A method of manufacturing segregated layers above a substrate, and a method for manufacturing a device

Abstract

This invention relates to a method for manufacturing an isolation layer on a substrate. It also relates to a method for manufacturing a photoresist layer, a photoresist pattern, a treated substrate, and an apparatus.

Description

Technical Field

[0001] This invention relates to a method for manufacturing an isolation layer on a substrate. It also relates to a method for manufacturing a photoresist layer, a photoresist pattern, a treated substrate, and an apparatus. Prior Technology

[0002] [background]

[0003] The trend towards smaller and higher-performance devices necessitates finer patterning in devices such as semiconductor devices and FPD devices. Photolithography using photoresist (hereinafter referred to as "resist") is commonly used for this fine-grained processing. To support highly detailed photoresist patterning, other functional layers have been developed, such as top anti-reflective coating (TARC), bottom anti-reflective coating (BARC), spin-on carbon (SOC) coatings, etc. However, this multi-layered structure can complicate the manufacturing process and make it time-consuming and expensive.

[0004] In these cases, a specific process concept using three layers of photoresist has been proposed to limit crystallization defects introduced during ion implantation in semiconductor devices (Patent Document 1). However, in Patent Document 1, some concepts have not been experimentally verified.

[0005] To reduce processing steps in semiconductor manufacturing, a self-isolating polymer composition isolated from the photoresist layer on the BARC layer has been proposed (Patent Document 2). However, Patent Document 2 only demonstrates patterning capability and not self-isolating capability. [Reference List] [Patent Literature]

[0006] Patent Document 1 US2014 / 0061738A

[0007] Patent Document 2 US2010 / 0009132A

[0008] Patent document 3 US9274426B2 Summary of the Invention

[0009] [Technical Issues]

[0010] The inventors have identified one or more significant problems that require improvement, as listed below: difficulty in achieving a good insulating layer using a single application method; time-consuming and expensive methods of applying multiple layers separately; difficulty in obtaining a silicon-rich upper surface in the insulating layer; insufficient reflectivity of the upper surface in the insulating layer; insufficient etching rate of the insulating layer and / or difficulty in adapting the method to a good fit; insufficient uniformity of the insulating layer; numerous voids and / or defects in the insulating layer; insufficient thermal stability of the insulating layer; insufficient gap filling of the components used in the method; insufficient solvent resistance of the upper surface in the insulating layer and difficulty in avoiding cross-mixing with the photoresist composition / layer; and difficulty in applying a photoresist composition / layer with good wetting ability to the insulating layer.

[0011] Then, the inventors of this case discovered that the present invention described below solves at least one of these problems. [Solution to the Problem]

[0012] The present invention provides a method for manufacturing an isolation layer on a substrate, comprising: (1) applying a composition to the substrate, wherein the composition comprises a solvent (A), a silicate polymer (B), and a high-carbon material (C); and (2) heating the substrate to form an isolation layer consisting of an anti-reflective coating derived from the silicate polymer (B) and a spin-coated carbon coating derived from the high-carbon material (C), wherein the anti-reflective coating, the spin-coated carbon coating, and the substrate are arranged in this order.

[0013] The present invention also provides a method for manufacturing a photoresist layer, comprising: (3) applying a photoresist composition onto the isolation layer; and (4) heating the substrate to form a photoresist layer.

[0014] The present invention also provides a method for manufacturing a photoresist pattern, comprising: (5) exposing the photoresist layer; and (6) developing the exposed layer to form a photoresist pattern.

[0015] The present invention also provides a method for manufacturing a treated substrate, comprising: (7) etching through the photoresist pattern as a mask; and (8) treating the substrate.

[0016] Similarly, the present invention provides a method for manufacturing an apparatus.

[0017] Another aspect of the present invention provides a composition for a self-isolating anti-reflective coating and a spin-coated carbon coating, comprising a solvent (A), a silicate polymer (B), and a high-carbon material (C). [Effects of the Invention]

[0018] This method allows for the fabrication of an isolation layer using a single application method. This method reduces the time and cost associated with separately applying spin-coated carbon coatings and anti-reflective coatings to a substrate. The isolation layer can have a silicon-rich upper surface. The upper surface of the isolation layer can have good reflectivity. The isolation layer can have good etching rate and etching resistance, which can be adjusted using high-carbon materials. This method can form an isolation layer with good uniformity. The isolation layer obtained by this method can reduce voids and / or defects. The isolation layer can have good thermal stability. The components used in this method can have good gap-filling properties. The isolation layer can have good solvent resistance and avoid cross-mixing with the upper photoresist components / layers. The upper surface of the isolation layer can have good wetting ability for the photoresist components / layers. Simple Explanation of the Diagram

[0019] Figure 1 shows the silicon content assessment data. Implementation

[0020] The above overview and the following details provide an explanation of the invention and are not intended to limit the scope of the claimed invention. [Detailed Description]

[0021] Throughout this patent specification, unless expressly limited or described otherwise, the symbols, units, abbreviations and terms defined below shall have the meanings provided in the following definitions, descriptions and embodiments.

[0022] The use of the singular includes the plural, and the words "a," "a kind," and "the" mean "at least one." Furthermore, the use of the terms "including" and other forms such as "includes" and "included" is not restrictive. Similarly, terms such as "element" or "component" include both elements or components comprising one unit and elements or components comprising more than one unit.

[0023] The term "and / or" refers to any combination of any of the foregoing elements, including the use of a single element.

[0024] When using "-", "to", or "~" in this document to specify a range of values, the range includes both the number indicated before and after the "-", "to", or "~" and both numbers must be in the same unit. For example, "5-25 moles%" means "5 moles% or more up to 25 moles% or less".

[0025] As used herein, terms such as “Cx-y”, “Cx-Cy”, and “Cx” represent the number of carbon atoms in a molecule or substituent. For example, “C1-6 alkyl” refers to an alkyl chain having 1-6 carbon atoms (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).

[0026] When a polymer as described herein has a plurality of repeating units, these repeating units are copolymerized. The copolymerization may be selected from any of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, and any combination thereof. When the polymer or resin is represented by a chemical structure, n, m, etc., placed in parentheses indicate the number of repetitions.

[0027] The temperature unit indicated in this article is Celsius. For example, "20 degrees" means "20°C".

[0028] When an additive (e.g., a crosslinking agent, a surfactant) is described, the additive means that the compound itself performs its function. For example, when a base-generating agent is described, it means a compound that generates a base. As a specific example that can be implemented, this compound may be dissolved or dispersed in a solvent and then contained in a composition. As in a specific example of the invention, the solvent is preferably contained in the isolated composition as solvent (A). [Composition]

[0029] Subsequently, a composition applied to a substrate in the manufacturing method of the present invention is described. This composition can be the isolating composition when it is isolated as an anti-reflective coating and a spin-coated carbon coating. In a specific embodiment of the present invention, the composition is essentially composed of an isolating composition.

[0030] The composition includes a solvent (A), a silicate polymer (B), and a high-carbon material (C).

[0031] In another embodiment of the invention, the composition comprises an anti-reflective coating and a spin-coated carbon coating, which are isolated from each other.

[0032] Another embodiment of the present invention uses a composition of a self-isolating anti-reflective coating and a spin-coated carbon coating, comprising an anti-reflective coating and a spin-coated carbon coating. [Solvent (A)]

[0033] Solvent (A) may comprise any type of solvent. In one specific embodiment of the invention, solvent (A) comprises an organic solvent. Preferably, the organic solvent comprises a hydrocarbon solvent, an ether solvent, an ester solvent, an alcohol solvent, a ketone solvent, or any mixture thereof.

[0034] Examples of solvents in (A) include: aliphatic hydrocarbon solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, and isobutylbenzene; and monoethanol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, n-pentanol, isopentanol, 2-methylbutanol, 2-ethylhexanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, cyclohexanol, benzyl alcohol, phenylmethylmethanol, diacetone alcohol, and methylbenzene. Phenols; polyol solvents, such as ethylene glycol, propylene glycol, 1,3-butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerol; ketone solvents, such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, trimethyl nonanone, cyclohexanone, cyclopentanone, methyl cyclohexanone, 2,4-pentanedione, acetone-based acetone, acetophenone, and fentanyl ketone; ether solvents, such as ethyl ether, isopropyl ether, n-butyl ether (DBE), n-hexyl ether, 2-ethylhexyl ether, dimethyl dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ... Hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran and 2-methyltetrahydrofuran; ester solvents, such as diethyl carbonate, methyl acetate, ethyl acetate, γ- Butyrolactone, γ-valerolactone, n-propyl acetate, isopropyl acetate, n-butyl acetate (nBA), isobutyl acetate, n-decyl acetate, n-butyl propionate, methyl lactate, ethyl lactate (EL), γ-butyrolactone, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, propylene glycol 1-monomethyl ether 2-acetate (PGMEA), di(propylene glycol) methyl ether acetate (Di(PGMEA)), propylene glycol monoethyl ether acetate, cyclohexyl hexanoate, and propylene glycol monopropyl ether acetate; nitrogen-containing solvents, such as N-methylmethamide; and sulfur-containing solvents, such as dimethyl sulfide. Any mixture of these solvents may also be used.

[0035] In one specific embodiment of the invention, the solvent (A) comprises at least one high-boiling-point solvent, preferably Di(PGMEA), cyclohexyl hexanoate, n-decyl acetate, and any mixture thereof; more preferably Di(PGMEA), n-decyl acetate, and any mixture thereof; and even more preferably a mixture of Di(PGMEA) and n-decyl acetate. While not intended to be theoretically definitive, the inventors believe that the presence of a high-boiling-point solvent extends the drying time of the composition after application to the substrate, allowing for better separation of the components into a layer. The solvent in solvent (A), other than the high-boiling-point solvent, may be a base solvent.

[0036] In one specific embodiment of this invention, the high-boiling solvent has a boiling point that is 50% higher than that of the base solvent (preferably 50-150%, more preferably 70-125%). If there are multiple high-boiling solvents or base solvents in the solvent (A), the boiling point is obtained by averaging the values ​​of each.

[0037] The base solvent is preferably PGME, PGMEA, EL, nBA, DBE and any mixture thereof; more preferably PGME, PGMEA and mixture thereof; and even more preferably a mixture of PGME and PGMEA.

[0038] The mass ratio of the high-boiling-point solvent to the base solvent is preferably 5-30%, more preferably 10-25%, and even more preferably 10-20%.

[0039] If the high-boiling-point solvent or base solvent is a mixture of two in each type, the mass ratio of the first solvent to the second solvent is preferably 90:10-10:90, more preferably 80:20-20:80. If the high-boiling-point solvent or base solvent is a mixture of three in each type, the mass ratio of the first solvent to the total of the three species is preferably 30-90% (more preferably 50-80%, further preferably 60-70%); the mass ratio of the second solvent to the total of the three species is preferably 10-50% (more preferably 20-40%); and the mass ratio of the third solvent to the total of the three species is preferably 5-40% (more preferably 5-20%, further preferably 5-15%).

[0040] The solvent (A) preferably comprises an organic solvent, and the amount of water in the solvent (A) is preferably 0.1% by mass or less, and more preferably 0.01% by mass or less. In view of its relationship with another layer or coating, the solvent (A) is preferably anhydrous.

[0041] In a specific embodiment of the present invention, the mass ratio of the solvent (A) is 60-99% by mass, more preferably 70-97% by mass, more preferably 80-95% by mass, and even more preferably 90-95% by mass, based on the total mass of the isolating composition. [Silicone Polymer (B)]

[0042] The siloxane polymer (B) may contain at least one unit selected from the group consisting of unit B1, unit B2 and unit B3.

[0043] Unit B1 is represented by equation B1.

[0044] Ah11 is a C1-5 aliphatic hydrocarbon. Preferably, Ah11 is methyl, ethyl, n-propyl, isopropyl, tributyl, vinyl (H2 C=CH-) or ethynyl (HC≡C-); more preferably methyl or tributyl; and even more preferably methyl.

[0045] R12 is a single bond of -Ah12, -O-Ah12, -O-*, -Si(H)p12(Ah12)q12, -O-Si(H)p12(Ah12)q12, or other units. R12 is preferably -Ah12, -O-Ah12, -Si(H)p12(Ah12)q12, or -O-Si(H)p12(Ah12)q12; more preferably -Ah12 or -O-Si(H)p12(Ah12)q12; even more preferably -Ah12. In a specific embodiment of the invention, R12 is -O-Si(H)p12(Ah12)q12.

[0046] The asterisk (*) signifies a single bond to other units and / or polymer terminals. This single bond may bind to other units via another single bond and / or aliphatic hydrocarbon in the polymer. The term "other units" does not include a unit B1 in which the single bond is present. However, in the case where the siloxane polymer (B) contains a plurality of units B1, the single bond may be bonded to other units B1 (units B1 in which the single bond is not present, and there is no self-crosslinking in a unit B1). Unless otherwise specifically described, the same applies hereafter.

[0047] "Single bond to other units" means a single bond that connects to other units. Unless otherwise specified, the same applies hereafter.

[0048] Ah12 is a C1-5 aliphatic hydrocarbon. Preferably, Ah12 is methyl, ethyl, n-propyl, isopropyl, tributyl, vinyl, or ethynyl; more preferably methyl, tributyl, or vinyl; further preferably methyl or vinyl; even more preferably methyl.

[0049] The following is an example of a silicone polymer (B) containing two units B1. The two middle units B1 provide -O-* R12 and single bonds to other units bonded to each other. The Ah11 of each of the two middle units B1 is methyl.

[0050] p12 = 0, 1, 2, or 3. p12 is preferably 0 or 1, even better than 0. q12 = 0, 1, 2, or 3. q12 is preferably 2 or 3, even better than 3. p12 + q12 = 3.

[0051] L11 series single bond or -O-, preferably -O-.

[0052] n11 is the number of times unit B is repeated.

[0053] The following example of unit B1 is not intended to limit the scope of the claims of this invention.

[0054] Unit B2 is represented by equation B2.

[0055] R21 is a single bond of -Ah21, -O-Ah21, -O-*, -Si(H)p21 (Ah21)q21, -O-Si(H)p21 (Ah21)q21 or other units. R21 is preferably a single bond of -O-Ah21, -O-*, -Si(H)p21 (Ah21)q21, -O-Si(H)p21 (Ah21)q21 or other units; more preferably -O-Ah21, -Si(H)p21 (Ah21)q21 or -O-Si(H)p21 (Ah21)q21; even more preferably -O-Si(H)p21 (Ah21)q21.

[0056] R22 is a single bond of -Ah22, -O-Ah22, -O-*, -Si(H)p22 (Ah22)q22, -O-Si(H)p22 (Ah22)q22 or other units. R22 is preferably a single bond of -O-Ah22, -O-*, -Si(H)p22 (Ah22)q22, -O-Si(H)p22 (Ah22)q22 or other units; more preferably -O-Ah22, -Si(H)p22 (Ah22)q22 or -O-Si(H)p22 (Ah22)q22; even more preferably -O-Si(H)p22 (Ah22)q22.

[0057] Ah21 and Ah22 are each independently C1-5 aliphatic hydrocarbons. Ah21 and Ah22 are each preferably methyl, ethyl, n-propyl, isopropyl, tributyl, vinyl (H2 C=CH-) or ethynyl (HC≡C-); more preferably methyl or tributyl; and even more preferably methyl.

[0058] p21, p22, q21, and q22 are each independently 0, 1, 2, or 3. It is preferable that p21 and p22 are each independently 0 or 1, more preferably 0. It is preferable that q21 and q22 are each independently 2 or 3, more preferably 3.

[0059] p21+q21=p22+q22=3.

[0060] L21 series single bond or -O-, preferably -O-.

[0061] The number of repetitions of unit B2 in the n21 series.

[0062] The following example of unit B2 is not intended to limit the scope of the claims of this invention.

[0063] Unit B3 is represented by equation B3.

[0064] R31 is a single bond of -Ah31, -O-Ah31, -O-*, -Si(H)p31(Ah31)q31, -O-Si(H)p31(Ah31)q31, or other units. R31 is preferably -Ah31, -O-Ah31, -Si(H)p31(Ah31)q31, or -O-Si(H)p31(Ah31)q31; more preferably -Ah31 or -O-Si(H)p31(Ah31)q31; even more preferably -Ah31. In a specific embodiment of the invention, R31 is -O-Si(H)p31(Ah31)q31.

[0065] Ah31 is a C1-5 aliphatic hydrocarbon. Preferably, Ah31 is methyl, ethyl, n-propyl, isopropyl, tributyl, vinyl, or ethynyl; more preferably methyl, tributyl, or vinyl; further preferably methyl or vinyl; even more preferably methyl.

[0066] p31 = 0, 1, 2, or 3. p31 is preferably 0 or 1, more preferably 0. q31 = 0, 1, 2, or 3. q31 is preferably 2 or 3, more preferably 3. p31 + q31 = 3.

[0067] R32 is a group consisting of at least two groups and / or linkers selected from the group consisting of: phenyl, phenylene, -O-, -(C=O)-, -COO-, -COOH, -NH-, C1-5 aliphatic hydrocarbon groups and C1-5 aliphatic hydrocarbon linkers. One linker of R32 may be bonded to other linkers to form a hydrocarbon ring or heterocyclic group, preferably an aromatic ring or heteroaromatic group, more preferably a heteroaromatic group.

[0068] The following are illustrative siloxane polymers (B) containing unit B3. R32 is composed of n-propyl (C3 aliphatic hydrocarbon linker), -NH-, -(C=O)-, secondary butyl (C4 aliphatic hydrocarbon linker) and -(C=O)- in this order, wherein the terminal -(C=O)- is bonded to -NH- to obtain a heteroaromatic group.

[0069] In a specific embodiment of the present invention, R32 is a group consisting of 2-7 (more preferably 2-6, further preferably 3-5) groups and / or linkers.

[0070] In one specific embodiment of the invention, R32 is a group consisting of at least two groups and / or linkers selected from the group consisting of: preferably phenyl, phenylene, -O-, -(C=O)-, -COO-, -COOH, -NH-, C1-5 aliphatic hydrocarbon group and C1-5 aliphatic hydrocarbon linker; more preferably phenylene, -O-, -(C=O)-, -COO-, -NH-, C1-5 aliphatic hydrocarbon group and C1-5 aliphatic hydrocarbon linker.

[0071] L31 series single bond or -O-, preferably -O-.

[0072] The number of repetitions of unit B3 in the n31 series.

[0073] The following example of unit B3 is not intended to limit the scope of the claims of this invention.

[0074] While not intending to go beyond theoretical boundaries, the inventors of this case considered a protecting group (e.g., tributyl, methoxymethyl ether) that serves to maintain the hydrophobic polysiloxane layer until phase separation occurs.

[0075] The weight average molecular weight (Mw) of the siloxane polymer (B) is preferably 1,000-100,000, more preferably 2,000-50,000, further preferably 3,000-20,000, and even more preferably 3,000-10,000.

[0076] Mw and Mn (number average molecular weight) can be measured by known methods. When the sample is a polymer, in a preferred embodiment, the measurement method is the one used in the operational examples, as described later herein. Monodisperse polystyrene can be used as a standard.

[0077] n11, n21, and n31 represent the number of repetitions of units B1, B2, and B3 in the siloxane polymer (B). The values ​​are: 0% ≤ n11 / (n11 + n21 + n31) ≤ 80%, 0% ≤ n21 / (n11 + n21 + n31) ≤ 80%, and 0% ≤ n31 / (n11 + n21 + n31) ≤ 80%.

[0078] The value of n11 / (n11 + n21 + n31) is preferably 5-75%, more preferably 10-70%, further preferably 20-70%, and further preferably 30-70%.

[0079] The value of n21 / (n11 + n21 + n31) is preferably 0-75%, more preferably 0-70%, further preferably 0-60%, and even more preferably 0-40%.

[0080] The ratio of n31 / (n11 + n21 + n31) is preferably 5-75%, more preferably 10-60%, further preferably 10-50%, and even more preferably 10-40%.

[0081] As for specific examples of the siloxane polymer (B), those used in the operational embodiments described herein may be proposed later.

[0082] In one specific embodiment of the invention, the siloxane polymer (B) system comprises 0.1-10% by mass, preferably 0.2-5% by mass, more preferably 0.5-5% by mass, further preferably 0.75-3% by mass, and even more preferably 0.90-2% by mass, based on the total mass of the isolating composition. [High-carbon materials (C)]

[0083] The spin-coated carbon coating produced by this invention is derived from a high-carbon material (C). Here, "derived from" means that the coating structure is mainly composed of the high-carbon material (C) itself or of compounds / polymers formed therefrom. For example, in a specific embodiment of this invention, a crosslinking agent (E) can be incorporated into the spin-coated carbon coating.

[0084] The spin-coated carbon coating of the present invention preferably has high etching resistance. A preferred embodiment of the present invention is that the number of atoms in the spin-coated carbon coating satisfies the following formula C1. 1.5 ≤ {total number of atoms / (number of C atoms - number of O atoms)} ≤ 3.5 (Equation C1)

[0085] The number of C atoms represents the number of carbon atoms in the total number of atoms, and the number of O atoms represents the number of oxygen atoms in the total number of atoms. The total number of atoms in formula C1 includes the number of hydrogen atoms.

[0086] This can be described as the atoms in the solid component of the composition being spin-coated carbon. It can also be described as the solid component of the spin-coated carbon coating being a component that forms the spin-coated carbon coating. For example, atoms in the solvent (A) are ignored when calculating the aforementioned atoms.

[0087] Equation C1 is preferably Equation C1', and more preferably Equation C1". 1.5 ≤ {total number of atoms / (number of C atoms - number of O atoms)} ≤ 2.4 (Equation C1') 1.8 ≤ {total number of atoms / (number of C atoms - number of O atoms)} ≤ 2.4 (Equation C1)

[0088] The high-carbon material (C) may contain at least one selected from the group consisting of unit C2, molecule C3 and unit C4.

[0089] Unit C2 is represented by the formula C2. Unit C2 can constitute a polymer.

[0090] Ar41 is a C6-60 hydrocarbon that is either unsubstituted or substituted with R41. Preferably, Ar41 does not contain a fused aromatic ring. Ar41 is preferably 9,9-diphenyl-phenylene, 9-phenyl-phenylene, phenyl, C6-60 linear polyphenylene, and C6-60 branched polyphenylene, each of which may be substituted with R41.

[0091] R41 is a linear, branched, or cyclic C1-20 alkyl, amino, or alkylamino group; preferably a linear, branched, or cyclic C1-10 alkyl or alkylamino group; more preferably a linear C1-3 alkyl, branched C1-3 alkyl, cyclopentyl, cyclohexyl, or dimethylamino group.

[0092] When the high-carbon material (C) contains a plurality of units C2, R41 can be inserted into and bonded to a plurality of Ar41 units as a connector. An Ar41 unit can be replaced by a single or a plurality of R41 units, preferably by a single R41 unit.

[0093] In a unit C2, a group enclosed in parentheses (e.g., a group enclosed in parentheses and described by p41 on the side) can be bonded to R41. In this case, the group is bonded to Ar41 via R41, which acts as a linker.

[0094] R12 is a compound of I, Br, or CN, with I or Br being preferred, and I being even more preferred.

[0095] The number of p41 series units is 0-5. In a specific embodiment of the invention, the high-carbon material (C) may comprise two C2 units, one after the other. One embodiment of this specific example is two Ar41 series phenyl units, and one p41 series 1 and other p41 series 2 units. In this case, the p41 series is generally 1.5. Unless otherwise specifically described in this patent specification, the same applies hereafter.

[0096] p41 is preferably 0, 1, 2, or 3, more preferably 0, 1, or 2, further preferably 0 or 1, and even more preferably 0. In another preferred embodiment of the invention, p41 is 1.

[0097] p42 represents the number of 0-1, preferably 0 or 1, and even more preferably 1.

[0098] q41 is a number from 0 to 5. q41 is preferably 0, 1, 2, or 3, more preferably 0, 1, or 2, further preferably 0 or 1, and even more preferably 0. In another preferred embodiment of the invention, q41 is 1.

[0099] q42 represents the number of 0s and 1s, preferably 0 or 1, and even more preferably 1.

[0100] r41 is a number from 0 to 5, preferably 0, 1, 2, 3, 4 or 5, more preferably 0, 1, 2 or 3, further preferably 1 or 2, and even more preferably 1. In another preferred embodiment of the invention, r41 is 0.

[0101] s41 is a number from 0 to 5. r41 is preferably 0, 1, 2 or 3, more preferably 0, 1 or 2, further preferably 0 or 1, and even more preferably 0. In another preferred embodiment of the invention, r41 is 1.

[0102] In a preferred embodiment of the present invention, in a unit C2, p41, q41 and r41 are not simultaneously 0.

[0103] When the high-carbon material (C) is a polymer, its molecular weight is expressed as weight average molecular weight (Mw).

[0104] Preferably, the molecular weight of the high-carbon material (C) containing unit C2 is 500-4,000, more preferably 500-3,000, and even more preferably 1,000-2,000.

[0105] The following description of the illustrative unit C2 is not intended to limit the scope of the invention.

[0106] The molecule C3 is represented by the formula C3. The molecule C3 can act as a unit that constitutes polymers of high-carbon materials (C).

[0107] Ar51 is a single bond, C1-6 alkyl, C6-12 cycloalkyl, or C6-14 aryl group. Ar51 is preferably a single bond, C1-6 alkyl, or phenyl; more preferably a single bond, linear C3 alkyl, linear C6 alkyl, tert-butyl, or phenyl; even more preferably a single bond or phenyl; and even more preferably phenyl.

[0108] Ar52 is a C1-6 alkyl, C6-12 cycloalkyl, or C6-14 aryl group. Preferred Ar52 groups are isopropyl, tributyl, C6 cycloalkyl, phenyl, naphthyl, phenanthryl, or biphenyl; more preferably phenyl.

[0109] R51 and R52 are each independently C1-6 alkyl, hydroxyl, halogen or cyano. R51 and R52 are each preferably independently methyl, ethyl, propyl, isopropyl, tributyl, hydroxyl, fluorine, chlorine or cyano; more preferably methyl, hydroxyl, fluorine or chlorine.

[0110] R53 is hydrogen, C1-6 alkyl, or C6-14 aryl. R53 is preferably hydrogen, C1-6 alkyl, or phenyl; more preferably hydrogen, methyl, ethyl, linear C5 alkyl, tert-butyl, or phenyl; further preferably hydrogen or phenyl; and even more preferably hydrogen.

[0111] In the case of Ar52 series C1-6 alkyl or C6-14 aryl and R53 series C1-6 alkyl or C6-14 aryl, Ar52 and R53 can bond to each other to form a hydrocarbon ring.

[0112] r51 and r52 are each independently an integer between 0 and 5. It is preferable that r51 and r52 are 0 or 1, and even more preferable that they are 0.

[0113] The Cy51, Cy52 and Cy53 rings enclosed by the dashed lines can selectively and independently be fused with the adjacent aromatic ring Ph51.

[0114] The Cy54, Cy55 and Cy56 rings enclosed by the dashed lines can selectively and independently be fused with the adjacent aromatic ring Ph52.

[0115] The bonding positions of R51, R52 and OH are not restricted.

[0116] The following compounds are specific examples of the C3 molecule of the present invention. The aromatic ring Ph51 and the aromatic ring Cy53 are fused together to form a naphthyl ring, and the OH group is bonded to the aromatic ring Cy53. Further, Ar51 is a single bond, Ar52 and R53 are phenyl groups, and Ar52 and R53 are bonded together to form a hydrocarbon ring ([unclear]).

[0117] The following description of the illustrative molecule C3 is not intended to limit the scope of the invention.

[0118] Unit C4 is represented by equation C4.

[0119] R61 is a hydrogen, C1-6 alkyl, halogen or cyano group, preferably hydrogen, methyl or tert-butyl, more preferably hydrogen or methyl, and even more preferably hydrogen.

[0120] R62 is a C1-6 alkyl, halogen, or cyano group, preferably methyl or tert-butyl, and more preferably methyl.

[0121] p61 represents the number of repetitions. p62 represents an integer from 0 to 5, preferably 0 to 1, and even more preferably 0.

[0122] In one embodiment of the present invention, the high-carbon material (C) may comprise a plurality of units C2, molecules C3, and units C4. The following description of specific examples is not intended to limit the scope of the invention.

[0123] In a specific embodiment of the present invention, the mass ratio of the high carbon material (C) is 0.5-30% by mass, preferably 1-20% by mass, more preferably 3-15% by mass, further preferably 5-10% by mass, and even more preferably 5-8% by mass, based on the total mass of the isolating composition. [Thermal Acid Generator (D)]

[0124] The components used in the manufacturing method of this invention may include a thermal acid generator (D) and / or a crosslinking agent (E). Upon heating, the thermal acid generator (TAG) can generate an acid, preferably a strong acid. The generated acid can catalyze the reaction of the crosslinking agent (E) and can help to process the material at a lower temperature and shorten the reaction time for forming the antireflective coating.

[0125] Preferred TAGs include those that are activated at temperatures exceeding 80 degrees Celsius. Examples of such TAGs include metal-free strontium salts and metal-free monium salts, such as triarylstrontium salts, dialkylarylstrontium salts, and diarylalkylstrontium salts of strong nonnucleophilic acids; and alkylaryl monium salts and diaryl monium salts of strong nonnucleophilic acids; and ammonium salts, alkylammonium salts, dialkylammonium salts, trialkylammonium salts, and tetraalkylammonium salts of strong nonnucleophilic acids.

[0126] Furthermore, covalent TAGs are also useful, and examples include 2-nitrobenzyl esters of alkyl or aryl sulfonic acids and other sulfonates that thermally decompose to provide free sulfonic acid. Examples include perfluoroalkyl sulfonate diaryl monazine, tris(fluoroalkyl guanylate) methylated diaryl monazine, bis(fluoroalkyl guanylate) methylated diaryl monazine, bis(fluoroalkyl guanylate) imidin diaryl monazine, and perfluoroalkyl sulfonate diaryl monazine quaternary ammonium. Examples of unstable esters include 2-nitrobenzyl toluenesulfonate, 2,4-dinitrobenzyl toluenesulfonate, 2,6-dinitrobenzyl toluenesulfonate, and 4-nitrobenzyl toluenesulfonate; benzenesulfonates, such as 2-trifluoromethyl-6-nitrobenzyl 4-chlorobenzenesulfonate and 2-trifluoromethyl-6-nitrobenzyl 4-nitrobenzenesulfonate; phenolsulfonates, such as phenyl 4-methoxybenzenesulfonate; trimethyl(fluoroalkyl)methylated quaternary ammonium, bis(fluoroalkyl)imidinium quaternary alkylammonium, and alkylammonium salts of organic acids, such as triethylammonium salt of 10-camphorsulfonic acid. Various aromatic (anthracene, naphthalene, or benzene derivative) sulfonamide salts can be used as TAGs.

[0127] The following description of specific examples of TAG(D) is not intended to limit the scope of the invention.

[0128] In a specific embodiment of the present invention, the mass ratio of the hot acid generator (D) is 10-50% by mass, more preferably 10-40% by mass, more preferably 15-30% by mass, and even more preferably 20-30% by mass, based on the total mass of the siloxane polymer (B). [Crosslinking agent (E)]

[0129] The crosslinking agent (E) can enhance the coating formation properties, prevent the isolation layer of the present invention from mixing with the upper coating (such as a photoresist coating), and eliminate the diffusion of low molecular weight components into the upper coating. By heating, the crosslinking agent (E) can bond to a high carbon material (C) to obtain a spin-coated carbon coating.

[0130] As for the crosslinking agent (E), melamine compounds, guanamine compounds, acetylenide compounds, or urea compounds can be used, which are substituted with at least one group selected from hydroxymethyl, alkoxymethyl, and acetylenicmethyl groups; epoxy compounds, thioepoxide compounds, isocyanate compounds, azide compounds, and compounds containing double bonds, such as alkenyl ether groups. These can be used as additives or can suspend groups introduced into the polymer side chain. Furthermore, compounds containing hydroxyl groups can also be used as the crosslinking agent.

[0131] Examples of the aforementioned epoxy compounds include tris(2,3-epoxypropyl) triisocyanate, trimethylolpropane trioxypropyl ether, trimethylolpropane trioxypropyl ether, and triethylolethane trioxypropyl ether. Examples of the melamine compounds include hexamethylol melamine, hexamethoxymethyl melamine, compounds derived from the methoxymethylation of 1-6 hydroxymethyl groups of hexamethylol melamine and mixtures thereof, hexamethoxyethyl melamine, hexachloromethyl melamine, and compounds derived from the acetoxymethylation of 1-6 hydroxymethyl groups of hexamethylol melamine or mixtures thereof. As for the guanidine compound, tetrahydroxymethylguanidine, tetramethoxymethylguanidine, compounds derived from the methoxymethylation of 1-4 hydroxymethyl groups of a mixture of tetrahydroxymethylguanidine and such compounds, tetramethoxyethylguanidine, tetraoxyguanidine, and compounds derived from the acetylation of 1-4 hydroxymethyl groups of a mixture of tetrahydroxymethylguanidine and such compounds. As for the acetylenoid compound, tetrahydroxymethylacetylenoid, tetramethoxyacetylenoid, tetramethoxymethylacetylenoid, compounds derived from the methoxymethylation of 1-4 hydroxymethyl groups of a mixture of tetrahydroxymethylacetylenoid or such compounds, and compounds derived from the acetylation of 1-4 hydroxymethyl groups of a mixture of tetrahydroxymethylacetylenoid or such compounds. As for the urea compound, tetrahydroxymethyl urea, tetramethoxymethyl urea, compounds derived from the methoxymethylation of 1-4 hydroxymethyl groups of tetrahydroxymethyl urea or mixtures thereof, tetramethoxyethyl urea, and analogues thereof may be used.

[0132] As for the compound including the alkenyl ether group, ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethyl glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, neopentyl tetraethylene glycol trivinyl ether, neopentyl tetraethylene glycol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether, and analogues thereof can be used.

[0133] The following description illustrates specific examples of the crosslinking agent (E) but is not intended to limit the scope of the invention.

[0134] In a specific embodiment of the present invention, based on the total mass of the high-carbon material (C), the mass ratio of the crosslinking agent (E) is 3-50% by mass, preferably 5-30% by mass, more preferably 5-20% by mass, and even more preferably 8-15% by mass. [Additive (F)]

[0135] The components used in the manufacturing method of this invention may include further additives (F) in addition to TAG (D) or crosslinking agent (E). These additives may include surfactants, thermal alkali generators (TBG), acids, alkalis, photopolymerization initiators, reagents for improving adhesion to substrates, or any mixture thereof.

[0136] In one specific embodiment of the invention, the mass ratio of the additive (F) (the sum of multiple species if present) is 0-10% by mass, preferably 0.0001-5% by mass, and more preferably 0.0001-3% by mass, based on the total mass of the isolating composition. In another embodiment of the invention, the additive (F) is not included in the isolating composition. [Surfactants]

[0137] A specific example of the additive (F) is a surfactant. The surfactant can reduce pinholes or streaks in coatings made from the composition and can increase the coating ability and / or solubility of the composition.

[0138] The amount of the surfactant is preferably 0-5% by mass, more preferably 0.00001-3% by mass, even more preferably 0.0001-2% by mass, and even more preferably 0.001-2% by mass. In another preferred embodiment of the invention, the composition does not contain any surfactant (0% by mass).

[0139] Examples of the surfactant include: polyoxyethylene alkyl ether compounds, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl ether compounds, such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxyethylene propyl block copolymer compounds; sorbitol fatty acid ester compounds, such as sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol trioleate, and sorbitol tristearate; and polyoxyethylene sorbitol fatty acid ester compounds, such as polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, and polyoxyethylene sorbitol tristearate. Other embodiments of this surfactant include: fluorinated surfactants such as EFTOP (trade names) EF301, EF303 and EF352 (Tohkem Products Corporation); MEGAFACE (trade names) F171, F173, R-08, R-30, R-41 and R-2011 (DIC Corporation); Fluorad FC430 and FC431 (Sumitomo 3M); AsahiGuard (trade name) AG710 (Asahi Glass), and SURFLON S-382, SC101, SC102, SC103, SC104, SC105 and SC106 (Asahi Glass); and organosiloxane polymers such as KP341 (Shin-Etsu Chemical). [Methods for manufacturing isolation layers]

[0140] The present invention provides a method for manufacturing an isolation layer on a substrate, comprising: (1) applying a composition to the substrate, wherein the isolation composition comprises a solvent (A), a silicate polymer (B), and a high-carbon material (C); and (2) heating the substrate to form an isolation layer consisting of an anti-reflective coating derived from the silicate polymer (B) and a spin-coated carbon coating derived from the high-carbon material (C), wherein the anti-reflective coating, the spin-coated carbon coating, and the substrate are arranged in this order.

[0141] For clarity, in this description of the method, unless otherwise specified, the number of parentheses throughout this patent specification indicates the order. For example, step (1) is performed before step (2).

[0142] Without intending to confine it to theoretical boundaries, the inventors of this invention believe that the phase separation is driven by the difference in surface energy and / or solubility between the siloxane polymer (B) and the high-carbon material (C). One embodiment of the invention is that the self-isolation system is caused by phase separation through the difference in surface energy and / or solubility (preferably surface energy) between the siloxane polymer (B) and the high-carbon material (C).

[0143] The insulating composition of the present invention can be applied to a substrate. The term "on a substrate" can indicate that the applied composition can form a coating directly on the substrate, i.e., in direct contact with the substrate, but also includes the possibility of inserting an intermediate layer between the substrate and the applied composition. The term "on" includes both "in direct contact with" and "intervened by an intervening layer".

[0144] Prior to this, the surface of the substrate may be pretreated, for example, with a solution of 1,1,1,3,3,3-hexamethyldisilazane. The upper surface of the substrate may be flat or uneven. The substrate used may be a metal-containing substrate or a silicon-containing substrate. The substrate may be a single-layer substrate or a multilayer substrate composed of multiple substrate layers. As for the substrate, any known substrate may be used, such as a silicon-coated substrate.

[0145] In one specific embodiment of the invention, the isolating composition is applied using suitable means, such as a spinner or coating machine. When the composition is applied to the substrate, the substrate and the composition are preferably in direct contact with each other. In another specific embodiment of the invention, the isolating composition can be applied with another thin coating layer (such as a substrate modification layer) inserted between the isolating composition and the substrate. Following the application of the composition, heating is performed to cause phase separation, thereby isolating the anti-reflective coating and the spin-coated carbon coating.

[0146] The heating process of (2) in this invention is typically carried out at 20-450°C for 0.1-30 minutes. Preferably, the heating is carried out in air, an inert gas, or a combination thereof.

[0147] For phase separation requiring a long time, heating is preferable. For this sample, several heating steps are preferred. Regarding the first heating step, low-temperature heating is preferred. In one embodiment of the invention, the substrate is heated at a low temperature under vacuum conditions, preferably from room temperature to 80°C, more preferably between 50-80°C, and even more preferably between 50-75°C. The heating time for this first heating step is selected from the range of 30-240 seconds (preferably 60-180 seconds, more preferably 90-150 seconds).

[0148] A preferred embodiment of the present invention is that the heating process includes multiple heating steps. For example, a second heating step, a third heating step, and a fourth heating step may be added. The heating conditions for four steps are illustrated below. The present invention does not always require all heating steps and can be simplified for high production volumes. In a more preferred embodiment of the present invention, the heating process consists of a two-step baking process consisting of a first heating step and a second heating step.

[0149] The second heating step can be carried out at 50-250°C (preferably 75-200°C, more preferably 100-200°C, and even more preferably 125-175°C) for 0.5-30 minutes (preferably 1-20 minutes, more preferably 5-15 minutes).

[0150] The third heating step can be carried out at 100-400°C (preferably 150-300°C, more preferably 200-300°C, and even more preferably 225-275°C) for 0.1-5 minutes (preferably 0.1-3 minutes, more preferably 0.5-2 minutes).

[0151] The fourth heating step can be carried out at 150-450°C (preferably 250-400°C, more preferably 300-400°C, and even more preferably 325-375°C) for 0.1-5 minutes (preferably 0.1-3 minutes, more preferably 0.5-2 minutes).

[0152] The subsequent heating step tends to involve high temperatures. The spin-coated carbon coating obtained from the high-carbon material (C) of this invention exhibits good heat resistance. Thus, high-temperature heating can be performed in this method.

[0153] In one specific embodiment of the present invention, the antireflective coating is prepared from a silicate polymer (B) having a thickness of 50-500 nanometers, preferably 50-200 nanometers, and more preferably 100-200 nanometers. In one specific embodiment of the present invention, the spin-coated carbon coating is prepared from a high-carbon material (C) having a thickness of 100-10,000 nanometers, preferably 100-1,500 nanometers, more preferably 100-1,000 nanometers, further preferably 100-500 nanometers, and even more preferably 100-200 nanometers.

[0154] This invention supports the silicone polymer (B) having a structure that allows the coating to have a suitable antireflective properties. Thus, the coating can function as an antireflective coating, preferably a bottom antireflective coating. While not intended to be theoretically definitive, the inventors believe that the upper interface obtained from the isolating composition is silicon-rich, and that the main component of the upper interface is the coating obtained from the silicone polymer (B). Therefore, the coating obtained from the isolating composition can function as a bottom antireflective coating.

[0155] In one specific embodiment of the invention, the coating is prepared from the composition of the invention and has a thickness of 150-2,000 nanometers (preferably 150-1,000 nanometers, more preferably 150-500 nanometers, and even more preferably 150-200 nanometers), which is the sum of the anti-reflective coating and the spin-coated carbon coating.

[0156] Both the antireflective coating derived from the siloxane polymer (B) and the spin-coated carbon coating derived from the high-carbon coating can be obtained and possess suitable etching resistance. These isolation layers can also be obtained and possess good etching resistance. For methods using this isolation composition, the atomic composition of the spin-coated carbon coating can be altered by modifying the high-carbon material (C) and other solid components, thereby effectively obtaining a suitable etching rate. The solid components including the high-carbon material (C) can possess good gap-filling properties, thus enabling the effective application of this isolation composition to uneven substrates. [Formation of the photoresist layer]

[0157] The present invention also provides a method for manufacturing a photoresist layer, comprising (3) applying a photoresist composition onto the isolation layer, and (4) heating the substrate to form a photoresist layer.

[0158] A photoresist composition is applied to an isolation layer manufactured as described above. The term "on the isolation layer" may indicate that the applied photoresist composition can be formed directly on the isolation layer, i.e., in direct contact with the upper side of the isolation layer, but it also includes the possibility that an intermediate layer can be inserted between the upper side of the isolation layer and the applied photoresist composition. Preferably, the applied photoresist composition is formed directly on the isolation layer.

[0159] The photoresist layer can be applied using known methods, such as spin coating. The applied photoresist composition is heated to remove the solvent from the composition, thus forming a photoresist layer. The heating temperature can vary depending on the composition to be used, but is preferably 70-150°C (more preferably 90-150°C, further preferably 100-140°C). On a heated plate, this can be performed for 10-180 seconds, preferably 30-90 seconds; or in a hot gas environment (e.g., in a clean oven), for 1 to 30 minutes. The formed photoresist layer preferably has a thickness of 0.40-5.00 micrometers (more preferably 0.40-3.00 micrometers, further preferably 0.50-2.00 micrometers). [Formation of photoresist patterns]

[0160] The present invention provides a method for manufacturing a photoresist pattern, comprising (5) exposing the photoresist layer and (6) developing the exposed layer to form a photoresist pattern.

[0161] The photoresist layer reacts under light / radiation exposure. Both positive and negative photoresist can be used. In the positive photoresist layer, the irradiated portion increases the solubility of the developer. Other layers (e.g., TARC) can be formed on this photoresist layer.

[0162] The photoresist layer is exposed through the provided mask. The wavelength of the light used for exposure is not particularly limited. The exposure is preferably performed with light having a wavelength of 13.5–365 nanometers (preferably 13.5–248 nanometers). KrF excimer laser (248 nanometers), ArF excimer laser (193 nanometers), or extreme ultraviolet light (13.5 nanometers) are preferred examples, with KrF excimer laser being more preferred. These wavelengths can vary within ±1%.

[0163] If necessary, heating can be performed following the exposure, also known as post-exposure baking (PEB). The temperature used for PEB is selected from the range of 80-150 ℃, preferably 90-140 ℃; and the heating time used for PEB is selected from the range of 0.3-5 minutes, preferably 0.5-2 minutes.

[0164] Next, development is performed using a developer. In the positive photoresist layer, the unexposed areas are removed by development, resulting in the formation of the photoresist pattern. An example of the developer is a 2.38% by mass (acceptable ±1% concentration variation) aqueous TMAH solution, but this is not intended to limit the scope of the invention. Additives such as surfactants can be added to the developer. The temperature of the developer is typically selected from the range of 5-50°C, preferably 25-40°C; and the development time is typically selected from the range of 10-300 seconds, preferably 30-90 seconds. As for the development method, known methods such as paddle development can be used.

[0165] After development, the photoresist pattern can be cleaned with water or a cleaning solution, such as by replacing the developer with water and / or a cleaning solution. The pattern can then be dried, for example, by a spin-drying method. [Etching]

[0166] The present invention provides a method for manufacturing a processed substrate, comprising (7) etching through the photoresist pattern as a mask, and (8) processing the substrate. This etching may form an intercalation layer and / or a pattern of the substrate. Known etching methods may be used, such as dry etching and wet etching (preferably dry etching). The term "intercalation layer" refers to a layer between the photoresist pattern and the substrate, comprising an isolation layer, an anti-reflective coating, and a spin-coated carbon coating. The pattern obtained from the intercalation layer may be used as a next mask to further process the underlying layer or substrate. Another embodiment of the present invention provides that the photoresist pattern may be used as a mask to process the isolation layer and the substrate in a single etching operation.

[0167] Wiring can be formed in the treated substrate.

[0168] The remaining layer / pattern on the substrate can be removed by known methods, such as dry etching of O2, CF4, CHF3, Cl2 or BCl3, preferably O2 or CHF3.

[0169] As for a specific example of the present invention, it is preferred to use CF4 or CHF3 (more preferably CHF3) to etch the anti-reflective coating, and then change the etching gas to O2 to etch the spin-coated carbon coating. [Equipment Manufacturing]

[0170] Subsequently, if necessary, the substrate is further processed to form a device. This further processing can be carried out using known methods. After the device is formed, if necessary, the substrate is diced into wafers, connected to a lead frame, and encapsulated in resin. Preferably, the device is a semiconductor device, a solar cell wafer, an organic light-emitting diode, or an inorganic light-emitting diode. A preferred embodiment of the device of the present invention is a semiconductor device. [Example]

[0171] The present invention will then be described using operational examples. These examples are provided for illustrative purposes only and are not intended to limit the scope of the invention. As used in the following description, unless otherwise stated, the term "parts" refers to parts by mass.

[0172] The Tokyo Electron Clean Track Act 8 was used for coating and baking of the samples.

[0173] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymer were measured by gel permeation chromatography (GPC) and corrected to polystyrene standards; and the degree of polymerization distribution (Mw / Mn) was calculated from them. [Preparation Example 1 of Composition 1]

[0174] Polymer C2-1 was prepared using the same method as described in US 9,274,426 (Synthesis of Polymer 1). The formulation was prepared by dissolving the following three materials in a mixture of PGMEA and PGME solvents. The formulation was heated to 50 °C and stirred for 4 hours.

[0175] 10% D-1 was prepared by dissolving decylbenzenesulfonic acid and triethylamine in a mixture of PGMEA and PGME. No heating was performed, but the mixture was stirred for 10 minutes. Then, while both solutions were at room temperature, this 10% D-1 was added to the other solutions described above.

[0176] Then, Di(PGMEA) and n-decyl acetate were added to the solution, along with silicate polymer 1. The solution was then heated to 50°C for 1 hour. The dissolution of the solute was visually confirmed. Once the formulation had cooled, it was filtered through a 0.2-micron polypropylene filter to obtain operational composition 1.

[0177] The mass percentage of each component and solvent in the solution is described in Table 1 below. [Table 1] Material percentage Polymer C2-1 4.49% C3-1 2.16% E-1 0.66% D-1 0.27% PGMEA 56.17% PGME 23.86% n-Decyl acetate 3.98% Di(PGMEA) 7.95% Silicon oxyalkane polymer 1 0.46% Total 100.00% [Preparation Examples of Compositions 2-7]

[0178] Except for changing silicone polymer 1 to silicone polymers 2, 3, 4, 5, 6 and 7 to obtain operational compositions 2, 3, 4, 5, 6 and 7, the same method as in preparation example 1 was used for preparation. [Synthetic Chemistry of Silicon Oxide Polymer 2]

[0179] Trimethoxy(methyl)silane (3.178 g; 23.330 mmol; 1.00 equivalent), tetraethyl orthosilicate (3.646 g; 17.500 mmol; 0.75 equivalent), 3-(trimethoxysilyl)propyl methacrylate (4.346 g; 17.500 mmol; 0.75 equivalent), and propan-2-ol (13.000 g; 216.324 mmol; 9.27 equivalent) were weighed directly (in air) into a 100 mL 3-necked RBF (round-bottom flask). The mixture was stirred in an ice-water bath until the temperature reached 0°C. A 25% tetramethylammonium hydroxide aqueous solution (4.120 g; 11.300 mmol; 0.48 equivalent) was added in portions over approximately 2 minutes. The reaction was slightly exothermic. After the addition, the temperature was increased to 10°C. Once the addition is complete, remove the ice bath. Stir the solution at 25°C (external) for 2 hours. The mixture should remain a clear, colorless solution. Add ethoxytrimethylsilane (5,000 mL; 31.493 mmol; 1.35 equivalents) and stir the mixture at 25°C for an additional 2 hours.

[0180] A 100 mL Erlenmeyer flask was filled with 33.6 g of deionized water, 1.200 g of hydrochloric acid (32%, 1.200 g; 11.519 mmol; 0.49 equivalents), and 16.800 g of n-propyl acetate (164.493 mmol; 7.05 equivalents). The reaction mixture in the RBF (a clear, colorless solution) was poured into the Erlenmeyer flask and stirred at 1,000 rpm to produce a white, turbulent solution. The mixture was stirred for 30 minutes. The mixture was transferred into a separatory funnel and allowed to stand for 10 minutes until complete phase separation occurred. The polymer was in the upper organic phase. The upper organic layer was slightly white and milky. The bottom aqueous phase (pH=1) was separated and discarded. 33.6 g of deionized water was added to the organic phase and the mixture was shaken thoroughly. 6.5 g of n-propyl acetate was added and the mixture was shaken, then left overnight. Separation did not occur. Add 6.5 grams of isopropanol. Remove and discard the bottom layer. Repeat the cleaning process again until the pH reaches 7.

[0181] First, the organic phase was rotary evaporated to 80 mbar, then 10 g of PGMEA was added. The mixture was further rotary evaporated to 23 mbar until a clear, colorless solution (13.5 g) was obtained. As a precaution, the solution was filtered through a syringe 0.45 μm filter. Molecular weight was determined by GPC extraction with THF (tetrahydrofuran). The solids content (150 °C, 30 min) was measured to be 48.4%. Mn Mw Mw / Mn 2426 5159 2.13 [Synthetic Chemistry of Silicon Oxide Polymer 3]

[0182] Trimethoxy(methyl)silane (3.178 g; 23.330 mmol; 1.00 equivalent), tetraethyl orthosilicate (3.646 g; 17.500 mmol; 0.75 equivalent), 2-methyl-N-[3-(trimethoxysilyl)propyl]prop-2-enylamine (4.329 g; 17.500 mmol; 0.75 equivalent), and propan-2-ol (13.000 g; 216.324 mmol; 9.27 equivalent) were weighed directly (in air) into a 100 mL three-necked round-bottom flask. The mixture was stirred at 600 rpm in an ice-water bath until the temperature reached 0 °C (internal temperature). A 25% tetramethylammonium hydroxide aqueous solution (4.120 g; 11.300 mmol; 0.48 equivalent) was added in portions over approximately 2 minutes. Before removing the cooling bath, stir the solution in the cooling bath for 15 minutes. Continue the reaction at room temperature for an additional 1 hour and 45 minutes. The mixture remains a clear, colorless solution (slightly pale yellow).

[0183] Add ethoxytrimethylsilane (5.000 mL; 31.493 mmol; 1.35 equivalence) at 25 °C and stir the mixture for an additional 4 hours. Charge a 100 mL Erlenmeyer flask with deionized water (33.6 g), hydrochloric acid (32%, 1.200 g; 11.519 mmol; 0.49 equivalence), and n-propyl acetate (16.800 g; 164.493 mmol; 7.05 equivalence). Pour the reaction mixture (clear, colorless solution) from the RBF into the Erlenmeyer flask while stirring at 1,000 rpm to produce a white turbulent solution. Stir the mixture for 30 minutes, then transfer it to a separatory funnel. Wait 10 minutes for complete phase separation to occur. Separate and discard the bottom aqueous phase (pH=5). Add deionized water (33.6 g) to the organic phase and shake well. Remove and discard the bottom phase (pH=7).

[0184] First, the organic phase was rotary evaporated to 80 mbar, then 9 g of PGMEA was added. The mixture was further rotary evaporated to 23 mbar until a clear, colorless solution (14.5 g) was obtained. As a precaution, the solution was filtered through a syringe 0.45-micron filter. The solids content (150 °C, 30 min) was 54%. The molecular weight was determined by GPC extraction with THF. Mn Mw Mw / Mn 1762 2633 1.49 [Synthetic Chemistry of Silicon Oxide Polymer 6]

[0185] Trimethoxy(methyl)silane (2.724 g; 20,000 mmol; 1.00 equivalent), tetraethyl orthosilicate (1.042 g; 5,000 mmol; 0.25 equivalent), 3,4-dimethyl-1-(3-triethoxysilylpropyl)pyrrole-2,5-dione (8.237 g; 25,000 mmol; 1.25 equivalent), and propan-2-ol (13,000 g; 216.324 mmol; 10.82 equivalent) were weighed directly (in air) into 100 mL of 3-necked RBF. The mixture was stirred at 600 rpm in an ice-water bath until the temperature reached 5 °C (internal temperature). Tetramethylammonium hydroxide (25% aqueous solution, 4.120 g; 11,300 mmol; 0.56 equivalent) was added dropwise over 3 minutes. The reaction is slightly exothermic, and the temperature increases by 5 to 10 °C after the addition. Once the addition is complete, remove the ice-water bath. The colorless solution is stabilized and stirred at 18 °C for 2 hours. Ethoxytrimethylsilane (5,000 mL; 31.493 mmol; 1.57 equivalents) is added all at once at room temperature. The solution is stirred for an additional 2 hours.

[0186] A 100 mL Erlenmeyer flask was filled with deionized water (33.6 g), hydrochloric acid (32%, 1.240 g; 11.903 mmol; 0.60 equivalent), and n-propyl acetate (16.800 g; 164.493 mmol; 8.22 equivalent). The reaction mixture in the RBF (a clear, colorless solution) was poured into the Erlenmeyer flask while stirring at 1,000 rpm to produce a white turbulent solution. The mixture was stirred for 0.5 h and then transferred to a separatory funnel. 20 minutes were allowed for complete phase separation. The polymer was in the upper organic phase. The bottom aqueous phase (pH=6) was separated and discarded. Deionized water (33.6 g) and propan-2-ol (6.5 g) were added to the organic phase and shaken thoroughly. Phase separation occurred within 10 minutes. The bottom phase (pH=7) was then removed and discarded. PGMEA (17 g) was added to the organic phase and the mixture was rotary evaporated to 4 mbar until a pale yellow viscous solution (10.6 g) was obtained. The solids content (150 °C, 30 min) was 59%. The molecular weight was determined by GPC extraction with THF. Mn Mw Mw / Mn 1707 2490 1.46 [Synthetic Chemistry of Silicon Oxide Polymer 7]

[0187] Diethoxydimethylsilane (2.966 g; 20,000 mmol; 2.00 equivalent), diethoxymethylvinylsilane (3.206 g; 20,000 mmol; 2.00 equivalent), and dimethoxy[4-(methoxymethoxy)phenyl]methylsilane (2.423 g; 10,000 mmol; 1.00 equivalent) were weighed directly (in air) into a 25 mL round-bottom flask. All of the mixture was added at once in the form of Ambersep® 900 hydroxide (2.500 g; 27.427 mmol; 2.74 equivalent), and the mixture was stirred at 30 °C for 18 hours, then at 50 °C for 48 hours. The temperature was increased to 80 °C and stirred for 30 hours, then cooled to room temperature, and then diethyl ether (10 mL) was added. The mixture was filtered through a 0.45 μm syringe filter. The filtrate was rotary evaporated until dried to maximum vacuum (10 mbar, 50 °C) to produce a concentrated pale yellow oil (3.86 g). The molecular weight was determined by GPC extraction with THF. Mn Mw Mw / Mn 6764 17118 2.53 [Substrate Preparation]

[0188] Each component was spin-coated onto a CZ-Si wafer. The spin conditions were 500 rpm for 10 seconds, then 1,500 rpm for 60 seconds, with an acceleration of 500 rpm.

[0189] Then, the wafer is heated at 70°C for 2 minutes on a heating plate. The wafer is then transferred to another heating plate and heated at 150°C for 10 minutes, then at 250°C for 1 minute and at 350°C for 2 minutes. [Uniformity Assessment]

[0190] The macroscopic film exhibits excellent uniformity across each Si wafer. No defects or color gradients are visible to the naked eye. Cross-sectional SEM reveals the absence of material degassing, voids, or defects. Atomic force microscopy (AFM) imaging shows good nanomorphology and a uniform phase across an area of ​​20 square micrometers. Surface roughness is <2-4 nanometers. [Contact Angle Assessment]

[0191] The contact angle was evaluated using the components listed in the table below. The comparative composition SOC was prepared using the same method as in Preparation Example 1, except that no silicone polymer was used. The substrate was prepared using the same method as described above.

[0192] The measurement system used a camera to record the contact angle of a pure water droplet on the surface of a coated wafer. The measurement was repeated at six different locations across the surface. The results showed that phase separation was driven, allowing the silica-rich interface to reach the upper surface. [Table 2] Membranes prepared by the following methods Contact angle (°) Operational Component 1 85±1 Operational Component 2 82±2 Operational Component 3 90±2 Operational Component 4 93±2 Operational Component 5 85±1 Operational Component 6 92±1 Comparison of composition SOC 69±5 [Silicone content assessment]

[0193] Silicon content was assessed using X-ray photoelectron spectroscopy (XPS) for each substrate. First, the content at the surface (0 nm) was examined. Then, CHF3 etching was performed, and the silicon content was continuously assessed. The results are shown in Figure 1. The results show that the silicon-rich interface has a reduced silicon content at depths throughout the film. [Preparation Example 8 of Composition 8]

[0194] Silicon oxane polymer 7 and D-1 (100:20.63, by mass) were dissolved in PGMEA to prepare a 15% by mass solution. The solution was then heated to 50°C for 1 hour. The dissolution of the solutes was visually confirmed. Once the formulation had cooled, it was filtered through a 0.2-micron polypropylene filter to obtain operational composition 8. [Soluble Resistance Assessment]

[0195] The working composition 8 was spin-coated onto a glass substrate at 500 rpm for 10 seconds, followed by 1,000 rpm for 30 seconds. The substrate was then dried on a hot plate at 100°C for 2 minutes. Next, the substrate was heated on a hot plate at 350°C for 5 minutes. The thickness of the resulting coating was measured using a profilometer. The substrate was then covered with PGMEA for 2 minutes. The volume was such that the surface tension of the PGMEA would retain the solvent on the substrate and prevent it from spreading to the edges. The substrate was then spin-coated at 1,500 rpm for 10 seconds and heated to 100°C for 2 minutes to remove any residual solvent. The thickness was again measured using a profilometer. The film retention was 98%. [Thermogravimetric Analysis]

[0196] The substrate was weighed. Composition 8 was rotary coated onto the glass substrate at 500 rpm for 10 seconds, then 1,000 rpm for 30 seconds, and the film was dried by baking at 70°C for 2 minutes. The substrate with the coating was then weighed. The substrate was heated from 30°C to 150°C by increasing the temperature by 40°C per minute. It was then held at 150°C for 10 minutes. Then, it was heated from 150°C to 250°C by increasing the temperature by 40°C per minute and held at 250°C for 2 minutes. Then, it was heated from 250°C to 350°C by increasing the temperature by 40°C per minute and held at 350°C for 2 minutes. The mass loss % was negatively correlated with the Mw of the siloxane. After these conditions, the film retention was 96% by mass.

[0197] none.

Claims

1. A method for manufacturing an isolation layer on a substrate, comprising: (1) applying a composition to the substrate, wherein the composition comprises a solvent (A), a silicate polymer (B), and a high-carbon material (C); and (2) heating the substrate to form an isolation layer comprising an antireflective coating derived from the silicate polymer (B) and a spin-coated carbon coating derived from the high-carbon material (C), wherein the antireflective coating, the spin-coated carbon coating, and the substrate are arranged in this order.

2. The method of claim 1, wherein the composition is isolated as the antireflective coating and the spin-coated carbon coating.

3. The method of claim 1 or 2, wherein the siloxane polymer (B) comprises at least one unit selected from the group consisting of unit B1, unit B2 and unit B3; each of unit B1, unit B2 and unit B3 is represented by formula B1, formula B2 and formula B3:

3. Ah11 series C1-5 aliphatic hydrocarbons; R12 series -Ah12, -O-Ah12, -O-*, -Si(H)p12(Ah12)q12, -O-Si(H)p12(Ah12)q12, or single bonds to other units; Ah12 series C1-5 aliphatic hydrocarbons; p12=0, 1, 2 or 3; q12=0, 1, 2 or 3; p12+q12=3; L11 series single bonds or -O-; and n11 series number of repetitions of unit B1; 3. R21 series: -Ah21, -O-Ah21, -O-*, -Si(H)p21(Ah21)q21, -O-Si(H)p21(Ah21)q21, or single bonds connected to other units; R22 series: -Ah22, -O-Ah22, -O-*, -Si(H)p22(Ah22)q22, -O-Si(H)p22(Ah22)q22, or single bonds connected to other units; Ah21 and Ah22 are each independently C1-5 aliphatic hydrocarbons; p21, p22, q21 and q22 are each independently 0, 1, 2 or 3; p21+q21=p22+q22=3; L21 series: single bonds or -O-; and n21 series: the number of repetitions of unit B2; 3. R31 series -Ah31, -O-Ah31, -O-*, -Si(H)p31(Ah31)q31, -O-Si(H)p31(Ah31)q31, or single bonds connected to other units; Ah31 series C1-5 aliphatic hydrocarbons; p31=0, 1, 2 or 3; q31=0, 1, 2 or 3; p31+q31=3; R32 is a group consisting of at least two groups and / or linkers selected from the group consisting of: phenyl, phenylene, -O-, -(C=O)-, -COO-, -COOH, -NH-, C1-5 aliphatic hydrocarbon group and C1-5 aliphatic hydrocarbon linker; L31 is a single bond or -O-; and n31 is the number of repetitions of unit B3; 0%n11 / (n11+n21+n31)80%, 0%n21 / (n11+n21+n31)80% and 0%n31 / (n11+n21+n31)80%.

4. The method of claim 1 or 2, wherein the number of atoms in the spin-coated carbon coating satisfies the following formula C1; 1.5 {total number of atoms / (number of C atoms - number of O atoms)} 3.5 Formula C1; wherein the number of C atoms is the number of carbon atoms in the total number of atoms, and the number of O atoms is the number of oxygen atoms in the total number of atoms.

5. The method of claim 1 or 2, wherein the high-carbon material (C) comprises at least one selected from the group consisting of unit C2, molecule C3 and unit C4, each of which is represented by the formula C2, C3 and C4; 5. Among them, Ar41 series refers to unsubstituted or R41-substituted C6-60 hydrocarbons; R41 series refers to linear, branched or cyclic C1-20 alkyl, amino or alkylamino groups; R42 series refers to I, Br or CN; p41 series refers to the number of 0-5, p42 series refers to the number of 0-1, q41 series refers to the number of 0-5, q42 series refers to the number of 0-1, r41 series refers to the number of 0-5, and s41 series refers to the number of 0-5.

5. Ar51 refers to single bonds, C1-6 alkyl, C6-12 cycloalkyl, or C6-14 aryl groups; Ar52 refers to C1-6 alkyl, C6-12 cycloalkyl, or C6-14 aryl groups; R51 and R52 are each independently C1-6 alkyl, hydroxyl, halogen, or cyano groups; R53 refers to hydrogen, C1-6 alkyl, or C6-14 aryl groups; Ar52 refers to C1-6 alkyl or C6-14 aryl groups and R53 refers to C1-6 alkyl or C6-14 aryl groups. In this case, Ar52 and R53 can bond together to form a hydrocarbon ring; r51 and r52 are each an integer from 0 to 5; Cy51, Cy52 and Cy53 rings enclosed by dashed lines can selectively and independently form aromatic rings fused with adjacent aromatic ring Ph51; Cy54, Cy55 and Cy56 rings enclosed by dashed lines can selectively and independently form aromatic rings fused with adjacent aromatic ring Ph52.

5. R61 refers to hydrogen, C1-6 alkyl, halogen, or cyano; R62 refers to C1-6 alkyl, halogen, or cyano; p61 refers to the number of repetitions, and p62 refers to integers from 0 to 5.

6. The method of claim 1 or 2, wherein the composition further comprises a hot acid generating agent (D) and / or a crosslinking agent (E).

7. The method of claim 1 or 2, wherein the solvent (A) comprises an organic solvent.

8. The method of claim 1 or 2, wherein the mass ratio of the solvent (A) is 60-99 by mass, based on the total mass of the composition.

9. The method of claim 1 or 2, wherein the heating system of (2) is carried out at 20-450°C for 0.1-30 minutes.

10. The method of claim 1 or 2, wherein the component is essentially composed of isolated components.

11. A method of manufacturing a photoresist layer, comprising: (3) applying a photoresist composition onto an isolation layer manufactured by one or more of claims 1 to 10; and (4) heating the substrate to form the photoresist layer.

12. A method of manufacturing a photoresist pattern, comprising: (5) exposing a photoresist layer manufactured as claimed in claim 11; and (6) developing the exposed photoresist layer to form a photoresist pattern.

13. A method of manufacturing a treated substrate, comprising: (7) etching by means of a photoresist pattern manufactured as claimed in claim 12 as a mask; and (8) treating the substrate.

14. A method of manufacturing an apparatus comprising using a substrate manufactured as claimed in claim 13.

15. The method of manufacturing apparatus as claimed in claim 14 further includes forming wiring in the treated substrate.

16. A composition for a self-isolating anti-reflective coating and a spin-coated carbon coating, comprising a solvent (A), a silicate polymer (B), and a high-carbon material (C).

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