Lower aromatic layer

Abstract

To provide aromatic underlayers which cure at relatively low temperatures, have good solubility in common processing solvents, and do not suffer from metal catalyst, boron, halogen, and / or phosphorus contamination.SOLUTION: The present invention provides a coating composition comprising a polymer and an organic solvent, wherein the polymer comprises a repeating unit represented by formula (1').SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention generally relates to the field of manufacturing electronic devices, and more specifically to the field of materials for use as underlayers in semiconductor manufacturing. [Background technology]

[0002] It is well known in lithography methods that when the resist pattern is very high (high aspect ratio), the resist pattern may collapse due to the surface tension from the developer used. Multilayer resist methods (e.g., 3- and 4-layer methods) have been devised to address this problem of pattern collapse when a high aspect ratio is desired. Such multilayer methods use a resist top layer, one or more middle layers, and a bottom (or lower) layer. In such multilayer resist methods, the photoresist top layer is imaged and developed in a typical manner to provide a resist pattern. The pattern is then typically transferred to one or more middle layers by etching. Each middle layer is selected to use a different etching method, such as different plasma etch. Finally, the pattern is typically transferred to the lower layers by etching. Such middle layers can be composed of various materials, but the lower layer material is typically composed of a high carbon content material. The lower layer material is selected to provide the desired anti-reflective properties, planar properties, and etch selectivity.

[0003] Current technologies for underlayers include chemical vapor deposition (CVD) carbon and solution-treated high-carbon polymers. CVD materials have several significant limitations, such as high ownership costs, inability to form a planarization layer on top of the surface morphology on the substrate, and high absorbance at 633 nm, which is used for pattern alignment. For these reasons, industry is proposing solution-treated high-carbon materials as underlayers. An ideal underlayer must satisfy the following properties: it must be cast onto the substrate by a spin-coating method; it must be able to thermally cure (cur) with low gas generation and sublimation when heated; it must be soluble in common processing solvents for good equipment compatibility; it must have appropriate n and k values ​​to work with currently used silicon hard masks and back-side anti-reflective coating (BARC) layers to provide the low reflectivity required for image formation of photoresists; and it must be thermally stable up to >400°C so as not to be damaged during the subsequent CVD process, e.g., silicon oxynitride (SiON), silicon nitride, silicon oxide, etc. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] S.Amou et al. “Synthesis of Regiocontrolled Polymer Having 2-Naphthol Unit by CuCl-amine Catalyzed Oxidative Coupling Polymerization,” Journal of Polymer Science:Part A:polymer Chemistry,Vol.37,pp 3702-3709,1999 [Overview of the project] [Problems that the invention aims to solve]

[0005] Aromatic building blocks are typically used to provide a lower layer material with desired thermal stability. However, lower layer materials having a high aromatic carbon content tend to have the drawback of insufficient solubility in common processing solvents. Various attempts have been made to prepare lower layer materials with a high aromatic content using conventional novolak polymerization methods that introduce hydroxyl groups and aliphatic carbon into the polymer. There is still a need for a lower layer material that cures at a relatively low temperature, has good solubility in common processing solvents, and has no drawbacks of metal catalyst, boron, halogen, and / or phosphorus contamination.

Means for Solving the Problems

[0006] The present invention provides (a) a step of providing an electronic device substrate, and (b) a step of coating a layer of a coating composition containing one or more curable compounds on the surface of the electronic device substrate, wherein the one or more curable compounds have the formula (1)

[0007]

Chemical formula

[0008] (wherein Z is a covalent chemical bond or O, C(=O), S, S(=O), S(=O)2, N(R), C 4 , 5 , m2 , 1-30 , 1 , 5-30 , 1-20 , 3 , 5-60 , 1-30 , 2 , 2-20 -hydrocarbylene, substituted C 1-100 -hydrocarbylene, -O-(C 1-20 -alkylene-O-) m1 , -O-(C 5-60 -arylene-O-) m2 and C(R 3 )(R 4 ) and is a divalent linking group selected from; R is H, C 1-20 -alkyl, C <00\00010>-aryl and C <00000\11>-unsaturated aliphatic moiety; each R 1 and each R 2 is independently H, OR, C 1-30 -hydrocarbyl, substituted C 1-30 -hydrocarbyl, -C(=O)-O-R 5, SR, S(=O)R, S(=O)2R, N(R 5 )(R 6 ) and N(R 7 )C(=O)R 5 Selected from; one R 1 And one R 2 Z and R can form a 5-6 membered ring together with the atoms to which they are bonded; 3 and R 4 Independently, C 1-20 -Alkyl and C 5-30 - Selected from the alphabet; R 3 and R 4 These can be condensed with the carbon atoms to which they are bonded to form one or more aromatic rings, and may optionally be substituted to form a 5 or 6-membered ring; R 5 and R 6 Independently, C 1-20 -alkyl or C 5-30 -Aryl; R 7 is H or R 6 And; R 5 and R 6 (These atoms can form a 5-6 membered ring with the atoms to which they are bonded; each of a1 and a2 is 0-5; each of m1 and m2 is 1-100; and n is 2-1000) The present invention provides a polymer containing repeating units, a step of (c) curing a layer of curable compound to form a lower layer, (d) coating a photoresist layer on the lower layer, (e) exposing the photoresist layer to a chemical beam through a mask, (f) developing the exposed photoresist layer to form a resist pattern, and (g) transferring the pattern to the lower layer to expose a portion of an electronic device substrate.

[0009] Furthermore, an electronic device comprising an electronic device substrate having a polymer layer on the surface of the electronic device substrate containing one or more curable compounds as polymerization units, wherein the one or more curable compounds are of formula (1)

[0010] [ka]

[0011] (In the formula, Z is a covalent chemical bond or O, C(=O), S, S(=O), S(=O)2, N(R), C 1-100 -Hydrocarbylene, substituted C 1-100 -hydrocarbylene, -O-(C 1-20 -Alkilen-O-) m1 ,-O-(C 5-60 -Ariren-O-) m2 and C(R 3 )(R 4 ) is a divalent linking group selected from; R is H, C 1-20 -alkyl, C 5-30 -Aryl and C 2-20 - Selected from the unsaturated aliphatic moiety; each R 1 and each R 2 These are H, OR, and C, independently. 1-30 - Hydrocarbyl, substituted C 1-30 -hydrocarbyl, -C(=O)-OR 5 , SR, S(=O)R, S(=O)2R, N(R 5 )(R 6 ) and N(R 7 )C(=O)R 5 Selected from; one R 1 And one R 2 Z and R can form a 5-6 membered ring together with the atoms to which they are bonded; 3 and R 4 Independently, C 1-20 -Alkyl and C 5-30 - Selected from the alphabet; R 3 and R 4 These can be condensed with the carbon atoms to which they are bonded to form one or more aromatic rings, and may optionally be substituted to form a 5 or 6-membered ring; R 5 and R 6 Independently, C 1-20 -alkyl or C 5-30 -Aryl; R 7 is H or R 6 And; R 5 and R 6can form a 5- to 6-membered ring together with the atoms to which they are attached; each of a1 and a2 is 0 to 5; each of m1 and m2 = 1 to 100; and n = 2 to 1000) An electronic device is provided by the present invention, which is a polymer containing the repeating unit of .

[0012] The present invention relates to formula (1)

[0013] [Chemical formula]

[0014] (In the formula, Z is a divalent linking group selected from a covalent chemical bond or O, C(=O), S, S(=O), S(=O)2, N(R), C 1-100 -hydrocarbylene, substituted C 1-100 -hydrocarbylene, -O-(C 1-20 -alkylene-O-) m1 -O-(C 5-60 -arylene-O-) m2 and C(R 3 )(R 4 )); R is selected from H, C 1-20 -alkyl, C 5-30 -aryl and C 2-20 -unsaturated aliphatic moieties; each R 1 and each R 2 is independently selected from H, OR, C 1-30 -hydrocarbyl, substituted C 1-30 -hydrocarbyl, -C(=O)-O-R 5 , SR, S(=O)R, S(=O)2R, N(R 5 )(R​​​​​​​​​​​​​​​​​​​and R 4 These can be condensed with the carbon atoms to which they are bonded to form one or more aromatic rings, and may optionally be substituted to form a 5 or 6-membered ring; R 5 and R 6 Independently, C 1-20 -alkyl or C 5-30 -Aryl; R 7 is H or R 6 And; R 5 and R 6 (These atoms can form a 5-6 membered ring with the atoms to which they are bonded; each of a1 and a2 is 0-5; each of m1 and m2 is 1-100; and n is 2-1000) Further polymers containing repeating units are provided.

[0015] The present invention also provides a method for filling gaps (or apertures), comprising the steps of: (a) providing a semiconductor substrate having a relief image on the surface of the substrate including a plurality of gaps to be filled; (b) applying one or more polymer coating layers described thereon onto the relief image; and (c) heating the coating layers to a temperature sufficient to cure the coating layers. [Modes for carrying out the invention]

[0016] When an element is said to be "on" another element, it will be understood that it may be directly adjacent to the other element, or that an intervening element may exist between them. In contrast, when an element is said to be "directly on" another element, no intervening element exists. As used herein, the terms "and / or" include any and all combinations of one or more of the related items described.

[0017] The terms first, second, third, etc., may be used herein to describe various elements, components, regions, layers, and / or areas, but it will be understood that these elements, components, regions, layers, and / or areas should not be limited by these terms. These terms are used simply to distinguish one element, component, region, layer, or area from another. Accordingly, the first element, component, region, layer, or area discussed below may be referred to as the second element, component, region, layer, or area without departing from the teachings of the present invention.

[0018] Throughout this specification, the following abbreviations shall have the following meanings unless the context explicitly indicates otherwise: °C = degrees Celsius; g = grams; mg = milligrams; L = liters; mL = milliliters; Å = angstroms; nm = nanometers; μm = microns = micrometers; mm = millimeters; sec. = seconds; min. = minutes; hr. = hours; DI = deionization; and Da = daltons. The abbreviation "weight %" means weight percentage based on the total weight of the referenced composition unless otherwise specified. Unless otherwise specified, all amounts are weight % and all ratios are molar ratios. All numerical ranges are inclusive and can be combined in any order unless it is clearly conditional that such numerical ranges sum to 100%. The articles "a," "an," and "it" mean singular and plural, respectively.

[0019] Unless otherwise specified, “alkyl” means linear, branched, and cyclic alkyl groups. Unless otherwise specified, “alkenyl” means linear, branched, and cyclic alkenyl groups. “Halogen” means fluorine, chlorine, bromine, and iodine. Unless otherwise specified, “alkyl” includes “heteroalkyl.” The term “heteroalkyl” means an alkyl group having one or more heteroatoms such as nitrogen, oxygen, sulfur, or phosphorus that substitute for one or more carbon atoms in the group, for example, in ethers or thioethers. In a preferred embodiment, “alkyl” does not include “heteroalkyl.” If the number of carbon atoms is not specified for any alkyl or heteroalkyl group, it can be 1 to 20 carbon atoms. If the number of carbon atoms is not specified for any alkenyl or alkynyl group, it can be 2 to 20 carbon atoms. “Aryl” includes aromatic carbocyclic and aromatic heterocyclic groups. Preferably, the aryl portion is an aromatic carbocyclic group. “Substituted aryl” is a group in which one or more of its hydrogen atoms are halogens, C 1-6 -alkyl, halo-C 1-6 -alkyl, C 1-6 -alkoxy, halo-C 1-6 -Alkoxy, phenyl and phenoxy, preferably halogen, C 1-6 -alkyl, halo-C 1-4 -alkyl, C 1-6 -alkoxy, halo-C 1-4 -alkoxy and phenyl, more preferably halogens, C 1-6 -alkyl, C 1-6- Means any aryl moiety substituted with one or more substituents selected from alkoxy, phenyl, and phenoxy. Preferably, the substituted aryl has 1 to 3 substituents, more preferably 1 or 2 substituents. The terms “hydrocarbyl” and “hydrocarbylen” mean saturated and unsaturated aliphatic and alicyclic moieties as well as aromatic hydrocarbon moieties, each of which may contain one or more heteroatoms selected from O, S, and N. Preferred “hydrocarbyl” moieties are alkyl, alkenyl, alkynyl, and aryl moieties. Similarly, preferred “hydrocarbylen” moieties are alkylene, alkenylene, alkynylene, and arylene. The terms “optionally substituted hydrocarbyl” or “optionally substituted hydrocarbylen” mean substituted and unsubstituted alkyl or alkylene, substituted and unsubstituted alken or alkenylene, substituted and unsubstituted alkynyl or alkynylene, and substituted and unsubstituted aryl or arylene. The terms "substituted hydrocarbyl" and "substituted hydrocarbylene" refer to a hydrocarbyl or hydrocarbylene moiety in which one or more hydrogen atoms are substituted by one or more inert substituents. The term "inert substituent" refers to any substituent that does not react during the polymerization process used to form this polymer. Typical inert substituents are C 1-20 -alkoxy, C 5-20 -Aryl, C 1-20 -alkyl, C 2-20 -Alkenil, C 2-20 - These are alkynyl, hydroxyl, and halogen compounds.

[0020] As used herein, the term “polymer” includes oligomers. The term “oligomer” means dimers, trimers, tetramers and other polymer materials that can be further cured. The term “curing” means any process, such as polymerization or condensation, that increases the total molecular weight of the polymer or removes solubility-enhancing groups from the polymer, or, instead, increases the total molecular weight and removes solubility-enhancing groups. “Curable” means any material that can be cured under certain conditions. As used herein, “gap” means any aperture on a semiconductor substrate into which a gap-filling composition is intended to be filled.

[0021] In the manufacture of an electronic device, the aromatic underlayer comprises (a) the step of providing an electronic device substrate and (b) the step of coating the surface of the electronic device substrate with a layer of a coating composition containing one or more curable compounds, wherein the one or more curable compounds are of formula (1)

[0022] [ka]

[0023] (In the formula, Z is a covalent chemical bond or O, C(=O), S, S(=O), S(=O)2, N(R), C 1-100 -Hydrocarbylene, substituted C 1-100 -hydrocarbylene, -O-(C 1-20 -Alkilen-O-) m1 ,-O-(C 5-60 -Ariren-O-) m2 and C(R 3 )(R 4 ) is a divalent linking group selected from; R is H, C 1-20 -alkyl, C 5-30 -Aryl and C 2-20 - Selected from the unsaturated aliphatic moiety; each R 1 and each R 2 These are H, OR, and C, independently. 1-30 - Hydrocarbyl, substituted C 1-30 -hydrocarbyl, -C(=O)-OR 5, SR, S(=O)R, S(=O)2R, N(R 5 )(R 6 ) and N(R 7 )C(=O)R 5 Selected from; one R 1 And one R 2 Z and R can form a 5-6 membered ring together with the atoms to which they are bonded; 3 and R 4 Independently, C 1-20 -Alkyl and C 5-30 - Selected from the alphabet; R 3 and R 4 These can be condensed with the carbon atoms to which they are bonded to form one or more aromatic rings, and may optionally be substituted to form a 5 or 6-membered ring; R 5 and R 6 Independently, C 1-20 -alkyl or C 5-30 -Aryl; R 7 is H or R 6 And; R 5 and R 6 (These atoms can form a 5-6 membered ring with the atoms to which they are bonded; each of a1 and a2 is 0-5; each of m1 and m2 is 1-100; and n is 2-1000) The polymer is made up of repeating units of the polymer, and is formed by a method comprising the steps of (c) curing a layer of curable compound to form a lower layer, (d) coating a layer of photoresist onto the lower layer, (e) exposing the photoresist layer to a chemical beam through a mask, (f) developing the exposed photoresist layer to form a resist pattern, and (g) transferring the pattern to the lower layer to expose a portion of the electronic device substrate. Next, the substrate is patterned and the patterned lower layer is removed. In one preferred embodiment, the photoresist layer is coated directly onto the lower layer. In another preferred embodiment, one or more layers of a silicon-containing composition, an organic anti-reflective composition (BARC), and combinations thereof are coated directly onto the lower layer before step (d) and optionally cured to form a core layer, and then the photoresist layer is coated directly onto one or more of the silicon-containing composition layers and BARC layers, or each of each layer. When a silicon-containing core layer is used, the pattern is transferred to the silicon-containing core layer after step (f) and before step (g).

[0024] Various electronic device substrates, such as multi-chip modules; flat panel display substrates; integrated circuit substrates; substrates for light-emitting diodes (LEDs) such as organic light-emitting diodes (OLEDs); semiconductor wafers; and packaging substrates such as polycrystalline silicon substrates, can be used in the present invention, with semiconductor wafers being preferred. Such substrates are typically composed of one or more of silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper, and gold. Suitable substrates may be in the form of wafers, such as wafers used in the manufacture of integrated circuits, optical sensors, flat panel displays, optical integrated circuits, and LEDs. As used herein, the term “semiconductor wafer” is intended to include “semiconductor substrates,” “semiconductor devices,” and various packages for various levels of interconnection, such as single-chip wafers, multiple-chip wafers, packages or other assemblies for various levels requiring solder connections. Such substrates may be of any suitable size. The preferred wafer substrate diameter is 200 mm to 300 mm, but wafers having smaller and larger diameters may be suitably used by the present invention. As used herein, the term “semiconductor substrate” includes any substrate having one or more semiconductor layers or structures which may optionally contain active or operable portions of a semiconductor device. A semiconductor device means a semiconductor substrate on which at least one microelectronic device is batch-fabricated or has been batch-fabricated on it.

[0025] Optionally, a layer of adhesion promoter may be applied to the substrate surface before deposition of the coating composition, and then cured to form the underlying layer. If an adhesion promoter is desired, any suitable adhesion promoter for polymer films may be used, such as silanes, preferably organosilanes such as trimethoxyvinylsilane, triethoxyvinylsilane, hexamethyldisilazane, or aminosilane coupling agents such as gamma-aminopropyltriethoxysilane. Particularly suitable adhesion promoters include those available from Dow Electronic Materials (Marlborough, Massachusetts), marketed under trade names AP3000, AP8000, and AP9000S.

[0026] A useful coating composition in the present invention comprises one or more curable compounds, the curable compounds being of formula (1)

[0027] [ka]

[0028] (In the formula, Z is a covalent chemical bond or O, C(=O), S, S(=O), S(=O)2, N(R), C 1-100 -Hydrocarbylene, substituted C 1-100 -hydrocarbylene, -O-(C 1-20 -Alkilen-O-) m1 ,-O-(C 5-60 -Ariren-O-) m2 and C(R 3 )(R 4 ) is a divalent linking group selected from; R is H, C 1-20 -alkyl, C 5-30 -Aryl and C 2-20 - Selected from the unsaturated aliphatic moiety; each R 1 and each R 2 These are H, OR, and C, independently. 1-30 - Hydrocarbyl, substituted C 1-30 -hydrocarbyl, -C(=O)-OR 5 , SR, S(=O)R, S(=O)2R, N(R 5 )(R6 ) and N(R 7 )C(=O)R 5 Selected from; one R 1 And one R 2 Z and R can form a 5-6 membered ring together with the atoms to which they are bonded; 3 and R 4 Independently, C 1-20 -Alkyl and C 5-30 - Selected from the alphabet; R 3 and R 4 These can be condensed with the carbon atoms to which they are bonded to form one or more aromatic rings, and may optionally be substituted to form a 5 or 6-membered ring; R 5 and R 6 Independently, C 1-20 -alkyl or C 5-30 -Aryl; R 7 is H or R 6 And; R 5 and R 6 (These atoms can form a 5-6 membered ring with the atoms to which they are bonded; each of a1 and a2 is 0-5; each of m1 and m2 is 1-100; and n is 2-1000) It is a polymer containing repeating units of Z. Preferred C 1-100 -The hydrocarbylene portion is C 1-50 -Alkylene, C 2-50 - Alkenylene, C 2-50 -Alkynylene and C 5-30 -Arirene, more C 1-20 -Alkylene, C 2-20 - Alkenylene, C 2-20 -Alkynylene and C 5-30 -Arylene. Z is a covalent chemical bond or O, C(=O), S, S(=O), S(=O)2, N(R), C 1-50 -hydrocarbylene, -O-(C 1-20 -Alkilen-O-) m1 ,-O-(C 5-60 -Ariren-O-) m2 and C(R 3 )(R 4A divalent linking group selected from ), more preferably a covalent chemical bond or O, C(=O), S, S(=O)2, C 1-50 -hydrocarbylene, -O-(C 5-60 -Ariren-O-) m2 and C(R 3 )(R 4 A divalent linking group selected from ), and more preferably a covalent chemical bond, O, C(=O), S, S(=O)2, C 5-60 -Ariren, -O-(C 5-60 -Ariren-O-) m2 and C(R 3 )(R 4 ) selected from, and more preferably from covalent chemical bonds, O, C(=O), S, C 5-60 -Ariren, -O-(C 5-60 -Ariren-O-) m2 and C(R 3 )(R 4 It is preferable to select from ). R is preferably H, C 1-20 -Alkyl and C 5-30 - Selected from the aryl group. Preferably, R 1 and R 2 Each of these is independently H, OR, and C 1-30 -Hydrocarbyl, more preferably independently H or C 1-30 - Hydrocarbyl, and even more so C 10-15 - Selected from hydrocarbyl. More preferably, one R 1 And one R 2 Z, along with the atoms to which they are bonded, forms a 5- or 6-membered ring. 1 and R 2 Preferred C 1-30 -The hydrocarbyl portion is C 1-30 -alkyl, C 2-30 -Alkenil, C 2-30 - Alkinyl and C 5-30 -Ayl, more comfortably C 1-20 -alkyl, C 1-20 -Alkenil, C 2-20 - Alkinyl and C 5-30-It is an aryl. Each of a1 and a2 is preferably 0 to 2, more preferably 0 or 1. In a preferred embodiment, a1 = a2, and even more preferably a1 = a2 = 0 or 1. Those skilled in the art will understand that each of the subscripts n, m1 and m2 means the number of repeating units. Preferably, each of m1 and m2 is 1 to 50, more preferably 1 to 25, and even more preferably 1 to 10. It is preferable that n = 2 to 500, more preferably 2 to 100, even more preferably 2 to 50, and even more preferably 2 to 20.

[0029] Preferred compounds of formula (1) are those in which a1 and a2 are each 0 or 1, Z = single covalent bond, O, phenylene, pyrenylene, anthracenylene, phenantracenylene, -O-phenylene-O-, -O-naphthylene-O-, -C(R 3 )(R 4 ) and -O-phenylene-C(R 3 )(R 4 It is a compound that is )-phenylene-O-. Z=-C(R 3 )(R 4 One preferred divalent linking group when )- is given by the following formula

[0030] [ka]

[0031] (In the equation, * indicates a connection point to part of equation (1)) This is the fluorenyl part. When Z=O, one R 1 And one R 2 These together form a 6-membered ring fused heterocycle, and more preferably, one R 1 And one R 2 This is the same as the following formula

[0032] [ka]

[0033] (In the equation, * indicates a connection point to part of equation (1)) It is even more preferable to form a portion of this.

[0034] The curable compounds of the present invention are typically prepared by oxidative coupling polymerization of monomers having a 2-naphthol moiety, using a copper chloride-amine complex as a catalyst. A preferred catalyst is di-μ-hydroxo-bis-[(N,N,N',N'-tetramethylethylenediamine)copper(II)] chloride. Such oxidative coupling polymerization is typically carried out in air at room temperature. A suitable oxidative coupling polymerization is disclosed in (Non-Patent Literature 1). A preferred monomer having a 2-naphthol moiety useful for preparing this curable polymer is given by formula (2):

[0035] [ka]

[0036] (In the formula, R 1 , R 2 (Z, a1 and a2 are as described above for equation (1), and the first is non-substitutive.) It is a compound of formula (2). The monomer of formula (2) is polymerized to form a curable polymer having the repeating unit of formula (1). The monomer of formula (2) must be unsubstituted at position 1. The monomer of formula (2) is bonded (i.e. polymerized) at position 1 of the 2-naphthol moiety as shown in the repeating unit of formula (1). This curable polymer is a homopolymer in which each end of the polymer is terminated with an unreacted 2-naphthol moiety. A preferred monomer of formula (2) is formula (2-1)

[0037] [ka]

[0038] (In the formula, R 1 , R 2 (Z, a1 and a2 are as described above for equation (1), and the first is non-substitutive.) These are monomers. Preferred monomers of formula (2-1) are the monomers of formulas (2a) to (2f).

[0039] [ka]

[0040] Using monomers (2a) to (2f), polymers having repeating units (1a) to (1f) are prepared (in each case, n means the degree of polymerization or the number of repeating units (n = 2 to 1000)).

[0041] [ka]

[0042] In addition to the one or more curable compounds described above, the coating composition may optionally contain one or more organic solvents, preferably. Suitable organic solvents are any organic solvents that dissolve one or more curable compounds, preferably organic solvents conventionally used in the manufacture of electronic devices. Organic solvents may be used alone or in mixtures. Suitable organic solvents include, but are not limited to, ketones, e.g., cyclohexanone and 2-heptanone; alcohols, e.g., 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol and 1-ethoxy-2-propanol; ethers, e.g., 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 and diethylene glycol dimethyl ether This includes ethers, anisoles; 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, and propylene glycol mono-tert-butyl ether acetate; lactones, such as gamma-butyrolactone, and any combination thereof. Preferred solvents are PGME, PGEE, PGMEA, EL, HBM, and combinations thereof.

[0043] The coating composition may also include one or more coating additives typically used in such coatings, such as a curing agent, a crosslinking agent, and a surface smoothing agent. The selection of such optional additives and their amounts is well within the capabilities of those skilled in the art. The curing agent is typically present in an amount of 0 to 20% by weight, preferably 0 to 3% by weight, based on the total solids. The crosslinking agent is typically used in an amount of 0 to 30% by weight, preferably 3 to 10% by weight, based on the total solids. The surface smoothing agent is typically used in an amount of 0 to 5% by weight, preferably 0 to 1% by weight, based on the total solids. The selection of such optional additives and their amounts is well within the capabilities of those skilled in the art.

[0044] A curing agent may be optionally used in the coating composition to accelerate the curing of the deposited curable compound. The curing agent is any component that causes the curing of the curable compound on the surface of the substrate. Preferred curing agents are acids and thermoacid generators. Suitable acids include, but are not limited to, aryl sulfonic acids, e.g., p-toluenesulfonic acid; alkyl sulfonic acids, e.g., methanesulfonic acid, ethanesulfonic acid, and propanesulfonic acid; and perfluoroalkyl sulfonic acids, e.g., trifluoromethanesulfonic acid and perfluoroarylsulfonic acid. A thermoacid generator is any compound that releases acid when exposed to heat. Thermoacid generators are well known in the art and are generally commercially available, for example, from King Industries (Norwalk, Connecticut). Typical thermoacid generators include, but are not limited to, amine-blocked strong acids, e.g., amine-blocked sulfonic acids such as amine-blocked dodecylbenzenesulfonic acid. It will also be understood by those skilled in the art that certain photoacid generators can release acid when heated and can function as thermoacid generators.

[0045] Any suitable crosslinking agent may be used in this composition, provided that such a crosslinking agent has at least two, preferably at least three, parts that can react with the aromatic resin reaction product under suitable conditions, such as acidic conditions. Typical crosslinking agents include, but are not limited to, novolac resins, epoxy-containing compounds, melamine compounds, guanamine compounds, isocyanate-containing compounds, benzocyclobutene, and preferably methylol, C1-C 10 Alkoxymethyl and C2-C 10 This includes any of the aforementioned crosslinking agents having two or more, preferably three or more, and more preferably four substituents selected from acyloxymethyl. Examples of suitable crosslinking agents are those represented by formulas (3) and (4).

[0046] [ka]

[0047] Such crosslinking agents are well known in this field and are commercially available from various suppliers.

[0048] This coating composition may optionally contain one or more surface spreaders (or surfactants). Any suitable surfactant may be used, but such surfactants are typically nonionic. Typical nonionic surfactants are nonionic surfactants containing alkylene oxy bonds, such as ethylene epoxy, propylene oxy, or a combination of ethylene epoxy and propylene oxy bonds.

[0049] The coating composition can be applied to an electronic device substrate by any suitable means, such as spin coating, slot die coating, doctor braiding, curtain coating, roller coating, spray coating, or immersion coating. Spin coating is preferred. In a typical spin coating method, the composition is applied to a substrate rotating at a speed of 500 to 4000 rpm for 15 to 90 seconds to obtain a desired layer of the coating composition on the electronic device substrate. It will be understood by those skilled in the art that the height of the coating composition layer can be adjusted by changing the spin speed.

[0050] After coating the substrate, the coating composition layer is optionally fired at a relatively low temperature to remove all organic solvents and other relatively volatile components from the layer. Typically, the substrate is fired at a temperature of 80 to 150°C, but other suitable temperatures may be used. The firing time is typically 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes, but longer or shorter times may be used. When the substrate is a wafer, such a firing process can be carried out by heating the wafer on a hot plate. After solvent removal, a layer, film, or coating of the curable compound is obtained on the substrate surface.

[0051] Next, the curable compound layer is sufficiently cured to form an aromatic underlayer, so that the film does not mix with any subsequently applied coating layers, such as photoresist or other layers coated directly on the aromatic underlayer. The underlayer can be cured in an oxygen-containing atmosphere such as air or an inert atmosphere such as nitrogen, preferably in an oxygen-containing atmosphere. The curing conditions used are sufficient to cure the film so that it does not mix with any subsequently applied organic layers, such as a photoresist layer, while maintaining the desired anti-reflective properties (n and k values), etch selectivity, gap filling, and planarization of the underlayer film. This curing process is preferably carried out on a hot plate type apparatus, but oven curing can be used to obtain uniform results. Typically, such curing is carried out by heating the underlayer at a curing temperature of ≥150°C, preferably ≥170°C, more preferably ≥200°C. The selected curing temperature may be sufficient to cure the aromatic underlayer. A suitable temperature range for curing the aromatic underlayer is 150-400°C, preferably 170-350°C, more preferably 200-250°C. Such a curing process may take 10 seconds to 10 minutes, preferably 1 to 3 minutes, more preferably 1 to 2 minutes, but other suitable times may be used.

[0052] An initial firing step may not be necessary if the curing process is carried out in such a way that rapid solvent release and by-product curing do not impair the quality of the underlying film. For example, gradient firing, starting at a relatively low temperature and then gradually increasing to a temperature of ≥200°C, can yield acceptable results. In some cases, it may be preferable to have a two-stage curing process in which the first stage is at a lower firing temperature of less than 150°C and the second stage is at a higher firing temperature of ≥200°C. A two-stage curing process facilitates the uniform filling and planarization of the surface morphology of the existing substrate surface, such as filling grooves and vias.

[0053] After the underlying layer has cured, one or more processing layers, such as a photoresist, silicon-containing layer, hard mask layer, or back-side anti-reflective coating (or BARC) layer, may be coated on top of the cured underlying layer. For example, the photoresist may be coated directly onto the surface of the silicon-containing layer or other central layer directly above the resin underlying layer by spin coating, or alternatively, the photoresist may be coated directly onto the cured underlying layer. A variety of photoresists, such as those used in 193nm lithography, such as those sold under the Epic® brand from Dow Electronic Materials (Marlborough, Massachusetts), can be suitably used. A suitable photoresist may be either a positive-tone developing or negative-tone developing resist. After coating, the photoresist layer is then imaged (exposed) using a patterning chemical line, and then the exposed photoresist layer is developed using a suitable developer to obtain a patterned photoresist layer. The pattern is then transferred from the photoresist layer to the underlying layer by a suitable etching technique. Typically, the photoresist is also removed during such an etching process. Next, the pattern is transferred to the substrate by a suitable etching technique known in the art, for example, by plasma etching, and the underlying layer is removed. After patterning the substrate, the underlying layer is removed using a conventional technique. Then, the electronic device substrate is processed according to conventional means.

[0054] A cured underlayer can be used as the bottom layer of a multilayer resist method. In such a method, layers of the coating composition are coated onto the substrate as described above and cured. Next, one or more central layers are coated onto the aromatic underlayer. For example, a silicon-containing layer or a hard mask layer is coated directly onto the aromatic underlayer. Typical silicon-containing layers, such as silicon-BARC, can be deposited by a spin-coating step on the underlayer followed by a curing step, or inorganic silicon layers such as SiON, SiN, or SiO2 can be deposited onto the underlayer by chemical vapor deposition (CVD). Any suitable hard mask can be used and deposited onto the underlayer by any suitable technique and cured as needed. Optionally, an organic BARC layer can be deposited directly onto the silicon-containing layer or hard mask layer and appropriately cured. Next, a photoresist, such as a photoresist used in 193 nm lithography, is coated directly onto the silicon-containing layer (in the 3-layer method) or directly onto the organic BARC layer (in the 4-layer method). Next, a patterned chemical line is used to image (expose) the photoresist layer, and then a suitable developer is used to develop the exposed photoresist layer to obtain a patterned photoresist layer. Next, the pattern is transferred from the photoresist layer to the layer directly beneath it by a suitable etching technique known in the art, such as plasma etching, to obtain a patterned silicon-containing layer in the 3-layer method and a patterned organic BARC layer in the 4-layer method. When the 4-layer method is used, a suitable pattern transfer technique, such as plasma etching, is used to transfer the pattern from the organic BARC layer to the silicon-containing layer or hard mask layer. After the silicon-containing layer or hard mask layer is patterned, the aromatic underlayer is then patterned using a suitable etching technique, such as O2 or CF4 plasma. All remaining patterned photoresist and organic BARC layers are removed during etching of the aromatic underlayer. Next, the pattern is transferred to the substrate, and all remaining silicon-containing layers or hard mask layers are removed, for example by a suitable etching technique, and then all remaining patterned aromatic underlayers are removed to obtain a patterned substrate.

[0055] The cured underlayer of the present invention can also be used in a self-aligning double patterning method. In such a method, a layer of the coating composition is coated onto a substrate, for example by spin coating. All remaining organic solvents are removed and the coating composition layer is cured to form a cured underlayer. A suitable core layer, such as a silicon-containing layer, is coated onto the cured underlayer. Next, a suitable photoresist layer is coated onto the core layer, for example by spin coating. Next, the photoresist layer is imaged (exposed) using a patterning chemical line, and then the exposed photoresist layer is developed using a suitable developer to obtain a patterned photoresist layer. Next, the pattern is transferred from the photoresist layer to the core layer and cured underlayer by a suitable etching technique to expose a portion of the substrate. Typically, the photoresist is also removed during such an etching process. Next, a silicon-containing conformal layer is placed on the patterned cured underlayer to expose a portion of the substrate. Such a silicon-containing layer is typically an inorganic silicon layer such as SiON, SiN, or SiO2, which is conventionally deposited by CVD. Such conformal coatings provide a silicon-containing layer on top of the patterns above and below the exposed portions of the substrate surface, that is, such a silicon-containing layer substantially covers the sides and top of the patterned underlayer. Next, the silicon-containing layer is partially etched (deburred) to expose the upper surface of the patterned polyarylene resin underlayer and a portion of the substrate. After this partial etching step, the pattern on the substrate includes multiple features, each feature including lines or columns in the cured underlayer, and the silicon-containing layer is directly adjacent to the sides of each feature in the cured underlayer. Next, the cured underlayer is removed by etching or the like to expose the substrate surface that was beneath the pattern of the cured underlayer, providing a patterned silicon-containing layer on the substrate surface, where such a patterned silicon-containing layer is twice as numerous as the patterned cured underlayer (i.e., twice as many lines and / or columns).

[0056] The coating compositions of the present invention are also useful for forming planarization layers, gap-filling layers, and protective layers in the manufacture of integrated circuits. When used as such planarization layers, gap-filling layers, or protective layers, one or more intervening material layers, such as silicon-containing layers, other aromatic resin layers, and hard mask layers, are typically present between the cured layer of the coating composition and any photoresist layer. Typically, such planarization layers, gap-filling layers, and protective layers are ultimately patterned. A gap-filling method according to the present invention comprises the steps of (a) providing a semiconductor substrate having a relief image on the surface of the substrate including a plurality of gaps to be filled, and (b) applying a gap-filling composition onto the relief image, wherein the gap-filling composition is of formula (1)

[0057] [ka]

[0058] (In the formula, Z is a covalent chemical bond or O, C(=O), S, S(=O), S(=O)2, N(R), C 1-100 -Hydrocarbylene, substituted C 1-100 -hydrocarbylene, -O-(C 1-20 -Alkilen-O-) m1 ,-O-(C 5-60 -Ariren-O-) m2 and C(R 3 )(R 4 ) is a divalent linking group selected from; R is H, C 1-20 -alkyl, C 5-30 -Aryl and C 2-20 - Selected from the unsaturated aliphatic moiety; each R 1 and each R 2 These are H, OR, and C, independently. 1-30 - Hydrocarbyl, substituted C 1-30 -hydrocarbyl, -C(=O)-OR 5 , SR, S(=O)R, S(=O)2R, N(R 5 )(R 6 ) and N(R 7 )C(=O)R 5 Selected from; one R 1 And one R 2Z and R can form a 5-6 membered ring together with the atoms to which they are bonded; 3 and R 4 Independently, C 1-20 -Alkyl and C 5-30 - Selected from the alphabet; R 3 and R 4 These can be condensed with the carbon atoms to which they are bonded to form one or more aromatic rings, and may optionally be substituted to form a 5 or 6-membered ring; R 5 and R 6 Independently, C 1-20 -alkyl or C 5-30 -Aryl; R 7 is H or R 6 And; R 5 and R 6 (These atoms can form a 5-6 membered ring with the atoms to which they are bonded; each of a1 and a2 is 0-5; each of m1 and m2 is 1-100; and n is 2-1000) The method comprises (c) a step of heating the gap-filling composition to a temperature that cures the one or more curable compounds, and one or more organic solvents. The composition substantially fills, preferably fills, and more preferably completely fills, a plurality of gaps in a semiconductor substrate.

[0059] The compounds of the present invention have good gap-filling properties. Films formed from the compounds of the present invention have good planarization and solvent resistance. [Examples]

[0060] Example 1. Monomer M-1 (4.66 g, 10 mmol) was dissolved in 41.71 g of ethyl lactate. To this solution, 0.23 g (0.5 mmol) of di-μ-hydroxo-bis-[(N,N,N',N'-tetramethylethylene-diamine)copper(II)] chloride (Cu-TMEDA) was added, and the reaction mixture was stirred in air at room temperature for 24 hours. The mixture was slowly added to a methanol mixture containing 1 M hydrochloric acid (200 mL, v / v=20 / 80). The precipitated product was collected by filtration and then redissolved in ethyl acetate. Next, the solution was slowly added to methanol, the precipitated product was collected, and dried under vacuum at 65°C for 2 days. Polymer P-1A (3.2 g) was obtained in a yield of 69%. GPC:M w =1.9K, PDI=1.4. This reaction is shown in reaction scheme 1.

[0061] Example 2. The procedure of Example 1 was repeated as follows. Monomer M-1 (4.66 g, 10 mmol) was dissolved in 43.80 g of ethyl lactate. 0.46 g (1.0 mmol) of Cu-TMEDA was added to this solution, and the reaction mixture was stirred in air at room temperature for 24 hours. The mixture was slowly added to a methanol mixture containing 1 M hydrochloric acid (200 mL, v / v=20 / 80). The precipitated product was collected by filtration and then redissolved in ethyl acetate. Next, the solution was slowly added to methanol, the precipitated product was collected, and dried under vacuum at 65°C for 2 days. Polymer P-1B (3.61 g) was obtained in a yield of 78%. GPC:M w =3.6K, PDI=1.5. This reaction is shown in reaction scheme 1.

[0062] Reaction Scheme 1 [ka]

[0063] Example 3. Monomer M-2 (4.51 g, 10 mmol) was dissolved in 44.73 g of ethyl lactate. 0.46 g (1.0 mmol) of Cu-TMEDA was added to this solution, and the reaction mixture was stirred in open air at room temperature for 24 hours. The mixture was slowly added to a methanol mixture containing 1 M hydrochloric acid (200 mL, v / v=20 / 80). The precipitated product was collected by filtration and then redissolved in ethyl acetate. Next, the solution was slowly added to methanol, the precipitated product was collected, and dried under vacuum at 65°C for 2 days to produce polymer P-2 (3.79 g) with a yield of 84%. GPC:M w =2.2K, PDI=1.6. This reaction is shown in reaction scheme 2.

[0064] Reaction Scheme 2 [ka]

[0065] Example 4. Monomer M-3 (3.94 g, 10 mmol) was dissolved in 17.64 g of ethyl lactate. 0.46 g (1.0 mmol) of Cu-TMEDA was added to this solution, and the reaction mixture was stirred in air at room temperature for 24 hours. The mixture was slowly added to a methanol mixture containing 1 M hydrochloric acid (200 mL, v / v=20 / 80). The precipitated product was collected by filtration and then redissolved in ethyl acetate. Next, the solution was slowly added to methanol, the precipitated product was collected, and dried under vacuum at 65°C for 2 days to yield 3.10 g of polymer P-3 with a yield of 79%. GPC:M w =195K, PDI=19. This reaction is shown in reaction scheme 3.

[0066] Reaction scheme 3 [ka]

[0067] Example 5. Monomer M-4 (6.35 g, 10 mmol) was dissolved in 27.25 g of ethyl lactate. 0.46 g (1.0 mmol) of Cu-TMEDA was added to this solution, and the reaction mixture was stirred in air at room temperature for 24 hours. The mixture was slowly added to a methanol mixture containing 1 M hydrochloric acid (200 mL, v / v=20 / 80). The precipitated product was collected by filtration and then redissolved in ethyl acetate. Next, the solution was slowly added to methanol, the precipitated product was collected, and dried under vacuum at 65°C for 2 days to produce 5.31 g of polymer P-4 with a yield of 83%. GPC:M w =3.0K, PDI=1.5. This reaction is shown in reaction scheme 4.

[0068] Reaction scheme 4 [ka]

[0069] Example 6: Solubility. Solubility was measured by mixing the compounds of the present invention with PGME and PGMEA, respectively, at a solid content of 5%. The mixtures were visually inspected and examined using a turbidimeter (Orbeco-Hellige Co). If the turbidity value was less than 1, the compound was evaluated as soluble ("S"), and if the turbidity value was greater than 1, it was evaluated as insoluble ("NS"). The results are recorded in Table 1. As can be seen from these data, all the compounds of the present invention are soluble in PGME and PGMEA, respectively.

[0070] [Table 1]

[0071] Example 7: Thermal Stability. The thermal stability of the compounds of the present invention was measured using a TA-Instrument thermogravimetric analyzer (TGA) Q500 under the following conditions: up to 700°C with a 10°C / min increase under N2 and up to 700°C with a 10°C / min increase under air. The temperature at which the material lost 5% of its weight (Td5% This is recorded in Table 2.

[0072] [Table 2]

[0073] Example 8. Solvent peel resistance was measured as an indication of film crosslinking. Compositions of the compounds of the present invention were prepared in PGMEA with a solid content of 4.5%. Each composition was spin-coated onto an 8-inch (200 mm) silicon wafer at a speed of 1500 rpm using ACT-8 Clean Track (Tokyo Electron Limited), and then baked at 350°C for 60 seconds to form a film. The initial film thickness was measured using OptiProbe® from Therma-Wave Co. Next, a commercial remover, PGMEA, was applied to each film for 90 seconds, followed by a post-peeling and baking process at 105°C for 60 seconds. The thickness of each film after post-peeling and baking was measured again to determine the amount of film thickness loss. The difference in film thickness before and after contact with the remover is recorded in Table 3 as a percentage of the remaining film thickness. As can be seen from the data, the films formed from polymers P-3 and P-4 of the present invention retained more than 99% of their thickness after contact with the remover.

[0074] [Table 3]

[0075] Example 9. The polymers of the present invention were measured to determine their gap-filling properties. Gap-filling templates were fabricated at CNSE Nano-FAB (Albany, NY). The templates had a SiO2 film thickness of 100 nm and various pitches and patterns. Before coating the coupons with the composition, the template coupons were dehydrated and calcined at 150°C for 60 seconds. Each coating composition (4.5% solids in PGMEA) was coated onto the template coupons using an ACT-8 Clean Track (Tokyo Electron Limited) spin coater at a spin speed of 1500 rpm + / - 200 rpm. The target film thickness after curing was 100 nm, and the dilution of the composition was adjusted accordingly to achieve approximately the target film thickness after curing. The films were cured by placing the wafers on a hot plate at 350°C for 60 seconds. Cross-sectional scanning electron microscope (SEM) images of the coated coupons were collected using a Hitachi S4800 SEM (Hitachi High-Technologies). Film planarization quality was obtained from SEM images using Hitachi Offline CD Measurement Software or CDM Software by measuring the difference (ΔFT) between the film thickness on the via and the film thickness on the groove. Films with ΔFT < 20 nm were considered to have "good" planarization, and films with ΔFT > 20 nm were considered to have "insufficient" planarization. Gap filling was evaluated by visually inspecting SEM images for any voids or bubbles within the groove pattern. Films without voids within the groove pattern were considered to have "good" gap filling, and films with voids within the groove pattern were considered to have "insufficient" gap filling. These results are recorded in Table 4.

[0076] [Table 4]

Claims

1. A coating composition comprising a polymer and an organic solvent, The aforementioned polymer is given by formula (1'): 【Chemistry 1】 (In the formula, Z is -O-(C) ５－６０ -Arirene-O-) ｍ２ And Z is -O-(1,4-phenylene-O-) ｍ２ but 【Chemistry 2】 nor; R is H, C １－２０ -alkyl, C ５－３０ -aryl and C ２－２０ -unsaturated aliphatic moiety; each R １ and each R ２ is independently H, OR, C １－３０ -hydrocarbyl, substituted C １－３０ -hydrocarbyl, -C(=O)-O-R ５ 、SR、S(=O)R、S(=O) ２ R、N(R ５ )(R ６ ) and N(R ７ )C(=O)R ５ selected from; R ５ and R ６ are independently C １－２０ -alkyl or C ５－３０ -aryl; R ７ is H or R ６ ; R ５ and R ６ can form a 5- to 6-membered ring together with the atoms to which they are attached; each of a1 and a2 is 0 to 5; m2 = 1; and n = 2 to 1000) A coating composition comprising repeating units.

2. The repeating unit of the above formula (1') is formula: 【Transformation 3】 and 【Chemistry 4】 A coating composition according to claim 1, selected from the following.

3. The coating composition according to claim 1 or 2, further comprising a curing agent and / or a surface smoothing agent.

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