ≥200°C may produce acceptable results. In some cases, it may be preferred to have a multi-stage curing process, such as a two-stage process, wherein the first stage is a lower baking temperature of less than 150°C and the second stage is a higher baking temperature of ≥200°C. A multi-stage curing process can facilitate uniform filling and planarization of pre-existing substrate surface topography, such as the filling of trenches and through-holes.

[0071] After curing the bottom layer, one or more processing layers, such as a photoresist, a silicon-containing layer, a hard mask layer, a bottom anti-reflective coating (or BARC) layer, etc., can be applied to the cured bottom layer. For example, the photoresist can be applied (such as by spin coating) directly on the surface of the silicon-containing layer or other intermediate layer directly on the resin bottom layer, or alternatively, the photoresist can be applied directly to the cured bottom layer. A wide variety of photoresists can be suitably used, such as those used for 193 nm lithography, such as those available from DuPont Electronics & Imaging (Marlborough, Mass.) under the trade name Epic TM Those sold under the brand name of . Suitable photoresists can be positive or negative. After coating, the photoresist layer is then imaged (exposed) using patterned activating radiation, and then the exposed photoresist layer is developed using a suitable developer to provide a patterned photoresist layer. The exposure of the photoresist layer to activating radiation mentioned herein indicates that the radiation can form a latent image in the photoresist layer. The photoresist layer can be exposed to activating radiation by a patterned photomask having optically opaque and optically transparent areas or by direct writing. Next, the pattern is transferred from the photoresist layer to the bottom layer by a suitable etching technique. Typically, the photoresist is also removed during this etching step. Next, the pattern is transferred to the substrate and the bottom layer is removed by a suitable etching technique known in the art (such as by plasma etching). After the patterned substrate, the bottom layer is removed using conventional techniques. The electronic device substrate is then processed according to conventional means.

[0072] The cured bottom layer can be used as the bottom layer of a multilayer resist process. In this process, a coating composition layer is coated on a substrate and cured as described above. Next, one or more intermediate layers are coated on an aromatic bottom layer. For example, a silicon-containing layer or a hard mask layer can be directly coated on an aromatic bottom layer. An exemplary silicon-containing layer such as silicon-BARC can be deposited on the bottom layer by spin coating and subsequently cured, or an inorganic silicon layer such as SiON or SiO can be deposited on the bottom layer by chemical vapor deposition (CVD). Any suitable hard mask can be used and can be deposited on the bottom layer by any suitable technique, and cured (when appropriate). Optionally, an organic BARC layer can be directly placed on a silicon-containing layer or a hard mask layer, and appropriately cured. Next, a photoresist (such as those used in 193nm lithography) is directly coated on the silicon-containing layer (in a three-layer process) or directly coated on the organic BARC layer (in a four-layer process). The photoresist layer is then imaged (exposed) using patterned activating radiation, and the exposed photoresist layer is then developed using an appropriate developer to provide a patterned photoresist layer. Next, the pattern is transferred from the photoresist layer to the layer directly below it by an appropriate etching technique known in the art (such as by plasma etching). This produces a patterned silicon-containing layer in a three-layer process and a patterned organic BARC layer in a four-layer process. If a four-layer process is used, then the pattern is transferred from the organic BARC layer to the silicon-containing layer or hard mask layer using an appropriate pattern transfer technique (such as plasma etching). After the silicon-containing layer or hard mask layer is patterned, the aromatic bottom layer is then patterned using an appropriate etching technique (such as O2 or CF4 plasma). During the etching of the aromatic bottom layer, any remaining patterned photoresist layer and organic BARC layer are removed. Next, the pattern is transferred to the substrate, such as by an appropriate etching technique, which also removes any remaining silicon-containing layer or hard mask layer, and any remaining patterned aromatic bottom layer is subsequently removed to provide a patterned substrate.

[0073] The cured bottom layer of the present invention can also be used for self-aligned double patterning process. In this process, the coating composition layer of the present invention is preferably coated on the substrate by spin coating. Any remaining organic solvent is removed and the coating composition layer is cured to form a cured bottom layer. A suitable intermediate layer such as a silicon-containing layer is coated on the cured bottom layer. Then a suitable photoresist layer is coated on the intermediate layer such as by spin coating. The photoresist layer is then imaged (exposed) in a patterned manner with activating radiation, and then the exposed photoresist layer is developed using a suitable developer to provide a patterned photoresist layer. Next, the pattern is transferred from the photoresist layer to the intermediate layer and the cured bottom layer by a suitable etching technique to expose a part of the substrate. Typically, the photoresist is also removed during this etching step. Next, a conformal silicon-containing layer is placed on the exposed portion of the patterned cured bottom layer and the substrate. Such silicon-containing layers are typically inorganic silicon layers, such as SiON or SiO2, deposited conventionally by CVD. Such conformal coating produces a silicon-containing layer on the exposed portion of the substrate surface and on the underlying pattern. That is, such silicon-containing layer substantially covers the sides and top of the patterned underlying layer. Next, the silicon-containing layer is partially etched (trimmed) to expose the top surface of the patterned polyarylene resin underlying layer and a portion of the substrate. After this partial etching step, the pattern on the substrate comprises a plurality of features, each of which comprises a line or column of a cured underlying layer, wherein the silicon-containing layer is directly adjacent to the side of each cured underlying feature, also referred to as a sidewall spacer. Next, the cured underlying layer is removed, such as by etching, to expose the substrate surface below the cured underlying pattern, and a patterned silicon-containing layer is provided on the substrate surface, wherein such patterned silicon-containing layer is double (i.e., twice as many lines and / or columns) compared to the patterned cured underlying layer.

[0074] In addition to their use in forming photoresist bottom layers and patterns as described above, the coating compositions of the present invention can be used to form planarization layers, gap filling layers, and protective layers in integrated circuit manufacturing. When used as such layers, one or more intervening material layers (such as silicon-containing layers, other aromatic resin layers, hard mask layers, etc.) are typically present between the cured layers of the coating compositions of the present invention and any photoresist layers. Typically, such planarization layers, gap filling layers, and protective layers are finally patterned.

[0075] The following non-limiting examples illustrate the invention.

[0076] Examples

[0077] Synthesis Example

[0078] Synthesis Example A

[0079] 4-iodophenyl acetate (24.75g), cuprous iodide (0.17g) and triethylamine (27.32g) are added to 22.82g of 1,4-dioxane at room temperature. Reactant mixture is purged with nitrogen for 1 hour. Bis(triphenylphosphine)palladium chloride (II) (0.63g) is added to the reaction mixture, and the mixture is heated to 70°C. Then a solution of 1,3,5-triethynylbenzene (4.5g) in degassed 1,4-dioxane (20g) is slowly added to the reaction mixture by a syringe pump. After completion of the addition, the reaction mixture is stirred overnight at 70°C under nitrogen. After the reaction is complete, the reaction mixture is cooled to room temperature, and the solvent is evaporated. The residue is diluted with ethyl acetate and filtered to remove solids. The solution is evaporated, and the residue is purified by column chromatography to obtain a light yellow solid. The solid obtained is then dissolved in THF (38g) under nitrogen. Lithium hydroxide monohydrate (3.81g) and water (16g) are added, and the mixture is stirred at 60°C for 1 hour. The mixture is then cooled to room temperature, and the solvent is removed. The residue is diluted with ethyl acetate and water, and then treated with hydrochloric acid until the pH of the water layer is 1. The organic phase is separated and the aqueous phase is extracted with ethyl acetate. The organic layers are merged and washed with water. The solvent is removed under vacuum, and the residue is purified by column chromatography to obtain 1,3,5-tris ((4-hydroxyphenyl) ethynyl) benzene (7.7g, 61% yield) as a light yellow solid. The reaction is shown in reaction scheme 1.

[0080]

[0081] Synthesis Example B

[0082] 5,5'-oxybis(1,3-dibromobenzene) (3.61g), cuprous iodide (0.21g) and triethylamine (3.42g) are added to 20g of 1,4-dioxane at room temperature. The reaction mixture is purged with nitrogen for 1 hour. Bis(triphenylphosphine)palladium chloride (II) (0.53g) is added to the reaction mixture, and the mixture is heated to 70°C. 4-ethynylphenyl acetate (4.81g) is dissolved in degassed 1,4-dioxane (17g), and then the solution is slowly added to the reaction mixture by a feed funnel. After completion of the addition, the reaction mixture is stirred overnight at 70°C under nitrogen. After the reaction is complete, the reaction mixture is cooled to room temperature, filtered, and the solvent is evaporated. The residue is purified by chromatography to obtain a light yellow solid. The solid obtained is then dissolved in THF (40g) under nitrogen. Lithium hydroxide monohydrate (1.26 g) and water (10 g) were added, and the mixture was stirred at 60 ° C for 1 hour. The reaction mixture was then diluted with ethyl acetate, and then treated with hydrochloric acid until the pH of the water layer was 1. The organic phase was separated and the aqueous phase was extracted with ethyl acetate. The organic layers were merged and washed with water. The solvent was removed under vacuum, and the residue was purified by column chromatography to obtain 5,5'-oxybis(1,3-bis((4-hydroxyphenyl)ethynyl)benzene) (3.1 g, 65% yield) as a light yellow solid. The reaction is shown in reaction scheme 2.

[0083]

[0084] Synthesis Example C

[0085] 1,3,5-tris((4-hydroxyphenyl)ethynyl)benzene (6.0 g) in anhydrous DMF (46 g) was stirred at room temperature for 15 minutes. The mixture was heated to 30 ° C and then K2CO3 (10.34 g) was added. The reaction mixture was heated to 50 ° C and 8.63 g of bromopropyne (80% in toluene) solution was added dropwise through an addition funnel. The temperature was maintained at 50 ° C for 24 hours. The reaction mixture was then cooled to room temperature and filtered to remove most of the K2CO3. The organic matter was precipitated into 2L water and stirred at room temperature for 0.5 hour. The precipitated polymer was collected by filtration to provide a light yellow solid product (5.8 g, 76% yield). The reaction is shown in reaction scheme 3.

[0086]

[0087] Synthesis Example D

[0088] Three-neck 50mL round-bottom flask is equipped with mechanical stirrer, thermocouple sleeve and condenser with nitrogen inlet.1-pyrenol (10.0g), 2-naphthaldehyde (7.2g) and PGME (40mL) are loaded into flask.Then the reaction mixture is stirred at room temperature under nitrogen.Clear solution is obtained after 30 minutes, and methanesulfonic acid (2.2g) is added to the reaction mixture.The reaction mixture is heated to 120 DEG C for 4 hours to provide a concentrated solution.Then the reaction mixture is cooled to room temperature.The mixture is added to 400mL methanol and water (v / v=4 / 1), a gray precipitate is produced.The precipitated resin is filtered with a Buchner funnel, and it is vacuum dried at 70 DEG C, to obtain a resin (11.3g, Mw=1229) in the form of a gray solid.Reaction is shown in reaction scheme 4.

[0089]

[0090] Synthesis Example E

[0091] 1,3,5-tris((4-hydroxyphenyl)ethynyl)benzene (50 g), Material A and PGMEA (72 g) were added to a 250 mL round bottom flask. Nitrogen was charged to the flask and the reaction mixture was stirred at room temperature until all solids were dissolved. The solution was then heated to 140°C. The mixture was cooled to room temperature and diluted with PGMEA (45 g). The resulting solution was then filtered through a 0.2 micron PTFE filter to produce B-stage Material E (Mw=1550). The reaction is shown in Reaction Scheme 5.

[0092]

[0093] Synthesis Example F

[0094] A mixture of 30.0 g 3,3′-(oxydi-1,4-phenylene)bis(2,4,5-triphenylcyclopentadienone), 18.1 g 1,3,5-tri(phenylethynyl)benzene and 102.2 g γ-butyrolactone was heated at 185° C. for 14 hours. The reaction was then cooled to room temperature and diluted with 21.5 g GBL. The crude reaction mixture was added to 1.7 L of a 1:1 mixture of IPA / PGME and stirred for 30 minutes. The solid was collected by vacuum filtration and washed with a 1:1 mixture of IPA / PGME. 0.4 L of water was added to the solid, and the slurry was heated to 50° C. and stirred at 50° C. for 30 minutes. The warm slurry was filtered by vacuum filtration. The wet cake was vacuum dried at 70° C. for 2 days to produce a polymer (34.1 g, 71% yield, Mw=3588, PDI=1.38). The reaction is shown in Reaction Scheme 6.

[0095]

[0096] Preparation of bottom layer composition

[0097] Example 1-26

[0098] The materials prepared as in the synthetic examples (including any added solvent) were added to a mixture of PGMEA / benzyl benzoate (97 / 3 by weight after the addition of the polymer and comparative material composition) to form a solution having about 5 wt% total solids. Other components, if any, were combined with the solution to provide a bottom layer composition formulation having the relative amounts of the components described in Table 1.

[0099] Table 1

[0100]

[0101] *The content of curable compounds, polymers and other solid materials does not include solvents; GMA = polyglycidyl methacrylate (Miwon Commercial Co., Ltd.); MF = MODAFLOW acrylic resin (Allnex Netherlands BV); HM = hexa(methoxymethyl)melamine (Nihon Cytec Industries Inc.); S275 = 1-naphthol / formaldehyde novolac polymer (Gun-Ei chemical); PHS = poly(4-hydroxystyrene) Mw 5000 (Toyota Tsusho America, Inc.); MA = copolymer of hydroxyethyl methacrylate / methyl methacrylate 40 / 60 (St. Jean Photochemical Company Photochemicals)); PB = PGMEA / benzyl benzoate (97 / 3 by weight after addition of material and comparative material composition); the values ​​for the components are based on wt% solids of the total base composition.

[0102] Evaluation of solvent resistance

[0103] Example 1-26

[0104] Each composition was spin-coated on a corresponding 200 mm silicon wafer at 1500 rpm on an ACT-8 Clean Track (Tokyo Electron Co.), and then cured at the temperature and time listed in Table 2 to form a film. TMThe metrology tool measures the initial film thickness.Then PGMEA remover is applied to each film for 90 seconds, and then stripped at 105°C and baked for 60 seconds.The thickness of each film is measured again to determine the amount of film thickness loss.The difference of film thickness before and after contact with PGMEA remover is listed in Table 2 with the percentage (% remaining film) of remaining film thickness on wafer.The crosslinking degree of this value indication polymer layer.

[0105] Table 2

[0106] Examples Bottom layer composition Curing temperature / time % Remaining Film 1 UC-1 350℃ / 60s ＞99％ 2 UC-2 300℃ / 60s ＞99％ 3 UC-3 300℃ / 60s ＞99％ 4 UC-4 240℃ / 60s ＞99％ 5 UC-5 240℃ / 60s ＞99％ 6 UC-6 300℃ / 60s ＞99％ 7 UC-7 240℃ / 60s ＞99％ 8 UC-8 300℃ / 60s 95％ 9 UC-9 240℃ / 60s ＞99％ 10 UC-10 220℃ / 60s ＞99％ 11 UC-11 220℃ / 60s ＞99％ 12 UC-12 220℃ / 60s ＞99％ 13 UC-13 220℃ / 60s 86％ 14 UC-14 220℃ / 60s ＞99％ 15 UC-15 220℃ / 60s ＞99％ 16 UC-16 220℃ / 60s ＞99％ 17 UC-17 350℃ / 90s ＞99％ 18 (Comparison) UC-18 350℃ / 60s 85％ 19 (Comparison) UC-19 300℃ / 60s 64％ 20(Comparison) UC-20 240℃ / 60s ＞99％ 21(Comparison) UC-21 300℃ / 60s 3％ 22 (Comparison) UC-22 240℃ / 60s 89％ 23 (Comparison) UC-23 300℃ / 60s 5％ 24 (Comparison) UC-24 240℃ / 60s 4％ 25(Comparison) UC-25 220℃ / 60s ＜5％ 26 (Comparison) UC-26 350℃ / 90s ＜10％

[0107] Gap filling and planarization evaluation

[0108] Examples 27-41

[0109] 300mm silicon wafers with various patterned features were used to evaluate the gap filling and planarization performance of the underlying compositions. These features were formed in a 100nm thick PECVD silicon oxide layer coated on the wafer. Before applying these compositions, the wafers were dehydrated and baked at 150°C for 60 seconds. The compositions were each coated on the corresponding wafers at 1300-1700rpm using ACT-8 Clean Track (Tokyo Electron) to achieve a target film thickness of approximately 100nm after curing. The coated compositions were cured by placing the wafer on a hot plate under the temperature and time conditions in Table 3. Cross-sectional images were taken on a Hitachi High Technology S4800 CD-SEM.

[0110] The gap filling performance was evaluated using SEM images by visual inspection of a 45nm 1:1 (90nm pitch) line / space pattern overcoated with a primer layer. The gap filling performance was considered good if no voids or bubbles were observed. The planarization performance of the primer composition was evaluated using a groove pattern (2 micron wide spaces defined between 3 micron wide lines) overcoated with a primer layer. A KLA Tencor P-7 stylus profilometer measured the height difference between the maximum height (on the groove line pattern) and the minimum height (on the groove spacing) of the primer layer. or less is considered to have good planarization and has a height difference greater than The films with a height difference of 1.34° and 1.63° are considered to have poor planarization. The results are listed in Table 3.

[0111] Table 3

[0112] Examples Bottom layer composition Curing temperature / time Gap Filling Flattening 27 UC-1 350℃ / 60s. good good 28 UC-6 300℃ / 60s. good good 29 UC-7 240℃ / 60s. good good 30 UC-8 300℃ / 60s. good good 31 UC-9 240℃ / 60s. good good 32 UC-10 220℃ / 60s. good good 33 UC-11 220℃ / 60s. good good 34 UC-14 220℃ / 60s. good good 35 UC-15 220℃ / 60s. good good 36 UC-16 220℃ / 60s. good good 37 UC-17 350℃ / 90s. good good 38 (Comparison) UC-18 350℃ / 60s. good Difference 39 (Comparison) UC-19 300℃ / 60s. good Difference 40(Comparison) UC-20 240℃ / 60s. good Difference 41(Comparison) UC-26 350℃ / 90s. good Difference

[0113] Coating quality evaluation

[0114] Examples 42-63

[0115] The bottom layer compositions were each spin coated on a corresponding 200 mm silicon wafer at 1500 rpm on an ACT-8 Clean Track (Tokyo Electron Co., Ltd.), and then cured under the temperature and time conditions in Table 4 to form bottom layer films. The coating quality was evaluated by visually inspecting the films with both the naked eye and an optical microscope. If any streaks or dewetting were observed, the coating quality was judged to be poor quality, and in the absence of them, good quality. The results are reported in Table 4.

[0116] Table 4

[0117]

Claims

1. A coating composition comprising: The first curable compound comprises: a core selected from a C6 carbocyclic aromatic ring, a C 2-5 Heterocyclic aromatic ring, C 9-30 Fused carbocyclic aromatic ring system, C 4-30 Fused heterocyclic aromatic ring system, C 1-20 Aliphatic and C 3-20 alicyclic; and three or more substituents having the formula (1) wherein at least two substituents having formula (1) are attached to the core, the core being optionally further substituted; and wherein: Ar 1 Selected from C6 carbocyclic aromatic ring, C 2-5 Heterocyclic aromatic ring, C 9-30 Fused carbocyclic aromatic ring systems and C 4-30 A fused heterocyclic aromatic ring system; Z is a substituent independently selected from the following: OR 1 , protected hydroxyl, carboxyl, protected carboxyl, SR 1 , protected thiol, -OC(=O)-C 1-6 Alkyl, Halogen and NHR 2 ; where each R 1 Independently selected from H, C 1-10 Alkyl, C 2-10 Unsaturated hydrocarbon and C 5-30 Aryl; each R 2 Independently selected from H, C 1-10 Alkyl, C 2-10 Unsaturated hydrocarbon group, C 5-30 Aryl, C(=O)-R 1 and S(=O)2-R 1 ; x is 1 to Ar 1 An integer representing the total number of available aromatic ring atoms in the core; and * indicates a point of attachment to the core or to a portion of the curable compound other than the core; provided that the substituents having formula (1) on the same aromatic ring of the core are not in ortho positions to each other; A polymer selected from the group consisting of acrylates, vinyl aromatic polymers, novolacs, polyphenylenes, polybenzoxazoles, polybenzimidazoles, polyethersulfones, and combinations thereof, or a B-stage reaction product of a second curable compound, the second curable compound comprising: a core selected from the group consisting of a C6 carbocyclic aromatic ring, a C 2-5 Heterocyclic aromatic ring, C 9-30 Fused carbocyclic aromatic ring system, C 4-30 Fused heterocyclic aromatic ring system, C 1-20 Aliphatic and C 3-20 alicyclic; and two or more substituents having formula (B-1) attached to the core, the core being optionally further substituted: Wherein in formula (B-1): Ar 1 Selected from C6 carbocyclic aromatic ring, C 2-5 Heterocyclic aromatic ring, C 9-30 Fused carbocyclic aromatic ring systems and C 4-30 A fused heterocyclic aromatic ring system; Z is a substituent independently selected from the following: OR 1 , protected hydroxyl, carboxyl, protected carboxyl, SR 1 , protected thiol, -OC(=O)-C 1-6 Alkyl, Halogen and NHR 2 ; where each R 1 Independently selected from H, C 1-10 Alkyl, C 2-10 Unsaturated hydrocarbon and C 5-30 Aryl; each R 2 Independently selected from H, C 1-10 Alkyl, C 2-10 Unsaturated hydrocarbon group, C 5-30 Aryl, C(=O)-R 1 and S(=O)2-R 1 ; x is 1 to Ar 1 an integer representing the total number of available aromatic ring atoms in the core; and * indicates a point of attachment to the core or to a portion of a curable compound other than the core; provided that the substituents having formula (B-1) on the same aromatic ring of the core are not in ortho positions to each other, the "B-stage" refers to the partially cured reaction product of a particular compound or compounds; and One or more solvents, wherein the total solvent content is 50 to 99 wt % based on the coating composition.

2. The coating composition according to claim 1, wherein Each Z in formula (1) is independently selected from OR 1 , protected hydroxyl, carboxyl, protected carboxyl, SH, -OC(=O)-C 1-6 Alkyl and NHR 2 .

3. The coating composition according to claim 2, wherein Each Z in formula (1) is a hydroxyl group.

4. The coating composition according to any one of claims 1 to 3, wherein The core of the first curable compound is selected from pyridine, benzene, naphthalene, quinoline, isoquinoline, anthracene, phenanthrene, pyrene, coronene, triphenylene, phenacene, benz[a]anthracene, dibenzo[a,h]anthracene and benzo[a]pyrene.

5. The coating composition according to any one of claims 1 to 3, wherein Each Ar in formula (1) 1 independently selected from pyridine, benzene, naphthalene, quinoline, isoquinoline, anthracene, phenanthrene, pyrene, coronene, triphenylene, phenacene, benz[a]anthracene, dibenzo[a,h]anthracene and benzo[a]pyrene.

6. The coating composition according to any one of claims 1 to 3, further comprising a curing agent, a surface leveling agent or a flow additive.

7. The coating composition of any one of claims 1 to 3, further comprising a crosslinking agent, the crosslinking agent being different from the first curable compound and the polymer.

8. A coated substrate comprising: Electronic device substrate; as well as A layer formed from the coating composition according to any one of claims 1 to 7 on the surface of the electronic device substrate.

9. A method of forming an electronic device, comprising: (a) providing an electronic device substrate; (b) applying a layer of the coating composition according to any one of claims 1 to 7 on the surface of the electronic device substrate; as well as (c) curing the layer of the curable compound to form a cured layer.

10. The method of claim 9, wherein: The solidified layer is a photoresist bottom layer, and the method further comprises: (d) forming a photoresist layer on the base layer; (e) pattern-wise exposing the photoresist layer to activating radiation; (f) developing the exposed photoresist layer to form a pattern in the photoresist layer; and (g) transferring the pattern to the base layer.

11. The method of claim 10, further comprising coating one or more of a silicon-containing layer, an organic anti-reflective coating, or a combination thereof on the base layer prior to step (d).

12. The method of claim 11, further comprising, after step (f) and before step (g), transferring the pattern to one or more of the silicon-containing layer, the organic anti-reflective coating, or a combination thereof.

13. The method of any one of claims 10 to 12, further comprising: (h) transferring the pattern to a layer of the electronic device substrate beneath the patterned bottom layer; as well as (i) Removing the patterned bottom layer.

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