Adhesive film-forming composition, method for forming pattern, and method for forming adhesive film

Abstract

To provide a composition for forming an adhesive film that provides good coating properties even on a hydrophobic underlying layer in a fine patterning process using a multilayer resist method in semiconductor device manufacturing, while also offering excellent pattern collapse suppression performance and the ability to remove resist residues at the bottom of the pattern, a pattern formation method using the composition, and a method for forming the adhesive film.SOLUTION: An adhesive film-forming composition, comprising (A) a resin containing repeating units represented by the general formula (1) below and repeating units having an organic sulfonyl anion structure, and (B) an organic solvent.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a composition for forming an adhesion film, a pattern forming method using the composition for forming an adhesion film, and a method for forming an adhesion film using the composition for forming an adhesion film. [Background technology]

[0002] As LSIs become more highly integrated and faster, pattern dimensions are becoming increasingly miniaturized. Lithography technology has achieved this by shortening the wavelength of light sources and selecting appropriate resist compositions to match. Single-layer positive photoresist compositions have become a key enabler. These single-layer positive photoresist compositions incorporate a backbone that provides etching resistance to dry etching using chlorine- or fluorine-based gas plasmas, and also incorporate a resist mechanism that dissolves exposed areas. This allows the exposed areas to be dissolved to form a pattern, and the remaining resist pattern is then used as an etching mask to dry etch a substrate coated with the photoresist composition.

[0003] However, if the thickness of the photoresist film used remains the same and the pattern width is made smaller, the resolution of the photoresist film will decrease, and if an attempt is made to develop the photoresist film into a pattern using a developer, the so-called aspect ratio will become too large, resulting in pattern collapse. For this reason, the thickness of the photoresist film has been made thinner as the pattern becomes smaller.

[0004] On the other hand, processing of substrates is typically performed by dry etching using a patterned photoresist film as an etching mask. However, in reality, there is no dry etching method that can achieve complete etching selectivity between the photoresist film and the substrate. Therefore, the photoresist film is also damaged during processing of the substrate, causing the photoresist film to collapse during processing, making it impossible to accurately transfer the resist pattern to the substrate. Therefore, with the trend toward finer patterns, photoresist compositions are required to have higher dry etching resistance. Furthermore, as exposure wavelengths become shorter, resins used in photoresist compositions with low light absorption at the exposure wavelength are required. In response to the shift to i-line, KrF, and ArF, novolac resins, polyhydroxystyrene, and resins with aliphatic polycyclic skeletons have been used. However, in reality, the etching rates under these dry etching conditions have become faster, and recent photoresist compositions with high resolution tend to have weaker etching resistance.

[0005] This means that substrates to be processed must be dry etched using thinner photoresist films with weaker etching resistance, and there is an urgent need to secure the materials and processes required for this processing step.

[0006] One method for solving these problems is the multilayer resist method, in which a resist intermediate film having etching selectivity different from that of a photoresist film (i.e., a resist top layer film) is interposed between the resist top layer film and the substrate to be processed, a pattern is formed on the resist top layer film, and then the pattern is transferred to the resist intermediate film by dry etching using the resist top layer film pattern as a dry etching mask, and the pattern is then transferred to the substrate to be processed by dry etching using the resist intermediate film as a dry etching mask.

[0007] One type of multilayer resist method is the three-layer resist method, which can be performed using a typical resist composition used in the single-layer resist method. In this three-layer resist method, for example, an organic film such as novolak is formed on a substrate to be processed as a resist underlayer, a silicon-containing film is formed on top of that as a silicon-containing resist intermediate layer, and a conventional organic photoresist film is formed on top of that as a resist upper layer. When dry etching is performed using fluorine-based gas plasma, the organic resist upper layer has a good etching selectivity relative to the silicon-containing resist intermediate layer, so the resist upper layer pattern is transferred to the silicon-containing resist intermediate layer by dry etching using fluorine-based gas plasma. Furthermore, when etching using oxygen gas or hydrogen gas, the silicon-containing resist intermediate layer has a good etching selectivity relative to the resist underlayer, so the silicon-containing resist intermediate layer pattern is transferred to the resist lower layer by etching using oxygen gas or hydrogen gas. According to this method, even if a photoresist composition that is difficult to form a pattern with a sufficient film thickness for directly processing a substrate to be processed or a photoresist composition that does not have sufficient dry etching resistance for processing a substrate is used, it is possible to transfer a pattern to a silicon-containing film (silicon-containing resist intermediate film), and obtain a pattern of an organic film (resist underlayer film) made of novolak or the like that has sufficient dry etching resistance for processing.

[0008] In recent years, vacuum ultraviolet (EUV) lithography with a wavelength of 13.5 nm has been attracting attention as a promising alternative to the combined use of ArF immersion lithography and multiple exposure processes. Using this technology, it has become possible to form fine patterns with a half pitch of 25 nm or less in a single exposure.

[0009] On the other hand, in EUV lithography, high sensitivity is strongly required for resist materials to compensate for the insufficient output of the light source. However, the increase in shot noise that accompanies high sensitivity leads to an increase in line edge roughness (LER, LWR) of the line pattern, and achieving both high sensitivity and low edge roughness has been cited as one of the important challenges in EUV lithography.

[0010] In recent years, the use of metallic materials in resist materials has been investigated as an attempt to increase the sensitivity of resist materials and reduce the impact of shot noise. Compounds containing metal elements such as barium, titanium, hafnium, zirconium, and tin have higher absorbance to EUV light than organic materials that do not contain metals, and are expected to improve the photosensitivity of resists and suppress the impact of shot noise. Furthermore, metal-containing resist patterns can be combined with a resist underlayer film made of a non-metallic material, which is expected to enable high-selectivity etching.

[0011] For example, resist materials containing added metal salts or organometallic complexes (Patent Documents 1 and 2) and non-chemically amplified resist materials using metal oxide nanoparticles (Patent Documents 3 and 4, Non-Patent Document 1) have been investigated. However, the resolution of these metal-containing resists has not yet reached the level required for practical use, and further improvement in resolution is required.

[0012] Furthermore, with the advent of ArF immersion lithography and EUV lithography, it is becoming possible to form even finer patterns, but on the other hand, ultra-fine patterns have a small contact area, making them extremely susceptible to collapse, and suppressing pattern collapse is a major challenge.On the other hand, resist residue at the bottom of the pattern due to insufficient light source output has begun to have a negative impact on the process.

[0013] As miniaturization increases, the difficulty of patterning increases, and as the structures of semiconductor devices become more complex, the manufacturing processes also become more diverse, making it necessary to perform lithography on a variety of underlayer films. Attempts have been made to form a resist adhesion film directly under the resist top layer to improve pattern adhesion and remove residue at the bottom of the pattern, but forming an adhesion film itself becomes difficult, especially when the underlayer film is highly hydrophobic.

[0014] To prevent pattern collapse, examples have been reported in which a resist underlayer film containing a polar functional group such as a lactone structure or a urea structure is used to improve adhesion to the resist overlayer film (Patent Documents 4 and 5), or to improve the rectangularity of the resist pattern (Patent Documents 6 and 7). However, these materials were unable to be formed on a hydrophobic underlayer film, or even if they could be formed, their ability to prevent collapse and to remove resist residue at the bottom of the pattern was insufficient. [Prior art documents] [Patent documents]

[0015] [Patent Document 1] Patent No. 5708521 [Patent Document 2] Patent No. 5708522 [Patent Document 3] U.S. Patent No. 9,310,684 [Patent Document 4] International Publication No. 2003 / 017002 [Patent Document 5] International Publication No. 2018 / 143359 [Patent Document 6] Japanese Patent Publication No. 2023-094359 [Patent Document 7] Japanese Patent Application Publication No. 2024-027459 [Non-patent literature]

[0016] [Non-Patent Document 1] Proc.SPIE Vol.7969,796915(2011) Summary of the Invention [Problem to be solved by the invention]

[0017] The present invention has been made in consideration of the above circumstances, and aims to provide a composition for forming an adhesion film that, in a fine patterning process using a multilayer resist method in a semiconductor device manufacturing process, provides an adhesion film that exhibits good coatability even on a hydrophobic underlayer film, while at the same time having good pattern collapse suppression performance and the ability to remove resist residue at the bottom of the pattern, a pattern formation method using the composition, and a method for forming the adhesion film. [Means for solving the problem]

[0018] In order to solve the above problems, the present invention provides a composition for forming an adhesion film, comprising: (A) a resin containing a repeating unit represented by the following general formula (1) and a repeating unit having an organic sulfonyl anion structure, and (B) an organic solvent, The present invention provides a composition for forming an adhesion film, which comprises: [ka] (wherein X is a single bond or an aromatic ring having 20 or less carbon atoms, and R 01 is a hydrogen atom or a methyl group, and R 02 is a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms, and R 02 When is an alkyl group, a hydrogen atom constituting the alkyl group may be substituted with a hydroxyl group.

[0019] Such a composition for forming an adhesion film can ensure good coating properties even on a hydrophobic underlayer film, and can remove residues at the bottom of the resist without increasing pattern roughness.

[0020] In the present invention, it is preferable that the ratio of the repeating units represented by the general formula (1) in the repeating units of the resin (A) is 70 mol % or more and 99.9 mol % or less.

[0021] Furthermore, in the present invention, it is preferable that the ratio of the repeating units having the organic sulfonyl anion structure in the repeating units of the resin (A) is 0.1 mol % or more and 30 mol % or less.

[0022] Such a composition for forming an adhesion film can ensure good coatability on various underlayer films and can remove residues at the bottom of the resist without increasing pattern roughness.

[0023] In the present invention, the weight average molecular weight of the (A) resin is preferably 1,000 to 70,000.

[0024] Such a composition for forming an adhesive film has excellent film-forming properties, and can suppress the generation of sublimates during heat curing, thereby preventing contamination of the device due to the sublimates.

[0025] In the present invention, the (B) organic solvent is preferably a mixture of one or more organic solvents having a boiling point of less than 150°C and one or more organic solvents having a boiling point of 150°C or higher and lower than 220°C.

[0026] Such a composition for forming an adhesion film has sufficient solvent solubility, and therefore, the occurrence of coating defects can be suppressed.

[0027] In the present invention, it is preferable that the composition further contains one or more selected from (C) a thermal acid generator, (D) a surfactant, and (E) a crosslinking agent.

[0028] The presence or absence / selection of these various additives makes it possible to fine-tune performance in accordance with customer requirements, such as film-forming properties, embedding properties, optical properties, and reduction of sublimation products, which is preferable from a practical standpoint.

[0029] The present invention also provides a method for forming a pattern on a substrate to be processed, comprising the steps of: (I-1) A step of applying the above-described composition for forming an adhesion film onto a substrate to be processed, followed by heat treatment to form an adhesion film; (I-2) forming a resist upper layer film on the adhesion film using a photoresist material; (I-3) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (I-4) a step of transferring the pattern to the adhesive film by dry etching using the resist upper layer film on which the circuit pattern is formed as a mask; and (I-5) a step of processing the substrate to be processed using the resist top layer film and / or adhesive film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed; The present invention provides a pattern forming method comprising the steps of:

[0030] The present invention also provides a method for forming a pattern on a substrate to be processed, comprising the steps of: (II-1) forming a resist underlayer film on a substrate to be processed; (II-2) forming a silicon-containing resist intermediate film on the resist underlayer film; (II-3) A step of applying the above-described composition for forming an adhesion film onto the silicon-containing resist intermediate film, followed by heat treatment to form an adhesion film; (II-4) forming a resist upper layer film on the adhesion film using a photoresist material; (II-5) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (II-6) a step of transferring the pattern to the adhesive film by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask; (II-7) a step of transferring the pattern to the silicon-containing resist intermediate film by dry etching using the resist upper layer film and / or adhesive film on which the pattern has been formed as a mask; (II-8) a step of transferring a pattern to the resist underlayer film by dry etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; and (II-9) a step of processing the substrate to be processed using the resist underlayer film to which the pattern has been transferred as a mask to form a pattern on the substrate to be processed; The present invention provides a pattern forming method comprising the steps of:

[0031] The present invention also provides a method for forming a pattern on a substrate to be processed, comprising the steps of: (III-1) forming a resist underlayer film on a substrate to be processed; (III-2) forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist underlayer film; (III-3) A step of applying the above-described composition for forming an adhesion film onto the inorganic hard mask intermediate film, followed by heat treatment to form an adhesion film; (III-4) forming a resist upper layer film on the adhesion film using a photoresist material; (III-5) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (III-6) a step of transferring the pattern to the adhesive film by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask; (III-7) a step of transferring a pattern onto the inorganic hard mask intermediate film by dry etching using the resist upper layer film and / or adhesive film on which the pattern has been formed as a mask; (III-8) transferring a pattern to the resist underlayer film by dry etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; and (III-9) a step of processing the substrate to be processed using the resist underlayer film to which the pattern has been transferred as a mask to form a pattern on the substrate to be processed; The present invention provides a pattern forming method comprising the steps of:

[0032] As described above, the composition for forming an adhesion film of the present invention can be suitably used in various pattern formation methods, such as a two-layer resist process or a four-layer resist process in which the adhesion film is formed on a silicon-containing intermediate film (silicon-containing resist intermediate film, inorganic hard mask intermediate film), and these pattern formation methods are suitable for photolithography of a resist upper layer film.

[0033] In this case, it is preferable that the inorganic hard mask intermediate film is formed by a CVD method or an ALD method.

[0034] In the present invention, the method for forming a circuit pattern on the resist upper layer film is preferably photolithography with a wavelength of 10 nm or more and 300 nm or less, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[0035] Furthermore, in the present invention, it is more preferable to use a photoresist material containing at least an organometallic compound and a solvent.

[0036] In the present invention, it is preferable to use alkaline development or development with an organic solvent as the development method.

[0037] In the present invention, by using the pattern formation method as described above, pattern formation can be carried out well and efficiently.

[0038] In addition, in the present invention, it is preferable to use, as the substrate to be processed, a semiconductor device substrate or a semiconductor device substrate having any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal carbide oxide film, and a metal oxynitride film formed thereon.

[0039] In this case, it is preferable to use silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or an alloy thereof as the metal.

[0040] According to the pattern forming method of the present invention, a pattern can be formed by processing the above-described substrate to be processed in the above-described manner.

[0041] The present invention also provides a method for forming an adhesion film used in the manufacturing process of a semiconductor device, which comprises spin-coating the above-described composition for forming an adhesion film on a substrate to be processed, and heat-treating the substrate coated with the composition for forming an adhesion film at a temperature of 100°C or higher and 300°C or lower for 10 to 600 seconds to form an adhesion film.

[0042] The present invention also provides a method for forming an adhesion film used in the manufacturing process of a semiconductor device, which comprises spin-coating the above-described composition for forming an adhesion film on a substrate to be processed, and heat-treating the substrate coated with the composition for forming an adhesion film in an atmosphere having an oxygen concentration of 0.1% or more and 21% or less, thereby forming an adhesion film.

[0043] By this method, the crosslinking reaction during the formation of the adhesive film can be promoted, and mixing with the resist upper layer film can be more effectively suppressed. In addition, by appropriately adjusting the heat treatment temperature, time, and oxygen concentration within the above ranges, it is possible to obtain an effect of suppressing pattern collapse of the adhesive film suitable for the application, and to obtain pattern shape adjustment properties of the resist upper layer film.

[0044] The present invention also provides a method for forming an adhesion film used in the manufacturing process of a semiconductor device, which comprises spin-coating the above-described composition for forming an adhesion film on a substrate to be processed, and heat-treating the substrate coated with the composition for forming an adhesion film in an atmosphere having an oxygen concentration of 0.0001% or more and less than 0.1%, thereby forming an adhesion film.

[0045] This method is useful because it promotes the crosslinking reaction during the formation of the adhesive film without causing deterioration of the substrate, even when the substrate contains a material that is unstable when heated in an oxygen atmosphere, and it can more effectively suppress intermixing with the overlying film. [Effects of the Invention]

[0046] As described above, the present invention can provide a composition for forming an adhesion film that has good coatability on various underlayer films. Furthermore, since this composition for forming an adhesion film can remove residues at the bottom of the resist without deteriorating the roughness of the resist pattern, it is extremely useful in multilayer resist processes, such as a four-layer resist process in which the adhesion film is formed on a silicon-containing resist intermediate film. Furthermore, the adhesion film forming method of the present invention can form an adhesion film that is sufficiently cured on the substrate to be processed and has high adhesion to the resist upper layer film. Furthermore, the pattern forming method of the present invention can form a fine pattern on the substrate to be processed with high precision in a multilayer resist process. [Brief explanation of the drawings]

[0047] [Figure 1] 1A to 1C are explanatory diagrams illustrating an example of a pattern formation method using a four-layer resist process according to the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0048] When an element is said herein to be "directly below" another element, it is in direct contact with the other element and there are no intervening elements present. In contrast, when an element is said to be "below" another element, there may be intervening elements between them. Similarly, when an element is said to be "directly above" another element, it is in direct contact with the other element and there are no intervening elements present, and when an element is said to be "on" another element, there may be intervening elements between them.

[0049] As described above, in the fine patterning process using the multilayer resist method in the semiconductor device manufacturing process, there has been a demand for a composition for forming an adhesion film that has good coatability on various underlayer films and is capable of removing residues at the bottom of the resist without deteriorating the roughness of the resist pattern, a pattern formation method using the composition, and a method for forming an adhesion film.

[0050] As a result of extensive research into the above-mentioned problems, the inventors have found that the above-mentioned problems can be solved by a composition for forming an adhesion film containing a resin of a specific structure, a pattern formation method using this composition for forming an adhesion film, and a method for forming an adhesion film using this composition for forming an adhesion film, and have thus completed the present invention.

[0051] That is, the present invention provides a composition for forming an adhesion film, (A) a resin containing a repeating unit represented by the following general formula (1) and a repeating unit having an organic sulfonyl anion structure, and (B) an organic solvent, The adhesive film-forming composition comprises: [ka] (wherein X is a single bond or an aromatic ring having 20 or less carbon atoms, and R 01 is a hydrogen atom or a methyl group, and R 02 is a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms, and R 02 When is an alkyl group, a hydrogen atom constituting the alkyl group may be substituted with a hydroxyl group.

[0052] The present invention will be described in detail below, but the present invention is not limited thereto.

[0053] [Adhesion film forming composition] The present invention provides a composition for forming an adhesion film, which comprises (A) a resin containing a repeating unit represented by the following general formula (1) and a repeating unit having an organic sulfonyl anion structure, and (B) an organic solvent. [ka] (wherein X is a single bond or an aromatic ring having 20 or less carbon atoms, and R 01 is a hydrogen atom or a methyl group, and R 02 is a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms, and R 02 When is an alkyl group, a hydrogen atom constituting the alkyl group may be substituted with a hydroxyl group.

[0054] In the composition for forming an adhesion film of the present invention, the (A) resin may be used alone or in combination of two or more. Furthermore, the composition for forming an adhesion film may contain components other than the components (A) and (B). Each component will be described below.

[0055] [(A) Resin] The resin (A) contained in the composition for forming an adhesion film of the present invention contains a repeating unit represented by the following general formula (1) and a repeating unit having an organic sulfonyl anion structure. [ka] (wherein X is a single bond or an aromatic ring having 20 or less carbon atoms, and R 01 is a hydrogen atom or a methyl group, and R 02 is a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms, and R 02 When is an alkyl group, a hydrogen atom constituting the alkyl group may be substituted with a hydroxyl group.

[0056] The structural unit represented by the general formula (1) functions as a crosslinking group and an adhesive group to the underlayer. Because it contains a nitrogen-hydrogen bond that acts as a hydrogen bond donor, it efficiently forms hydrogen bonds even on the hydrophobic underlayer film, thereby suppressing the occurrence of coating errors. Meanwhile, because this structural unit itself has crosslinking properties, the curability of the film is not impaired even if a large amount of this unit is introduced into the resin.

[0057] In the general formula (1), X is a single bond or an aromatic ring having 20 or less carbon atoms, and is preferably a single bond, a benzene ring, or a naphthalene ring. By using a structure with a relatively small molecular weight as described above, the number of hydrogen bond donors per unit molecular weight increases, resulting in excellent coatability on hydrophobic surfaces.

[0058] In the above general formula (1), R 01 is a hydrogen atom or a methyl group. However, when X is an aromatic ring, from the viewpoint of polymerization reactivity during raw material synthesis, R 01is preferably a hydrogen atom. When X is a single bond, R 01 Whether the group is a hydrogen atom or a methyl group, the polymerization reactivity during raw material synthesis is sufficient, and the polymerization reactivity can be suitably adjusted by selecting this structure.

[0059] In the above general formula (1), R 02 is a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms, and R 02 When R is an alkyl group, a hydrogen atom constituting the alkyl group may be substituted with a hydroxyl group. 02 is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.

[0060] R in the above general formula (1) 02 Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, a cyclopentyl group, a cyclohexyl group, and organic groups in which a hydrogen atom constituting these alkyl groups has been substituted with a hydroxyl group.

[0061] In the above general formula (1), OR 02 The structure is released during baking, generating carbocations. These carbocations react with other structures and bond, resulting in cross-linking. 02 By making R have a small molecular weight structure, it is possible to suppress film shrinkage during baking, and to prevent coating errors during baking. 02 If the molecular weight of R is made larger, the resin structure becomes bulkier, which increases the viscosity of the resin during application, and it is possible to suppress the occurrence of application errors during spin drying. 02is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.

[0062] Preferred examples of the repeating unit represented by the general formula (1) include the following structures: 01 is the same as above.

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] Furthermore, the presence of an organic sulfonyl anion structure in the resin generates an acid derived from the organic sulfonyl anion structure on the surface of the underlayer film, which contributes to the removal of residues at the bottom of the resist film. Meanwhile, since this acid is bonded to the resin in the composition for forming an adhesion film, the diffusion length is extremely short and the adverse effect on pattern roughness is minimal.

[0067] In addition, known structural units having an organic sulfonyl anion structure can be suitably used. For example, the anion of a monomer that gives an organic sulfonyl anion structure can be one having the structure shown below, but is not limited thereto. In the following formula, R A are each independently a hydrogen atom or a methyl group, and X BI are each independently an iodine atom, a bromine atom, or a fluorine atom.

[0068] [ka]

[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0080]

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[0081]

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[0082]

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[0083]

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[0085]

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[0086]

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[0088]

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[0089]

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[0090]

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[0091]

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[0093]

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[0097]

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[0098]

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[0100]

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[0101] [ka]

[0102] [ka]

[0103] [ka]

[0104] [ka]

[0105] [ka]

[0106] [ka]

[0107] [ka]

[0108] [ka]

[0109] Counter cations of the above anions may include known ammonium cations, sulfonium cations, and iodonium cations, such as, but not limited to, those having the structures described in paragraphs

[0043] to

[0045] of Japanese Patent No. 5415982 and those having the structures described below.

[0110] The sulfonium cation is preferably one represented by the following general formula (2), and the iodonium cation is preferably one represented by the following general formula (3). [ka]

[0111] In the above general formulas (2) and (3), R 4 ~R 8 are each independently a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom.

[0112] R 4 ~R 8 Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0113] R 4 ~R 8The hydrocarbyl group having 1 to 20 carbon atoms represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl groups; cyclic saturated hydrocarbyl groups having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl groups; alkenyl groups having 2 to 20 carbon atoms, such as vinyl, propenyl, butenyl, and hexenyl groups; and ethynyl groups. alkynyl groups having 2 to 20 carbon atoms such as a cyclohexenyl group, a propynyl group, or a butynyl group; cyclic unsaturated hydrocarbyl groups having 3 to 20 carbon atoms such as a cyclohexenyl group or a norbornenyl group; aryl groups having 6 to 20 carbon atoms such as a phenyl group, a methylphenyl group, an ethylphenyl group, an n-propylphenyl group, an isopropylphenyl group, an n-butylphenyl group, an isobutylphenyl group, a sec-butylphenyl group, a tert-butylphenyl group, a naphthyl group, a methylnaphthyl group, an ethylnaphthyl group, an n-propylnaphthyl group, an isopropylnaphthyl group, an n-butylnaphthyl group, an isobutylnaphthyl group, a sec-butylnaphthyl group, or a tert-butylnaphthyl group; aralkyl groups having 7 to 20 carbon atoms such as a benzyl group or a phenethyl group; and groups obtained by combining these.

[0114] Furthermore, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom, and some of the -CH- groups of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom, and as a result, the hydrocarbyl group may contain a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a mercapto group, a carbonyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-OC(=O)-), a haloalkyl group, etc.

[0115] Also, R 4 and R 5 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded. In this case, the ring preferably has the following structure: [ka] (In the formula, the dashed lines represent bonds.)

[0116] Specific examples of the sulfonium cation represented by the above general formula (2) include, but are not limited to, those shown below. [ka]

[0117] [ka]

[0118] [ka]

[0119] [ka]

[0120] [ka]

[0121]

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[0142] [ka]

[0143] [ka]

[0144] [ka]

[0145] [ka]

[0146] Specific examples of the iodonium cation represented by the above general formula (3) include, but are not limited to, those shown below. [ka]

[0147] [ka]

[0148] The structural unit having the organic sulfonyl anion structure preferably contains an iodine atom, which has a high atomic absorption of EUV light and therefore has a sensitizing effect to EUV light, thereby removing residues at the bottom of the pattern and improving pattern roughness.

[0149] It is preferable that the ratio of the repeating units represented by the general formula (1) in the repeating units of the resin (A) is 70 mol % or more and 99.9 mol % or less.

[0150] Furthermore, the ratio of the repeating units represented by the general formula (1) among the repeating units of the resin (A) is more preferably 80 mol % to 99.9 mol %, and even more preferably 80 mol % to 99 mol %, but is not limited thereto. As described above, the nitrogen-hydrogen bond of the repeating unit represented by the general formula (1) contributes to coatability, so a high content of the repeating units is preferred from the viewpoint of ensuring coatability.

[0151] Furthermore, the ratio of repeating units having the organic sulfonyl anion structure among the repeating units of the (A) resin is preferably 0.1 mol% or more and 30 mol% or less, more preferably 0.1 mol% or more and 20 mol% or less, and even more preferably 1 mol% or more and 20 mol% or less, but is not limited thereto.

[0152] By adjusting the ratio of the organic sulfonyl anion structure in the repeating unit of the resin (A), it is possible to impart appropriate patterning performance required in each step.

[0153] In addition, when the molar fraction of the repeating unit represented by the general formula (1) and the repeating unit having an organic sulfonyl anion structure does not add up to 100%, the (A) resin contains other structural units. In this case, existing structural units can be suitably used as the other structural units. For example, other acrylic acid esters, other methacrylic acid esters, other acrylic acid amides, other methacrylic acid amides, crotonates, maleates, itaconic acid esters, and other α,β-unsaturated carboxylic acid esters; α,β-unsaturated carboxylic acids; methacrylic acid, acrylic acid, maleic acid, itaconic acid, and other α,β-unsaturated lactones; acrylonitrile; methacrylonitrile; α,β-unsaturated lactones such as 5,5-dimethyl-3-methylene-2-oxotetrahydrofuran; norbornene derivatives; tetracyclo[4.4.0.1] 2,5 .1 7,10] Any structural unit derived from cyclic olefins such as dodecene derivatives; α,β-unsaturated carboxylic anhydrides such as maleic anhydride and itaconic anhydride; allyl ethers; vinyl ethers; vinyl esters; or vinylsilanes can be used in combination, but is not limited to these.

[0154] When the resist top layer film is exposed to EUV light, it is preferable that the other structural units contain iodine atoms. Iodine atoms have a high atomic absorption of EUV light and therefore have a sensitizing effect to EUV light. Therefore, this is preferable from the viewpoint of removing residues at the bottom of the pattern and improving pattern roughness.

[0155] When it is desired to suppress collapse of the resist upper layer film, it is preferable that the other structural units contain a phenolic hydroxyl group. The phenolic hydroxyl group forms a hydrogen bond with the upper layer resist composition, thereby contributing to suppression of collapse. Examples of structural units having a phenolic hydroxyl group include, but are not limited to, structural units contained in resins described in paragraphs

[0058] to

[0059] of JP 2023-094359 A. Since a phenolic hydroxyl group can also serve as a hydrogen bond donor, the inclusion of such a structural unit has little adverse effect on coatability, and is also preferable from the viewpoint of coatability on hydrophobic surfaces.

[0156] Furthermore, it is preferable that the resin (A) does not contain an epoxide structure or an oxetane structure.

[0157] If the resin contains an epoxide structure or an oxetane structure that cannot serve as a hydrogen bond donor, hydrogen bonding between the adhesive film derived from the adhesive film-forming composition of the present invention and the underlayer film may be inhibited, which may make coating errors more likely to occur. Therefore, it is preferable that the resin does not contain these structures in order to ensure coatability on hydrophobic surfaces.

[0158] The weight-average molecular weight (Mw) of the (A) resin is preferably 1,000 to 70,000, more preferably 10,000 to 50,000. An Mw of 1,000 or more provides excellent film-forming properties, suppresses the generation of sublimates during heat curing, and prevents contamination of the apparatus by the sublimates. On the other hand, an Mw of 70,000 or less can prevent poor coating properties and coating defects due to insufficient solubility in organic solvents. The (A) resin also preferably has a molecular weight distribution (Mw / Mn) of 1.0 to 2.8, more preferably 1.0 to 2.5. In the present invention, Mw and molecular weight distribution are measured in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. The measurement temperature was 40°C.

[0159] By using a composition for forming an adhesion film containing such a resin in the formation of a multilayer resist film that is applied to microfabrication in the manufacturing process of a semiconductor device or the like, it is possible to provide a composition for forming an adhesion film, a method for forming an adhesion film, and a method for forming a pattern that have good coatability even on a hydrophobic underlayer film and can improve residues at the bottom of the resist while maintaining good pattern roughness.

[0160] The resin (A) can be synthesized by polymerizing each monomer, optionally protected with a protecting group, using a known method, followed by a deprotection reaction as needed. The polymerization reaction is not particularly limited, but is preferably radical polymerization or anionic polymerization. For these methods, see JP-A-2004-115630.

[0161] [(B) Organic solvent] The organic solvent (B) contained in the adhesive film-forming composition of the present invention is not particularly limited as long as it dissolves the resin (A) and, if present, other additives, etc., but it is preferred that the organic solvent (B) is a mixture of one or more organic solvents having a boiling point of less than 150° C. and one or more organic solvents having a boiling point of 150° C. or more and less than 220° C. Specifically, examples of the organic solvents include ketones such as cyclohexanone, cyclopentanone, methyl-2-n-pentyl ketone, and 2-heptanone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and diacetone alcohol; propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, and ethylene glycol monoethyl ether, as described in paragraphs

[0144] and

[0145] of JP-A No. 2008-111103. Examples of suitable organic solvents include ethers such as ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol monotert-butyl ether acetate; and lactones such as γ-butyrolactone. Preferred organic solvents with a boiling point of less than 150°C include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, cyclopentanone, and mixtures of one or more of these. Preferred organic solvents with a boiling point of 150°C or higher and less than 220°C include cyclohexanone, diacetone alcohol, ethyl lactate, γ-butyrolactone, and mixtures of one or more of these.

[0162] The amount of (B) organic solvent added is preferably 5,000 parts by mass or more, more preferably 8,000 parts by mass or more, per 100 parts by mass of the (A) resin.

[0163] [Additives] In addition to the components (A) and (B), the adhesion film-forming composition of the present invention may further contain one or more selected from the group consisting of (C) a thermal acid generator, (D) a surfactant, and (E) a crosslinking agent. By adjusting the types and amounts of these additives, various properties of the adhesion film-forming composition, such as its curing temperature, coatability, and patterning performance, can be optimized. Each component will be described below.

[0164] [(C) Thermal acid generator] In the composition for forming an adhesion film of the present invention, a thermal acid generator (C) can be added to promote the crosslinking reaction by heat.

[0165] Examples of the thermal acid generator (C) that can be used in the composition for forming an adhesion film of the present invention include those represented by the following general formula (4).

[0166] [ka] (In the formula, K - represents a non-nucleophilic counter ion. R8, R9, R 10 and R 11 each represents a hydrogen atom, a linear, branched, or cyclic alkyl group or oxoalkyl group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkenyl group or oxoalkenyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxoalkyl group having 7 to 12 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with an alkoxy group or the like. 10 may be bonded to each other to form a ring, and when a ring is formed, R and R, and R, R and R 10 represents an alkylene group having 3 to 10 carbon atoms, or a heteroaromatic ring having a nitrogen atom in the ring.

[0167] Above, R8, R9, R 10 and R 11may be the same or different, and specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl. Alkenyl groups include vinyl, allyl, propenyl, butenyl, hexenyl, and cyclohexenyl. Oxoalkyl groups include 2-oxocyclopentyl and 2-oxocyclohexyl groups, such as 2-oxopropyl, 2-cyclopentyl-2-oxoethyl, 2-cyclohexyl-2-oxoethyl, and 2-(4-methylcyclohexyl)-2-oxoethyl. Examples of the oxoalkenyl group include a 2-oxo-4-cyclohexenyl group and a 2-oxo-4-propenyl group. Examples of the aryl group include a phenyl group, a naphthyl group, and the like; alkoxyphenyl groups such as a p-methoxyphenyl group, a m-methoxyphenyl group, an o-methoxyphenyl group, an ethoxyphenyl group, a p-tert-butoxyphenyl group, and a m-tert-butoxyphenyl group; alkylphenyl groups such as a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, and a dimethylphenyl group; alkylnaphthyl groups such as a methylnaphthyl group and an ethylnaphthyl group; alkoxynaphthyl groups such as a methoxynaphthyl group and an ethoxynaphthyl group; dialkylnaphthyl groups such as a dimethylnaphthyl group and a diethylnaphthyl group; and dialkoxynaphthyl groups such as a dimethoxynaphthyl group and a diethoxynaphthyl group. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a phenethyl group, etc. Examples of the aryloxoalkyl group include a 2-aryl-2-oxoethyl group such as a 2-phenyl-2-oxoethyl group, a 2-(1-naphthyl)-2-oxoethyl group, and a 2-(2-naphthyl)-2-oxoethyl group.

[0168] Also, R8 and R9, and R8, R9 and R 10Examples of heteroaromatic rings having a nitrogen atom in the ring in the formula include imidazole derivatives (e.g., imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazan derivatives, pyrroline derivatives (e.g., pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (e.g., pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, , 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (e.g., quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives, etc.

[0169] Above K -Examples of the non-nucleophilic counter ion include halide ions such as chloride ion and bromide ion; fluoroalkyl sulfonates such as triflate, 1,1,1-trifluoroethanesulfonate, and nonafluorobutanesulfonate; aryl sulfonates such as tosylate, benzenesulfonate, 4-fluorobenzenesulfonate, and 1,2,3,4,5-pentafluorobenzenesulfonate; alkyl sulfonates such as mesylate and butanesulfonate; imido acids such as bis(trifluoromethylsulfonyl)imide, bis(perfluoroethylsulfonyl)imide, and bis(perfluorobutylsulfonyl)imide; methide acids such as tris(trifluoromethylsulfonyl)methide and tris(perfluoroethylsulfonyl)methide; and sulfonates substituted with fluoro at the α-position as shown in the following general formula (5) and sulfonates substituted with fluoro at the α- and β-positions as shown in the following general formula (6).

[0170] [ka]

[0171] In the above general formula (5), R 12 is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, an acyl group or alkenyl group having 2 to 20 carbon atoms, or an aryl group or aryloxy group having 6 to 20 carbon atoms. 13 is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0172] Specific examples of the thermal acid generator (C) include the following: [ka]

[0173] The thermal acid generator (C) contained in the composition for forming an adhesion film of the present invention can be used alone or in combination of two or more. The amount of the thermal acid generator (C) added is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the resin (A). If the amount is 0.05 parts by mass or more, the amount of acid generated is sufficient and the crosslinking reaction proceeds sufficiently, while if the amount is 30 parts by mass or less, the mixing phenomenon caused by the acid migrating to the upper resist layer does not occur.

[0174] [(D) Surfactant] A (D) surfactant can be added to the adhesion film-forming composition of the present invention to improve the coating properties in spin coating. The (D) surfactant can be used alone or in combination of two or more. Examples of the (D) surfactant that can be used include those described in paragraphs

[0142] to

[0147] of JP-A No. 2009-269953. When the (D) surfactant is added, the amount added is preferably 0.001 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, per 100 parts by mass of the (A) resin.

[0175] [(E) Crosslinking agent] Furthermore, a crosslinking agent (E) may be added to the adhesion film-forming composition of the present invention to enhance curability and further suppress intermixing with the resist upper layer film. The crosslinking agent is not particularly limited, and a wide variety of known crosslinking agents can be used. Examples include melamine-based crosslinking agents, glycoluril-based crosslinking agents, benzoguanamine-based crosslinking agents, urea-based crosslinking agents, β-hydroxyalkylamide-based crosslinking agents, isocyanurate-based crosslinking agents, aziridine-based crosslinking agents, oxazoline-based crosslinking agents, epoxy-based crosslinking agents, and polynuclear phenol-based crosslinking agents.

[0176] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylated melamine, hexabutoxymethylated melamine, alkoxy- and / or hydroxy-substituted products thereof, and partial self-condensates thereof. Specific examples of glycoluril crosslinking agents include tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, alkoxy and / or hydroxy substituted products thereof, and partial self-condensates thereof. Specific examples of benzoguanamine-based crosslinking agents include tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, alkoxy- and / or hydroxy-substituted products thereof, and partial self-condensates thereof. Specific examples of urea-based crosslinking agents include dimethoxymethylated dimethoxyethylene urea, its alkoxy and / or hydroxy substituted derivatives, and partial self-condensates thereof. A specific example of the β-hydroxyalkylamide crosslinking agent is N,N,N',N'-tetra(2-hydroxyethyl)adipamide. Specific examples of the isocyanurate crosslinking agent include triglycidyl isocyanurate and triallyl isocyanurate. Specific examples of the aziridine crosslinking agent include 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate]. Specific examples of the oxazoline-based crosslinking agent include 2,2'-isopropylidenebis(4-benzyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), 2,2'-methylenebis(4,5-diphenyl-2-oxazoline), 2,2'-methylenebis(4-phenyl-2-oxazoline), 2,2'-methylenebis(4-tert-butyl-2-oxazoline), 2,2'-bis(2-oxazoline), 1,3-phenylenebis(2-oxazoline), 1,4-phenylenebis(2-oxazoline), and 2-isopropenyloxazoline copolymer. Specific examples of epoxy-based crosslinking agents include diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, poly(glycidyl methacrylate), trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, and pentaerythritol tetraglycidyl ether.

[0177] Specific examples of polynuclear phenol-based crosslinking agents include compounds represented by the following general formula (7). [ka] (In the formula, Q is a single bond or a q-valent hydrocarbon group having 1 to 20 carbon atoms. R 14 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and q is an integer of 1 to 5.

[0178] Q is a single bond or a q-valent hydrocarbon group having 1 to 20 carbon atoms. q is an integer of 1 to 5, preferably 2 or 3. Specific examples of Q include groups in which q hydrogen atoms have been removed from methane, ethane, propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, methylpentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylisopropylbenzene, diisopropylbenzene, methylnaphthalene, ethylnaphthalene, and eicosane. R 14 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, an octyl group, an ethylhexyl group, a decyl group, and an eicosanyl group, and a hydrogen atom or a methyl group is preferred.

[0179] Specific examples of the compound represented by the general formula (7) include the following compounds: Among these, hexamethoxymethylated products of triphenolmethane, triphenolethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene are preferred from the viewpoint of improving the curability and film thickness uniformity of the adhesive film.

[0180] [ka]

[0181] [ka]

[0182] The (E) crosslinking agent can be used alone or in combination of two or more. The amount of the (E) crosslinking agent added is preferably 10% by mass to 50% by mass, more preferably 10% by mass to 30% by mass, based on 100 parts by mass of the (A) resin. If the amount added is 10% by mass or more, sufficient curability is obtained and intermixing with the resist upper layer film can be suppressed. On the other hand, if the amount added is 50% by mass or less, the proportion of the (A) resin in the composition remains high, so that the coatability on hydrophobic surfaces is not deteriorated.

[0183] The thickness of the film formed from the adhesion film-forming composition of the present invention may be appropriately selected, but is preferably 2 to 100 nm, and more preferably 5 to 20 nm.

[0184] Furthermore, the composition for forming an adhesion film of the present invention is extremely useful as an adhesion film material for multilayer resist processes such as a two-layer resist process or a four-layer resist process using a resist underlayer film and a silicon-containing intermediate film.

[0185] The silicon-containing intermediate film can be a silicon-containing resist intermediate film or an inorganic hard mask intermediate film depending on the pattern formation method described below. The inorganic hard mask intermediate film is preferably selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film.

[0186] In the present invention, the film formed from the composition containing components (A) and (B) is called an "adhesion film," but as described above, the film formed by the present invention may also be what is called an "underlayer film" or an "intermediate film" in a multilayer resist method. Regardless of the name, any organic film that is cured by heat treatment or the like from a film formed from a composition containing components (A) and (B) is included within the scope of the present invention.

[0187] [Method for forming adhesive film] The present invention provides a method for forming an adhesion film using the above-mentioned composition for forming an adhesion film, which has good coatability even on a hydrophobic underlayer film and can improve residues at the bottom of the resist while maintaining good pattern roughness, in a fine patterning process using a multilayer resist method in a semiconductor device manufacturing process.

[0188] In the method for forming an adhesion film of the present invention, the above-described adhesion film-forming composition is coated onto a substrate to be processed by spin coating or the like. After spin coating, the organic solvent is evaporated, and baking (heat treatment) is performed to promote the crosslinking reaction and prevent intermixing with the resist top layer film or the silicon-containing intermediate film. Baking is preferably performed at 100°C or higher and 300°C or lower for 10 to 600 seconds, more preferably 200°C or higher and 250°C or lower for 10 to 300 seconds. Considering the effect on damage to the adhesion film and wafer deformation, the upper limit of the heating temperature in the lithography wafer process is preferably 300°C or lower, more preferably 250°C or lower.

[0189] That is, the present invention provides a method for forming an adhesion film used in the manufacturing process of a semiconductor device, which comprises spin-coating the above-described composition for forming an adhesion film on a substrate to be processed, and heat-treating the substrate coated with the composition for forming an adhesion film at a temperature of 100°C or higher and 300°C or lower for 10 to 600 seconds to form an adhesion film.

[0190] In addition, in the method for forming an adhesion film of the present invention, the adhesion film-forming composition of the present invention can be coated on a substrate to be processed by spin coating or the like as described above, and the adhesion film-forming composition can be baked and cured in an atmosphere with an oxygen concentration of 0.1% or more and 21% or less to form an adhesion film. By baking the adhesion film-forming composition of the present invention in such an oxygen atmosphere, a sufficiently cured adhesion film can be obtained. The baking temperature, etc. can be the same as described above.

[0191] That is, the present invention provides a method for forming an adhesion film used in the manufacturing process of a semiconductor device, which comprises spin-coating the above-described composition for forming an adhesion film on a substrate to be processed, and heat-treating the substrate coated with the composition for forming an adhesion film in an atmosphere with an oxygen concentration of 0.1% or more and 21% or less to form an adhesion film.

[0192] The atmosphere during baking may be air, or an inert gas such as N2, Ar, or He may be enclosed. In this case, the atmosphere may have an oxygen concentration of 0.0001% or more but less than 0.1%. The baking temperature and the like may be the same as those described above. By baking the adhesion film-forming composition of the present invention in such an oxygen atmosphere, the crosslinking reaction during adhesion film formation can be promoted without causing deterioration of the substrate to be processed, even if the substrate contains a material that is unstable when heated in an oxygen atmosphere.

[0193] That is, the present invention provides a method for forming an adhesion film used in the manufacturing process of a semiconductor device, which comprises spin-coating the above-described composition for forming an adhesion film on a substrate to be processed, and heat-treating the substrate coated with the composition for forming an adhesion film in an atmosphere with an oxygen concentration of 0.0001% or more and less than 0.1%, thereby forming an adhesion film.

[0194] [Pattern formation method] In the present invention, there is provided a method for forming a pattern on a substrate to be processed, comprising the steps of: (I-1) A step of applying the above-described composition for forming an adhesion film onto a substrate to be processed, followed by heat treatment to form an adhesion film; (I-2) forming a resist upper layer film on the adhesion film using a photoresist material; (I-3) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (I-4) a step of transferring the pattern to the adhesive film by dry etching using the resist upper layer film on which the circuit pattern is formed as a mask; and (I-5) a step of processing the substrate to be processed using the resist top layer film and / or adhesive film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed; The present invention provides a pattern forming method comprising the steps of:

[0195] The pattern forming method of the present invention will be described below taking a four-layer resist process as an example, but is not limited to this process.First, a method for forming a pattern on a substrate to be processed, comprising at least forming a resist underlayer film on the substrate to be processed using an organic film material, forming a silicon-containing intermediate film (silicon-containing resist intermediate film) on the resist underlayer film using a resist intermediate film material containing silicon atoms (silicon-containing resist intermediate film), forming an adhesion film on the silicon-containing resist intermediate film using an adhesion film-forming composition of the present invention, forming a resist upper layer film on the adhesion film using a resist upper layer film material consisting of a photoresist composition to form a multi-layer resist film, exposing the pattern circuit area of ​​the resist upper layer film, and then developing with a developer to form a resist upper layer film pattern on the resist upper layer film obtained. The present invention provides a pattern forming method that includes etching an adhesion film using a resist upper layer film pattern as an etching mask to form the adhesion film pattern, etching the silicon-containing resist intermediate film using the resist upper layer film pattern and / or adhesion film pattern remaining after etching as an etching mask to form a silicon-containing resist intermediate film pattern, etching the resist underlayer film using the silicon-containing resist intermediate film pattern obtained as an etching mask to form a resist underlayer film pattern, and further etching the workpiece substrate using the resist underlayer film pattern obtained as an etching mask to form a pattern on the workpiece substrate.

[0196] That is, the present invention provides a method for forming a pattern on a substrate to be processed, comprising the steps of: (II-1) forming a resist underlayer film on a substrate to be processed; (II-2) forming a silicon-containing resist intermediate film on the resist underlayer film; (II-3) A step of applying the above-described composition for forming an adhesion film onto the silicon-containing resist intermediate film, followed by heat treatment to form an adhesion film; (II-4) forming a resist upper layer film on the adhesion film using a photoresist material; (II-5) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (II-6) a step of transferring the pattern to the adhesive film by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask; (II-7) a step of transferring the pattern to the silicon-containing resist intermediate film by dry etching using the resist upper layer film and / or adhesive film on which the pattern has been formed as a mask; (II-8) a step of transferring a pattern to the resist underlayer film by dry etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; and (II-9) a step of processing the substrate to be processed using the resist underlayer film to which the pattern has been transferred as a mask to form a pattern on the substrate to be processed; The present invention provides a pattern forming method comprising the steps of:

[0197] Polysilsesquioxane-based interlayers are also preferred as the silicon-containing resist interlayer in the four-layer resist process. By imparting anti-reflection properties to the silicon-containing resist interlayer, reflection can be suppressed. For 193 nm exposure, in particular, using a resist underlayer containing a material with a high aromatic group content and high substrate etching resistance results in a high k value and high substrate reflection. However, by suppressing reflection with a silicon-containing resist interlayer, substrate reflection can be reduced to 0.5% or less. Preferred silicon-containing resist interlayers with anti-reflection properties are anthracene for 248 nm and 157 nm exposure, and polysilsesquioxanes with pendant light-absorbing groups having phenyl groups or silicon-silicon bonds and crosslinked by acid or heat for 193 nm exposure.

[0198] In this case, forming a silicon-containing resist intermediate film by spin coating is easier and more cost-effective than forming it by CVD.

[0199] Alternatively, an inorganic hard mask intermediate film may be formed as the silicon-containing intermediate film. In this case, at least a resist underlayer film is formed on a substrate to be processed using an organic film material, an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the resist underlayer film, an adhesion film is formed on the inorganic hard mask intermediate film using the composition for forming an adhesion film of the present invention, a resist upper layer film is formed on the adhesion film using a resist upper layer film material comprising a photoresist composition, and a pattern circuit region of the resist upper layer film is exposed to light and then developed with a developer to form a resist upper layer film pattern in the resist upper layer film, the adhesion film is etched using the obtained resist upper layer film pattern as an etching mask to form an adhesion film pattern, the inorganic hard mask intermediate film is etched using the obtained adhesion film pattern as an etching mask to form an inorganic hard mask intermediate film pattern, the resist underlayer film is etched using the obtained inorganic hard mask intermediate film pattern as an etching mask to form a resist underlayer film pattern, and further, the substrate to be processed is etched using the obtained resist underlayer film pattern as an etching mask to form a pattern on the substrate to be processed.

[0200] That is, the present invention provides a method for forming a pattern on a substrate to be processed, comprising the steps of: (III-1) forming a resist underlayer film on a substrate to be processed; (III-2) forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist underlayer film; (III-3) A step of applying the above-described composition for forming an adhesion film onto the inorganic hard mask intermediate film, followed by heat treatment to form an adhesion film; (III-4) forming a resist upper layer film on the adhesion film using a photoresist material; (III-5) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (III-6) a step of transferring the pattern to the adhesive film by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask; (III-7) a step of transferring a pattern onto the inorganic hard mask intermediate film by dry etching using the resist upper layer film and / or adhesive film on which the pattern has been formed as a mask; (III-8) transferring a pattern to the resist underlayer film by dry etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; and (III-9) a step of processing the substrate to be processed using the resist underlayer film to which the pattern has been transferred as a mask to form a pattern on the substrate to be processed; The present invention provides a pattern forming method comprising the steps of:

[0201] As described above, when forming an inorganic hard mask intermediate film on a resist underlayer film, a silicon oxide film, a silicon nitride film, or a silicon oxynitride film (SiON film) can be formed by a CVD method, an ALD method, or the like. That is, the inorganic hard mask intermediate film is preferably formed by a CVD method or an ALD method. For example, methods for forming a silicon nitride film are described in JP 2002-334869 A and WO 2004 / 066377 A. The thickness of the inorganic hard mask intermediate film is preferably 5 to 200 nm, more preferably 10 to 100 nm. Furthermore, a SiON film, which is highly effective as an anti-reflective coating, is most preferably used as the inorganic hard mask intermediate film. Since the substrate temperature during SiON film formation is 300 to 500°C, the resist underlayer film must be able to withstand temperatures of 300 to 500°C.

[0202] The resist top layer film in the four-layer resist process may be either positive or negative, and the same photoresist compositions commonly used as photoresists can be used. The photoresist material preferably contains at least an organometallic compound and a solvent. The organometallic compound preferably contains at least one selected from titanium, cobalt, copper, zinc, zirconium, lead, indium, tin, antimony, and hafnium, but is not limited thereto. After spin-coating the photoresist composition, pre-baking is performed, preferably at 60 to 180°C for 10 to 300 seconds. Subsequently, exposure is performed according to conventional methods, followed by post-exposure baking (PEB) and development to obtain a resist top layer film pattern. The thickness of the resist top layer film is not particularly limited, but is preferably 30 to 500 nm, and more preferably 50 to 400 nm.

[0203] When the photoresist material is a composition containing at least an organometallic compound and a solvent, it has the effect of suppressing collapse of a fine pattern and can appropriately adjust the pattern shape, exposure sensitivity, etc. of the resist upper layer film. At the same time, it can prevent contamination of the substrate to be processed by the metal compound when using a photoresist material containing an organometallic compound and a solvent.

[0204] A circuit pattern (resist upper layer film pattern) is formed on the resist upper layer film. As a method for forming the circuit pattern on the resist upper layer film, photolithography with a wavelength of 10 nm or more and 300 nm or less, direct writing with an electron beam, nanoimprinting, or a combination thereof is preferably used.

[0205] Examples of exposure light include high-energy rays with a wavelength of 300 nm or less, specifically far ultraviolet rays, KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F2 laser light (157 nm), Kr2 laser light (146 nm), Ar2 laser light (126 nm), soft X-rays (EUV) of 3 to 20 nm, electron beams (EB), ion beams, X-rays, and the like.

[0206] As a method for developing the circuit pattern, it is preferable to use alkaline development or development with an organic solvent.

[0207] Next, etching is performed using the obtained resist upper layer film pattern as a mask. In the four-layer resist process, etching of the adhesive film is performed using an oxygen-based gas with the resist upper layer film pattern as a mask. This forms an adhesive film pattern.

[0208] Next, etching is performed using the resist upper layer film pattern and / or adhesive film pattern remaining after etching as a mask. The silicon-containing resist intermediate film or inorganic hard mask intermediate film is etched using a fluorocarbon-based gas, using the resist upper layer film pattern and / or adhesive film pattern remaining after etching as a mask. This forms a silicon-containing resist intermediate film pattern or inorganic hard mask intermediate film pattern.

[0209] The etching of the adhesive film may be carried out prior to and consecutively with the etching of the silicon-containing intermediate film, or the etching of the adhesive film alone may be carried out and then the etching of the silicon-containing intermediate film may be carried out by changing the etching equipment, for example.

[0210] Next, the resist underlayer film is etched using the resulting silicon-containing resist intermediate film pattern or inorganic hard mask intermediate film pattern as a mask.

[0211] The next step, etching of the substrate to be processed, can also be done using standard methods; for example, if the substrate to be processed is made of SiO2, SiN, or a silica-based low-k dielectric insulating film, etching is done primarily with fluorocarbon-based gases, while for p-Si, Al, or W, etching is done primarily with chlorine- or bromine-based gases. If the substrate is etched with fluorocarbon-based gases, the silicon-containing intermediate film pattern in the three-layer resist process is stripped at the same time as the substrate is processed. If the substrate is etched with chlorine- or bromine-based gases, the silicon-containing intermediate film pattern must be stripped separately by dry etching using fluorocarbon-based gases after substrate processing.

[0212] The substrate to be processed is not particularly limited, and may be a semiconductor device substrate, or a semiconductor device substrate having a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal carbide oxide film, or a metal oxynitride film formed thereon. The metal may be silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or an alloy thereof.

[0213] Specifically, substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, and Al, and substrates with a work layer formed thereon, are used. The work layer may be a variety of low-k films and their stopper films, such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, and Al-Si, and can be formed to a thickness of typically 50 to 10,000 nm, and particularly 100 to 5,000 nm. When forming a work layer, the substrate and work layer are made of different materials.

[0214] An example of a four-layer resist process is specifically shown below with reference to Figure 1. In the four-layer resist process, as shown in Figure 1(A), a resist underlayer film 3 is formed using an organic film material on a processable layer 2 laminated on a substrate 1, and then a silicon-containing intermediate film 4 is formed thereon, and an adhesion film 5 is formed thereon using the adhesion film-forming composition of the present invention, and a resist upper layer film 6 is formed thereon.

[0215] Next, as shown in FIG. 1(B), the exposed portion 7 of the resist top layer film is exposed, followed by PEB and development to form a resist top layer film pattern 6a (FIG. 1(C)). Using the resulting resist top layer film pattern 6a as a mask, the adhesion film 5 is etched using an O2-based gas to form an adhesion film pattern 5a (FIG. 1(D)). Using the resulting adhesion film pattern 5a as a mask, the silicon-containing intermediate film 4 is etched using a CF2-based gas to form a silicon-containing intermediate film pattern 4a (FIG. 1(E)). After removing the adhesion film pattern 5a, the resist underlayer film 3 is etched using an O2-based gas to form a resist underlayer film pattern 3a (FIG. 1(F)). After removing the silicon-containing intermediate film pattern 4a, the processable layer 2 is etched using the resist underlayer film pattern 3a as a mask to form a pattern 2a (FIG. 1(G)).

[0216] As described above, the pattern forming method of the present invention makes it possible to form a fine pattern on a substrate to be processed with high precision in a multi-layer resist process. [Example]

[0217] The present invention will be explained in more detail below with reference to Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited thereto. Molecular weight measurements were performed by gel permeation chromatography (GPC) using tetrahydrofuran (THF) or N,N-dimethylformamide (DMF) as an eluent, and the polydispersity (Mw / Mn) was calculated from the weight-average molecular weight (Mw) and number-average molecular weight (Mn) in terms of polystyrene. The measurement temperature was 40°C.

[0218] The polymers (A1) to (A24) and comparative polymers (R1) to (R5) used as the resin (A) for the adhesive film-forming material were synthesized using the following monomers (B1) to (B21).

[0219] [ka]

[0220] [Synthesis Example 1] Synthesis of polymer (A1) Under a nitrogen atmosphere, 64.9 g of monomer (B1), 35.1 g of monomer (B17), 4.13 g of V-601 (2,2'-azobis(isobutyrate) dimethyl, manufactured by Wako Pure Chemical Industries, Ltd.), and 340 g of DAA (diacetone alcohol) were weighed into a 1 L flask and degassed with stirring to prepare a monomer-polymerization initiator solution. 60 g of DAA was weighed into another 1 L flask under a nitrogen atmosphere, degassed with stirring, and then heated to an internal temperature of 80°C. The monomer-polymerization initiator solution was added dropwise over 4 hours, and stirring was continued for 16 hours while maintaining the temperature of the polymerization solution at 80°C. The polymerization solution was then cooled to room temperature. The resulting polymerization solution was added dropwise to 1,500 g of vigorously stirred hexane, and the precipitated polymer was filtered off. The resulting polymer was washed twice with 600 g of hexane and then vacuum dried at 50° C. for 20 hours to obtain a white powdery polymer (A1) (yield: 98.4 g, 95%). The weight average molecular weight (Mw) and polydispersity (Mw / Mn) of the polymer (A1) were determined by GPC to be Mw=27,900 and Mw / Mn=1.92. [ka]

[0221] [Synthesis Examples 2 to 24, Comparative Synthesis Examples 1 and 2] Synthesis of polymers (A2) to (A24) and comparative polymers (R1) to (R2) Polymers (A2) to (A24) and comparative polymers (R1) to (R2) were obtained as products by carrying out the reaction and post-treatment under the same conditions as in Synthesis Example 1, except that the monomers and polymerization initiators shown in Table 1 were used. The weight average molecular weight (Mw), dispersity (Mw / Mn), and polymer (A1) determined by GPC are also shown.

[0222] [Table 1]

[0223] [Comparative Synthesis Example 3] Synthesis of Comparative Polymer (R3) Under a nitrogen atmosphere, 62.8 g of monomer (B9), 37.2 g of monomer (B10), 1.45 g of V-601, and 340 g of PGMEA were weighed into a 1 L flask and degassed with stirring to prepare a monomer-polymerization initiator solution. 60 g of PGMEA was weighed into a separate 1 L flask under a nitrogen atmosphere, degassed with stirring, and then heated to an internal temperature of 80°C. The monomer-polymerization initiator solution was added dropwise over 4 hours, and the polymerization solution was stirred for 16 hours while maintaining the temperature at 80°C. It was then cooled to room temperature. The resulting polymerization solution was added dropwise to 1,500 g of vigorously stirred hexane, and the precipitated polymer was filtered. The resulting polymer was washed twice with 600 g of hexane and then vacuum-dried at 50°C for 20 hours to obtain a white powdery comparative polymer (R3) (yield: 97.5 g, 96%). The weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer (R3) were determined by GPC, and were found to be Mw=33,500 and Mw / Mn=1.88. [ka]

[0224] [Comparative Synthesis Example 4] Synthesis of Comparative Polymer (R4) Under a nitrogen atmosphere, 64.3 g of monomer (B9), 35.7 g of monomer (B11), 1.49 g of V-601, and 340 g of PGMEA were weighed into a 1 L flask and degassed with stirring to prepare a monomer-polymerization initiator solution. 60 g of PGMEA was weighed into a separate 1 L flask under a nitrogen atmosphere, degassed with stirring, and then heated to an internal temperature of 80 °C. The monomer-polymerization initiator solution was added dropwise over 4 hours, and the polymerization solution was stirred for 16 hours while maintaining the temperature at 80 °C. It was then cooled to room temperature. The resulting polymerization solution was added dropwise to 1,500 g of vigorously stirred hexane, and the precipitated polymer was filtered. The resulting polymer was washed twice with 600 g of hexane and then vacuum-dried at 50 °C for 20 hours to obtain a white powdery comparative polymer (R4) (yield: 96.5 g, 95%). The weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer (R4) were determined by GPC, and were found to be Mw=32,200 and Mw / Mn=1.80. [ka]

[0225] [Comparative Synthesis Example 5] Synthesis of Comparative Polymer (R5) Under a nitrogen atmosphere, 66.1 g of monomer (B9), 33.9 g of monomer (B16), 1.49 g of V-601, and 340 g of PGMEA were weighed into a 1 L flask and degassed with stirring to prepare a monomer-polymerization initiator solution. 60 g of PGMEA was weighed into a separate 1 L flask under a nitrogen atmosphere, degassed with stirring, and then heated to an internal temperature of 80 °C. The monomer-polymerization initiator solution was added dropwise over 4 hours, and the polymerization solution was stirred for 16 hours while maintaining the temperature at 80 °C. It was then cooled to room temperature. The resulting polymerization solution was added dropwise to 1,500 g of vigorously stirred hexane, and the precipitated polymer was filtered. The resulting polymer was washed twice with 600 g of hexane and then vacuum-dried at 50 °C for 20 hours to obtain a white powdery comparative polymer (R5) (yield: 97.0 g, 96%). The weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer (R5) were determined by GPC, and were found to be Mw=31,200 and Mw / Mn=1.82. [ka]

[0226] [Comparative Synthesis Example 6] Synthesis of Comparative Polymer (R6) A comparative polymer (R6) was synthesized according to the method described in paragraph

[0136] of Patent Document 6. [ka]

[0227] [Comparative Synthesis Example 7] Synthesis of Comparative Polymer (R7) A comparative polymer (R7) was synthesized according to the method described in paragraph

[0155] of Patent Document 7. [ka]

[0228] Preparation of adhesive film materials (AL-1 to 33, comparative AL-1 to 7) The above polymers (A1) to (A24), comparative polymers (R1) to (R7), the additives (AD1) to (AD7) shown below, and propylene glycol monomethyl ether acetate (PGMEA) containing 0.01 mass% of PF6320 (manufactured by OMNOVA), diacetone alcohol (DAA), or ethyl lactate (EL) were dissolved in the proportions shown in Table 2, and then filtered through a 0.1 μm fluororesin filter to prepare adhesion film materials (AL-1 to 33, comparative AL-1 to 7). Note that comparative AL-7 was prepared to have the same composition as AL8 described in paragraph

[0165] of Patent Document 7.

[0229] [ka]

[0230] [Table 2]

[0231] The compositions in Table 2 are as follows: Organic solvents: PGMEA (Propylene Glycol Monomethyl Ether Acetate) DAA (diacetone alcohol) EL (Ethyl lactate)

[0232] Example 1 Coatability test on wafers with various films (Examples 1-1 to 1-33, Comparative Examples 1-1 to 1-7) The above-mentioned adhesion film materials (AL1-33, Comparative AL1-7) were applied to substrates that had been treated with hexamethyldisilazane (HMDS) at 120°C for 60 seconds, or to substrates with CVD-SiO2, CVD-SiON, CVD-amorphous Si, CVD-amorphous carbon, or CVD-SiN films, and baked at 250°C for 60 seconds to form adhesion films with thicknesses of 5 nm (AL-1-2, 4-33, Comparative AL-1-7) or 20 nm (AL-3). The film surfaces were then observed with an optical microscope to check for and confirm the number of coating errors. The results are shown in Table 3. The notations in the table correspond to the following: ++: No abnormalities +: 1 to 5 pinhole-like dispensing errors were found -: 6 to 10 pinhole-like dispensing errors were found --: 11 or more pinhole-like coating errors or countless coating errors occur, making it impossible to form a film

[0233] [Table 3]

[0234] As shown in Table 3, Examples 1-1 to 1-33, which used adhesion film materials (AL-1 to 33), which are adhesion film-forming compositions of the present invention, generally resulted in few pinhole-like coating errors. It can be seen that those containing a larger amount of the structural unit represented by general formula (1) have particularly excellent coating properties. On the other hand, Comparative Examples 1-3 to 1-6, which used Comparative Examples AL-3 to AL-6, which do not have the structural unit represented by general formula (1), resulted in slightly inferior coating properties compared to the others.

[0235] Example 2 Coatability test on silicon-containing resist intermediate film (Examples 2-1 to 2-33, Comparative Examples 2-1 to 2-7) A silicon-containing resist interlayer film composition SHB-A940 (manufactured by Shin-Etsu Chemical Co., Ltd.) was applied to a silicon wafer substrate and baked at 215°C for 60 seconds to form a 20 nm thick silicon-containing resist interlayer film. The above-mentioned adhesion film materials (AL1-33, Comparative AL1-7) were then applied thereon and baked at 250°C for 60 seconds to form adhesion films with thicknesses of 5 nm (AL-1-2, 4-33, Comparative AL-1-7) or 20 nm (AL-3). The film surface was then observed under an optical microscope to confirm the presence and number of coating errors. The results are shown in Table 4. The following symbols correspond to the following: ++: No abnormalities +: 1 to 5 pinhole-like dispensing errors were found -: 6 to 10 pinhole-like dispensing errors were found --: 11 or more pinhole-like coating errors or countless coating errors occur, making it impossible to form a film

[0236] [Table 4]

[0237] As shown in Table 4, Examples 2-1 to 2-33, which used adhesion film materials (AL-1 to 33), which are adhesion film-forming compositions of the present invention, showed good coatability even on silicon-containing resist intermediate films. Furthermore, Comparative Examples 2-3 to 2-6, which used Comparative Examples AL-3 to AL-6, which do not contain the structure represented by general formula (1), showed more coating errors than the other examples, indicating that the introduction of this structural unit improved coatability.

[0238] Example 3 ArF immersion lithography pattern formation test (Examples 3-1 to 3-23, Comparative Examples 3-1 to 3-3) A silicon wafer substrate was coated with spin-on carbon ODL-301 (88% carbon by mass) manufactured by Shin-Etsu Chemical Co., Ltd. and baked at 350°C for 60 seconds to form a 200 nm thick resist underlayer film. A CVD-SiON hard mask intermediate film was then formed on top of this, followed by coating with the above-mentioned adhesion film materials (AL-1-6, 8, 10-16, 23-27, 30-33, and Comparative AL-1-2, 7) and baking at 250°C for 60 seconds to form a 5 nm thick (AL-1-2, 4-6, 8, 10-16, 23-27, 30-33, and Comparative AL-1-2, 7) or 20 nm thick (AL-3). A positive resist toplayer material (single-layer resist for ArF) was then coated on top of this and baked at 105°C for 60 seconds to form a 100 nm thick resist toplayer film. An immersion protective film material (TC-1) was applied onto the resist top layer film and baked at 90° C. for 60 seconds to form a protective film with a thickness of 50 nm.

[0239] The positive resist top layer film material (ArF single-layer resist) was prepared by dissolving a polymer (PRP-A1), an acid generator (PAG1), and a basic compound (Amine1) in the proportions shown in Table 5 in a solvent containing 0.1 mass% of FC-430 (manufactured by Sumitomo 3M Limited), and filtering the solution through a 0.1 μm fluororesin filter.

[0240] [Table 5]

[0241] Polymer: PRP-A1 Molecular weight (Mw)=8,600 Dispersity (Mw / Mn)=1.88 [ka]

[0242] Acid generator: PAG1 [ka]

[0243] Basic Compound: Amine1 [ka]

[0244] The immersion protective film material (TC-1) was prepared by dissolving the protective film polymer (PP1) in an organic solvent in the ratio shown in Table 6 and filtering the solution through a 0.1 μm fluorine resin filter.

[0245] [Table 6]

[0246] Protective film polymer: PP1 Molecular weight (Mw)=8,800 Dispersity (Mw / Mn)=1.69 [ka]

[0247] The pattern was then exposed using an ArF immersion exposure system (Nikon Corporation; NSR-S610C, NA 1.30, σ 0.98 / 0.65, 35° dipole s-polarized illumination, 6% halftone phase-shift mask), baked at 100°C for 60 seconds (PEB), and developed in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds, yielding a 40 nm 1:1 line-and-space pattern. The cross-sectional shape and roughness of this pattern were observed using an electron microscope. Furthermore, the minimum dimension at which the lines could be resolved without collapsing when the line dimensions were narrowed by increasing the exposure dose was determined, and this was taken as the collapse limit (nm). A smaller value indicates higher collapse resistance, which is preferable.

[0248] The cross-sectional shape of the obtained pattern was evaluated using an electron microscope (S-4700) manufactured by Hitachi, Ltd., and the pattern roughness was evaluated using an electron microscope (CG4000) manufactured by Hitachi High-Technologies Corp. The results are shown in Table 7.

[0249] [Table 7]

[0250] As shown in Table 7, Examples 3-1 to 3-23, which used adhesion film materials (AL-1 to 6, 8, 10 to 16, 23 to 27, 30 to 33), which are adhesion film-forming compositions of the present invention, showed less pattern roughness and better pattern shapes than the comparative examples. Focusing on the collapse limit, improvements were observed in Examples 3-18 to 3-19, which used structural units containing phenolic hydroxyl groups, and it was found that this structure contributed to the collapse suppression ability.

[0251] Example 4 EUV Exposure Pattern Formation Test Using Positive Resist (Examples 4-1 to 4-15, Comparative Examples 4-1 to 4-4) A silicon wafer substrate was coated with spin-on carbon ODL-301 (carbon content: 88% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. and baked at 350°C for 60 seconds to form a 100 nm thick resist underlayer film. A silicon-containing spin-on hard mask SHB-A940 (silicon content: 43% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. was then coated thereon and baked at 215°C for 60 seconds to form a 15 nm thick silicon-containing intermediate film. The above-mentioned adhesion film materials (AL-4, 5, 8, 10, 14-16, 23-29, 32, Comparative AL-1, 2, 7) were then coated thereon and baked at 250°C for 60 seconds to form a 5 nm thick adhesion film. A positive resist top layer film-forming composition (EUV single-layer resist) was then coated thereon and baked at 100°C for 60 seconds to form a 40 nm thick resist top layer film. In addition, after forming a silicon-containing intermediate film using the same method as above, a composition for forming a positive resist upper layer film (single-layer resist for EUV) was also applied directly onto the silicon-containing intermediate film without forming an adhesive film.

[0252] A composition for forming a positive resist upper layer film (EUV single-layer resist) was prepared by dissolving polymer compound PRP1 and quencher Q1 in a solvent containing 0.1 mass% of FC-4430 (manufactured by Sumitomo 3M Limited) in the proportions shown in Table 8, and filtering the solution through a 0.1 μm fluororesin filter. [Table 8]

[0253] Polymer compound: PRP1 Molecular weight (Mw)=9,200 Dispersity (Mw / Mn)=1.8 [ka]

[0254] Quencher: Q1 [ka]

[0255] Next, an 18 nm line and space (LS) 1:1 pattern was exposed using an EUV exposure system (ASML EUV Scanner NXE3400, NA 0.33, σ 0.9, 90-degree dipole illumination), baked at 90°C for 60 seconds (PEB), and developed in a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds, yielding a line and space pattern with a space width of 18 nm and a pitch of 36 nm. The cross-sectional shape and roughness of this pattern were observed using an electron microscope. In addition, the exposure dose required to form the line and space pattern was gradually increased to narrow the line dimensions, and the minimum dimension at which the lines could be resolved without collapsing was determined, and this was taken as the collapse limit (nm). The smaller the value, the higher the collapse resistance, making it preferable.

[0256] The cross-sectional shape of the obtained pattern was evaluated using an electron microscope (S-4700) manufactured by Hitachi, Ltd., and the pattern roughness was evaluated using an electron microscope (CG6300) manufactured by Hitachi High-Technologies Corporation. The results are shown in Table 9. Note that Comparative Example 4-4 shows the results of forming a silicon-containing intermediate film, and then applying a composition for forming a positive resist upper layer film (single-layer resist for EUV) directly on the silicon-containing intermediate film without forming an adhesive film, followed by patterning.

[0257] [Table 9]

[0258] As shown in Table 9, Examples 4-1 to 4-15, which used adhesion film materials (AL-4, 5, 8, 10, 14-16, 23-29, and 32), which are adhesion film-forming compositions of the present invention, exhibited less pattern roughness and better pattern shapes than the comparative examples. Examples 4-9 to 4-11, which used AL-24 to 26, which contained iodine atoms in structural units containing an organic sulfonyl anion structure, and Examples 4-13 to 4-14, which used AL-28 to 29, which incorporated iodine-containing structural units, exhibited particularly small pattern roughness. Regarding the comparative examples, Comparative Example 4-3, which used Comparative Example AL-7, a composition described in Patent Document 7, exhibited good results. However, Comparative Examples 4-1 and 4-2, which used Comparative Examples AL-1 and AL-2, which did not contain an organic sulfonyl anion structure, exhibited patterns with a footing shape and poor pattern roughness. Furthermore, in the case of Comparative Example 4-4, in which a composition for forming a positive resist upper layer film (single-layer resist for EUV) was applied directly onto a silicon-containing intermediate film and patterned, the pattern shape had a slight tailing and the pattern roughness was also high, which shows that the four-layer resist process using the composition for forming an adhesion film of the present invention has improved patterning performance compared to a three-layer resist process that does not use it.

[0259] Example 5 EUV Exposure Pattern Formation Test 2 Using Positive Resist (Examples 5-1 to 5-12, Comparative Examples 5-1 to 5-4) A silicon wafer substrate was coated with spin-on carbon ODL-301 (carbon content: 88% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. and baked at 350°C for 60 seconds to form a 100 nm thick resist underlayer film. A silicon-containing spin-on hard mask SHB-A940 (silicon content: 43% by mass) manufactured by Shin-Etsu Chemical Co., Ltd. was then coated thereon and baked at 215°C for 60 seconds to form a 15 nm thick silicon-containing intermediate film. The above-mentioned adhesion film materials (AL-14 to 16, 23 to 29, 32, 33, Comparative AL-1, 2, 7) were then coated thereon and baked at 250°C for 60 seconds to form a 5 nm thick adhesion film. Positive resist upper layer film-forming composition-2 was then coated thereon and baked at 105°C for 60 seconds to form a 50 nm thick resist upper layer film. In addition, after forming a silicon-containing intermediate film in the same manner as above, composition-2 for forming a positive resist upper layer film was applied directly onto the silicon-containing intermediate film without forming an adhesive film.

[0260] Positive resist top layer film forming composition-2 (EUV single-layer resist) was prepared by dissolving polymer compound PRP2, thermal acid generator PAG2, and quencher Q2 in a propylene glycol monomethyl ether acetate (PGMEA) and diacetone alcohol (DAA) solvent containing 0.01 mass% PF636 (manufactured by OMNOVA) in the proportions shown in Table 10, and filtering the solution through a 0.1 μm fluororesin filter.

[0261] [Table 10]

[0262] Polymer compound: PRP2 Molecular weight (Mw)=5,200 Dispersity (Mw / Mn)=1.45 [ka]

[0263] Thermal acid generator: PAG2 [ka]

[0264] Quencher: Q2 [ka]

[0265] The resist top layer was then exposed to light using an ASML EUV scanner NXE3400 (NA 0.33, σ 0.9 / 0.6, quadrupole illumination, a 40 nm pitch on the wafer, +20% bias hole pattern mask). PEB was performed on a hot plate at 80°C for 60 seconds, followed by development in a 2.38 wt% TMAH aqueous solution for 30 seconds to form a 20 nm hole pattern. The cross-sectional shape and CDU of this pattern were observed using an electron microscope. The dimensions of 50 holes were measured at an exposure dose required to form 20 nm holes, and the CDU was calculated as three times the standard deviation (σ) (3σ).

[0266] The cross-sectional shape of the pattern obtained was evaluated using an electron microscope (S-4700) manufactured by Hitachi, Ltd., and the CDU was evaluated using an electron microscope (CG6300) manufactured by Hitachi High-Technologies Corp. The results are shown in Table 11.

[0267] [Table 11]

[0268] As shown in Table 11, Examples 5-1 to 5-12, which used adhesion film materials (AL-14 to 16, 23 to 29, 32, and 33), which are adhesion film-forming compositions of the present invention, had smaller CDUs and better pattern shapes than the comparative examples. Examples 5-5 to 5-7, which used AL-24 to 26, which contain iodine atoms in structural units containing an organic sulfonyl anion structure, and Examples 5-9 to 5-10, which used AL-28 to 29, which incorporate iodine-containing structural units, had particularly small CDUs. Regarding the comparative examples, Comparative Example 5-3, which used Comparative AL-7, a composition described in Patent Document 7 that showed good results in Comparative Example 4-3, also produced a pattern with a footing shape, demonstrating that the organic sulfonyl anion structure is effective in improving the footing shape of the pattern. Furthermore, in the case of Comparative Example 5-4, in which a composition for forming a positive resist upper layer film was applied directly onto a silicon-containing intermediate film and patterned, the pattern shape became a tailing shape and the CDU was also large, which shows that the four-layer resist process using the composition for forming an adhesion film of the present invention has significantly improved patterning performance compared to the three-layer resist process not using the composition.

[0269] Example 6 Electron beam pattern formation test (Examples 6-1 to 6-12, Comparative Examples 6-1 to 6-3) The above adhesion film materials (AL-14 to 16, 23 to 29, 32, 33, Comparative AL-1, 6, 7) were applied to a silicon wafer substrate and baked at 250°C for 60 seconds to form an adhesion film with a thickness of 5 nm, and then a resist top layer film material (metal-containing resist) was applied thereon and baked at 180°C for 60 seconds to form a resist top layer film with a thickness of 50 nm.

[0270] The resist top layer film material (metal-containing resist) was prepared by dissolving a titanium-containing compound (AM-1) and a metal salt sensitizer (S-1) in 4-methyl-2-pentanol (MIBC) containing 0.1 mass% FC-4430 (Sumitomo 3M Limited) in the proportions shown in Table 12, and filtering the solution through a 0.1 μm fluororesin filter.

[0271] [Table 12]

[0272] Synthesis of titanium-containing compound (AM-1) A solution of 284 g of titanium tetraisopropoxide (Tokyo Chemical Industry Co., Ltd.) in 500 g of 2-propanol (IPA) was added dropwise to the resulting solution over 2 hours with stirring. 180 g of 2,4-dimethyl-2,4-octanediol was added and stirred at room temperature for 30 minutes. The resulting solution was concentrated under reduced pressure at 30°C and then heated to 60°C until no more distillate was produced. When no more distillate was observed, 1,200 g of 4-methyl-2-pentanol (MIBC) was added and the mixture was heated at 40°C under reduced pressure until no more IPA was produced, yielding 1,000 g of a MIBC solution of titanium-containing compound AM-1 (compound concentration: 25% by mass). The molecular weight of this compound measured in terms of polystyrene was found to be Mw = 1,200.

[0273] Metal salt sensitizer: S-1 [ka]

[0274] Next, writing was performed in a vacuum chamber using a JBX-9000MV (manufactured by JEOL Ltd.) at an accelerating voltage of 50 kV. Immediately after writing, the wafer was baked (PEB) at 200°C for 60 seconds, and then puddle developed with butyl acetate for 20 seconds to obtain a negative pattern.

[0275] The resulting negative patterns were evaluated as follows. The exposure dose required to resolve 100 nm lines and spaces (LS) at a 1:1 ratio was defined as sensitivity, and the minimum dimension at which the lines could be resolved without collapsing at that exposure dose was determined and defined as the collapse limit (nm). The smaller the value, the higher the collapse resistance, which is preferable. The results are shown in Table 13.

[0276] [Table 13]

[0277] As shown in Table 13, Examples 6-1 to 6-12, which used adhesion film materials (AL-14 to 16, 23 to 29, 32, and 33), which are adhesion film-forming compositions of the present invention, had smaller collapse limits than Comparative Examples 6-1 to 6-3, which used Comparative Examples AL-1, 6, and 7. This is thought to be due to the interaction of the nitrogen-hydrogen bond in the structure represented by general formula (1) with the metal oxide in the metal-containing resist pattern. From the above, it can be seen that the present invention can also be suitably used in lithography processes for metal-containing resists.

[0278] From the above, the composition for forming an adhesion film of the present invention is extremely useful as a composition for forming an adhesion film to be used in a multilayer resist method, since it can form an adhesion film that exhibits good coatability even on a hydrophobic underlayer film and has good pattern collapse suppression performance and the ability to remove resist residue at the bottom of the pattern, and the pattern formation method of the present invention using this composition can form a fine pattern on the substrate to be processed with high precision.

[0279] The present specification includes the following aspects. [1]: A composition for forming an adhesion film, (A) a resin containing a repeating unit represented by the following general formula (1) and a repeating unit having an organic sulfonyl anion structure, and (B) an organic solvent, A composition for forming an adhesion film, comprising: [ka] (wherein X is a single bond or an aromatic ring having 20 or less carbon atoms, and R 01 is a hydrogen atom or a methyl group, and R 02 is a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms, and R 02 When is an alkyl group, a hydrogen atom constituting the alkyl group may be substituted with a hydroxyl group. [2]: The composition for forming an adhesion film according to [1] above, characterized in that the ratio of the repeating unit represented by the general formula (1) among the repeating units of the resin (A) is 70 mol % or more and 99.9 mol % or less. [3]: The composition for forming an adhesion film according to [1] or [2], characterized in that the ratio of the repeating units having the organic sulfonyl anion structure in the repeating units of the resin (A) is 0.1 mol % or more and 30 mol % or less. [4]: The composition for forming an adhesion film according to any one of [1] to [3] above, wherein the weight average molecular weight of the resin (A) is 1,000 to 70,000. [5]: The composition for forming an adhesion film according to any one of [1] to [4], wherein the (B) organic solvent is a mixture of one or more organic solvents having a boiling point of less than 150°C and one or more organic solvents having a boiling point of 150°C or more and less than 220°C. [6]: The composition for forming an adhesion film according to any one of [1] to [5] above, further comprising one or more selected from (C) a thermal acid generator, (D) a surfactant, and (E) a crosslinking agent. [7]: A method for forming a pattern on a workpiece substrate, (I-1) A step of applying any one of the compositions for forming an adhesion film according to [1] to [6] above onto a substrate to be processed, followed by heat treatment to form an adhesion film; (I-2) forming a resist upper layer film on the adhesion film using a photoresist material; (I-3) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (I-4) a step of transferring the pattern to the adhesive film by dry etching using the resist upper layer film on which the circuit pattern is formed as a mask; and (I-5) a step of processing the substrate to be processed using the resist top layer film and / or adhesive film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed; A pattern forming method comprising the steps of: [8]: A method for forming a pattern on a workpiece substrate, (II-1) forming a resist underlayer film on a substrate to be processed; (II-2) forming a silicon-containing resist intermediate film on the resist underlayer film; (II-3) A step of applying any one of the compositions for forming an adhesion film according to [1] to [6] above onto the silicon-containing resist intermediate film, followed by heat treatment to form an adhesion film; (II-4) forming a resist upper layer film on the adhesion film using a photoresist material; (II-5) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (II-6) a step of transferring the pattern to the adhesive film by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask; (II-7) a step of transferring the pattern to the silicon-containing resist intermediate film by dry etching using the resist upper layer film and / or adhesive film on which the pattern has been formed as a mask; (II-8) a step of transferring a pattern to the resist underlayer film by dry etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; and (II-9) a step of processing the substrate to be processed using the resist underlayer film to which the pattern has been transferred as a mask to form a pattern on the substrate to be processed; A pattern forming method comprising the steps of: [9]: A method for forming a pattern on a workpiece substrate, (III-1) forming a resist underlayer film on a substrate to be processed; (III-2) forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist underlayer film; (III-3) A step of applying any one of the compositions for forming an adhesion film according to [1] to [6] above onto the inorganic hard mask intermediate film, followed by heat treatment to form an adhesion film; (III-4) forming a resist upper layer film on the adhesion film using a photoresist material; (III-5) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (III-6) a step of transferring the pattern to the adhesive film by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask; (III-7) a step of transferring a pattern onto the inorganic hard mask intermediate film by dry etching using the resist upper layer film and / or adhesive film on which the pattern has been formed as a mask; (III-8) transferring a pattern to the resist underlayer film by dry etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; and (III-9) a step of processing the substrate to be processed using the resist underlayer film to which the pattern has been transferred as a mask to form a pattern on the substrate to be processed; A pattern forming method comprising the steps of:

[10] : The pattern forming method according to [9] above, wherein the inorganic hard mask intermediate film is formed by a CVD method or an ALD method.

[11] : The pattern forming method according to any one of [7] to

[10] above, characterized in that a circuit pattern is formed on the resist upper layer film by using photolithography with a wavelength of 10 nm or more and 300 nm or less, direct writing using an electron beam, nanoimprinting, or a combination thereof.

[12] : The pattern forming method according to any one of [7] to

[11] above, wherein the photoresist material contains at least an organometallic compound and a solvent.

[13] : The pattern forming method according to any one of [7] to

[12] above, characterized in that alkali development or development with an organic solvent is used as the development method.

[14] : The pattern forming method according to any one of [7] to

[13] above, characterized in that the substrate to be processed is a semiconductor device substrate, or a semiconductor device substrate having any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film formed thereon.

[15] : The pattern formation method according to

[14] , characterized in that the metal used is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or an alloy thereof.

[16] : A method for forming an adhesion film used in the manufacturing process of a semiconductor device, comprising spin-coating a composition for forming an adhesion film according to any one of [1] to [6] above onto a substrate to be processed, and heat-treating the substrate coated with the composition for forming an adhesion film at a temperature of 100°C or higher and 300°C or lower for 10 to 600 seconds to form an adhesion film.

[17] : A method for forming an adhesion film used in the manufacturing process of a semiconductor device, comprising spin-coating a composition for forming an adhesion film according to any one of [1] to [6] above onto a substrate to be processed, and heat-treating the substrate coated with the composition for forming an adhesion film in an atmosphere having an oxygen concentration of 0.1% or more and 21% or less, thereby forming an adhesion film.

[18] : A method for forming an adhesion film used in the manufacturing process of a semiconductor device, comprising spin-coating a composition for forming an adhesion film according to any one of [1] to [6] above onto a substrate to be processed, and heat-treating the substrate coated with the composition for forming an adhesion film in an atmosphere having an oxygen concentration of 0.0001% or more and less than 0.1%, thereby forming an adhesion film.

[0280] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention. [Explanation of symbols]

[0281] 1...substrate, 2...processed layer, 2a...pattern (pattern formed on the processed layer), 3...resist underlayer film, 3a...resist underlayer film pattern, 4...silicon-containing interlayer film, 4a...silicon-containing interlayer film pattern, 5...adhesive film, 5a...adhesive film pattern, 6...resist upper layer film, 6a...resist upper layer film pattern, 7...exposed portion.

Claims

1. A composition for forming an adhesion film, (A) a resin containing a repeating unit represented by the following general formula (1) and a repeating unit having an organic sulfonyl anion structure, and (B) an organic solvent, A composition for forming an adhesion film, comprising: 【Chemistry 1】 (wherein X is a single bond or an aromatic ring having 20 or less carbon atoms, R ０１ is a hydrogen atom or a methyl group, and R ０２ is a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms, and R ０２ When is an alkyl group, a hydrogen atom constituting the alkyl group may be substituted with a hydroxyl group.

2. 2. The adhesive film-forming composition according to claim 1, wherein the ratio of the repeating unit represented by the general formula (1) to the repeating units of the resin (A) is 70 mol % or more and 99.9 mol % or less.

3. 2. The adhesive film-forming composition according to claim 1, wherein the ratio of the repeating unit having the organic sulfonyl anion structure to the repeating units of the resin (A) is 0.1 mol % or more and 30 mol % or less.

4. 2. The adhesive film-forming composition according to claim 1, wherein the weight average molecular weight of the resin (A) is 1,000 to 70,000.

5. 2. The adhesive film-forming composition according to claim 1, wherein the organic solvent (B) is a mixture of one or more organic solvents having a boiling point of less than 150°C and one or more organic solvents having a boiling point of 150°C or more and less than 220°C.

6. 2. The adhesive film-forming composition according to claim 1, further comprising at least one selected from the group consisting of (C) a thermal acid generator, (D) a surfactant, and (E) a crosslinking agent.

7. A method for forming a pattern on a workpiece substrate, comprising: (I-1) A step of applying the composition for forming an adhesion film according to any one of claims 1 to 6 onto a substrate to be processed, followed by heat treatment to form an adhesion film; (I-2) forming a resist upper layer film on the adhesion film using a photoresist material; (I-3) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (I-4) a step of transferring the pattern to the adhesive film by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask; and (I-5) a step of processing the substrate to be processed using the resist top layer film and / or adhesive film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed; A pattern forming method comprising the steps of:

8. A method for forming a pattern on a workpiece substrate, comprising: (II-1) forming a resist underlayer film on a substrate to be processed; (II-2) forming a silicon-containing resist intermediate film on the resist underlayer film; (II-3) A step of applying the composition for forming an adhesion film according to any one of claims 1 to 6 onto the silicon-containing resist intermediate film, and then performing a heat treatment to form an adhesion film; (II-4) forming a resist upper layer film on the adhesion film using a photoresist material; (II-5) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (II-6) a step of transferring the pattern to the adhesive film by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask; (II-7) a step of transferring the pattern to the silicon-containing resist intermediate film by dry etching using the resist upper layer film and / or adhesive film on which the pattern has been formed as a mask; (II-8) a step of transferring a pattern to the resist underlayer film by dry etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; and (II-9) a step of processing the substrate to be processed using the resist underlayer film to which the pattern has been transferred as a mask to form a pattern on the substrate to be processed; A pattern forming method comprising the steps of:

9. A method for forming a pattern on a workpiece substrate, comprising: (III-1) forming a resist underlayer film on a substrate to be processed; (III-2) forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the resist underlayer film; (III-3) A step of applying the composition for forming an adhesion film according to any one of claims 1 to 6 onto the inorganic hard mask intermediate film, and then heat-treating the composition to form an adhesion film; (III-4) forming a resist upper layer film on the adhesion film using a photoresist material; (III-5) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a circuit pattern on the resist upper layer film; (III-6) a step of transferring the pattern to the adhesive film by dry etching using the resist upper layer film on which the circuit pattern has been formed as a mask; (III-7) a step of transferring a pattern onto the inorganic hard mask intermediate film by dry etching using the resist upper layer film and / or adhesive film on which the pattern has been formed as a mask; (III-8) transferring the pattern to the resist underlayer film by dry etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; and (III-9) a step of processing the substrate to be processed using the resist underlayer film to which the pattern has been transferred as a mask to form a pattern on the substrate to be processed; A pattern forming method comprising the steps of:

10. 10. The pattern formation method according to claim 9, wherein the inorganic hard mask intermediate film is formed by a CVD method or an ALD method.

11. 8. The pattern forming method according to claim 7, wherein a method for forming a circuit pattern on the resist upper layer film is photolithography with a wavelength of 10 nm or more and 300 nm or less, direct writing using an electron beam, nanoimprinting, or a combination thereof.

12. 8. The pattern forming method according to claim 7, wherein the photoresist material contains at least an organometallic compound and a solvent.

13. 8. The pattern forming method according to claim 7, wherein the development is carried out using an alkali development or an organic solvent.

14. 8. The pattern forming method according to claim 7, wherein the workpiece substrate is a semiconductor device substrate, or a semiconductor device substrate having any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film formed thereon.

15. 15. The pattern formation method according to claim 14, wherein the metal is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, cobalt, manganese, molybdenum, or an alloy thereof.

16. A method for forming an adhesion film used in a manufacturing process of a semiconductor device, comprising spin-coating the composition for forming an adhesion film according to any one of claims 1 to 6 onto a substrate to be processed, and heat-treating the substrate coated with the composition for forming an adhesion film at a temperature of 100°C or higher and 300°C or lower for 10 to 600 seconds, thereby forming an adhesion film.

17. A method for forming an adhesion film used in the manufacturing process of a semiconductor device, comprising spin-coating a composition for forming an adhesion film according to any one of claims 1 to 6 onto a substrate to be processed, and heat-treating the substrate coated with the composition for forming an adhesion film in an atmosphere having an oxygen concentration of 0.1% or more and 21% or less, thereby forming an adhesion film.

18. A method for forming an adhesion film used in the manufacturing process of a semiconductor device, comprising spin-coating a composition for forming an adhesion film according to any one of claims 1 to 6 onto a substrate to be processed, and heat-treating the substrate coated with the composition for forming an adhesion film in an atmosphere having an oxygen concentration of 0.0001% or more and less than 0.1%, thereby forming an adhesion film.

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