Composition for forming organic film, method for forming organic film, method for forming pattern and surfactant

Abstract

The invention relates to a composition for forming an organic film, a method for forming an organic film, a method for forming a pattern, and a surfactant. Provided is a composition which is capable of forming an organic film having excellent film-forming properties, landfill properties, and bump suppression properties, and also having excellent processing margin when used as an organic film. A composition for forming an organic film, comprising: a material for forming an organic film; an aryl benzyl ether compound having a partial structure represented by general formula (B1); and a solvent. In the formula # imgabs0, R1 represents a hydrogen atom or an arbitrary fluorine-containing group represented by formula (B2), and in R1, when the ratio of the hydrogen atom is alpha and the ratio of the group represented by formula (B2) is beta, the relationships alpha + beta = 1, 0.1 < = alpha < = 0.5, and 0.5 < = beta < = 0.9 are satisfied. R2 is a C1-30 saturated or unsaturated monovalent organic group, a = 0 or 1, b is 1-5 when a = 0, c is 0-4, b is 1-7 when a = 1, c is 0-6, and * represents an atomic bond with other atoms. # imgabs1 #

Description

Technical Field

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

[0002] In recent years, with the high integration and high speed of semiconductor elements, finer patterning rules have been required. As a general-purpose technology, in lithography using optical exposure, various technical developments have been made on how to perform finer and more accurate pattern processing for the light source used.

[0003] Regarding the light source for lithography used when forming a resist pattern, optical exposure using g-ray (436 nm) or i-ray (365 nm) of a mercury lamp as the light source is widely used in parts with a low density. On the other hand, in parts with a high density where finer patterning is required, lithography using a KrF excimer laser (248 nm) or an ArF excimer laser (193 nm) with a shorter wavelength has been put into practical use. In the most advanced generation that requires even finer patterning, lithography using extreme ultraviolet (EUV, 13.5 nm) has also approached practical use.

[0004] If the thinning of the resist pattern continues as described above, in the single-layer resist method, which is a typical photoresist pattern forming method, it is known that the ratio of the height of the pattern to the line width of the pattern (aspect ratio) increases, and pattern collapse occurs due to the surface tension of the developing solution during development. When forming a pattern with a high aspect ratio on a substrate with a height difference, the multi-layer resist method of forming a pattern by laminating films with different dry etching characteristics is excellent. A two-layer resist method (Patent Document 1, etc.) combining a photoresist layer made of a silicon-containing photosensitive polymer and a lower layer made of an organic polymer having carbon, hydrogen, and oxygen as main constituent elements, such as a novolak-based polymer, and a three-layer resist method (Patent Document 2, etc.) combining a photoresist layer made of an organic photosensitive polymer used in the single-layer resist method, an intermediate layer made of a silicon-based polymer or a silicon-based CVD film, and a lower layer made of an organic polymer have been developed.

[0005] In this three-layer resist method, for example, an organic film made of novolak or the like is uniformly formed as an underlayer resist film on a substrate to be processed, a silicon-containing resist intermediate film is formed thereon as an intermediate resist film, and a normal organic photoresist film is formed thereon as an upper layer resist film. For dry etching with a fluorine-based gas plasma, the organic upper layer resist film can achieve a good etching selectivity with respect to the silicon-containing resist intermediate film. Therefore, the resist pattern can be transferred to the silicon-containing resist intermediate film by dry etching using a fluorine-based gas plasma. According to this method, even when using a resist composition that is difficult to form a pattern with a sufficient film thickness for directly processing the substrate to be processed or a resist composition with insufficient dry etching resistance for processing the substrate, it is still possible to transfer the pattern to the silicon-containing resist intermediate film. If the pattern transfer using dry etching with an oxygen-based gas plasma is continued, a pattern with an organic film (such as an underlayer resist film like a novolak film) having sufficient dry etching resistance for processing can be obtained.

[0006] As described above, multiple techniques for the above-mentioned organic film (organic underlayer film) are already known (for example, Patent Document 3). However, with the recent progress in miniaturization, in addition to dry etching characteristics, the necessity for excellent filling characteristics has also increased. There is a need for an organic film material that can be uniformly formed even on a substrate to be processed with a complex shape and has filling characteristics that can fill the necessary pattern without voids.

[0007] For the above-mentioned organic film, a coater / developer capable of performing processes such as a spin coating step, an EBR step, and a baking step is used to form the film when manufacturing a semiconductor substrate or the like. The EBR (Edge Bead Removal) step refers to a step of removing the film at the edge of the substrate after a film is formed on the substrate (wafer) by spin coating in order to prevent contamination of the substrate transfer arm of the coater / developer. The removing liquid used in the EBR step is, for example, a mixed liquid of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether (30% by mass: 70% by mass). Such a removing liquid is widely used in the EBR step of the upper layer resist film, the underlayer resist film (silicon-containing resist intermediate film, organic film).

[0008] Due to the influence of the removing agent in the EBR step, a state where the film thickness is relatively thick (bulge) may sometimes be formed at the outer peripheral portion of the organic film. In the dry etching step during the above-mentioned substrate processing, the bulge may cause defects, so an organic film with suppressed bulge is required.

[0009] Further, after the organic film forms a spin-coated film, in order to be used in a multi-layer resist process, a baking treatment is performed to form a hardened film. In order to coat a silicon-containing resist intermediate film on the upper layer, it needs to be an insoluble and infusible organic film. The surface of the organic film formed by the baking treatment will form a hydrophobic surface due to the surfactant contained in the organic film-forming composition, and sometimes it will induce abnormal coating of the silicon-containing resist intermediate film. In order to improve the coatability of the silicon-containing resist intermediate film and increase the processing margin, it is necessary to control the contact angle of the surface of the organic film.

[0010] [Prior Art Documents]

[0011] [Patent Documents]

[0012] [Patent Document 1] Japanese Patent Laid-Open No. 6-118651

[0013] [Patent Document 2] Japanese Patent Laid-Open No. 2005-128509

[0014] [Patent Document 3] Japanese Patent Laid-Open No. 2004-205685 Summary of the Invention

[0015] [Problems to be Solved by the Invention]

[0016] In view of the above situation, an object of the present invention is to provide an organic film-forming composition capable of forming an organic film having excellent film-forming properties (in-plane uniformity) and filling characteristics on a substrate (wafer), excellent bulge suppression properties during the EBR step, and excellent processing margins when used as an organic film for multi-layer resists, an organic film-forming method and a pattern-forming method using this composition, and a surfactant of a compound used in the above-mentioned organic film-forming composition.

[0017] [Means for Solving the Problems]

[0018] In order to solve the above problems, the present invention provides an organic film-forming composition, which is characterized by containing:

[0019] (A) A material for forming an organic film,

[0020] (B) An aryl benzyl ether compound having a partial structure represented by the following general formula (B1), and

[0021] (C) A solvent.

[0022] [Chemical Formula 1]

[0023]

[0024] In the formula, R1 is a hydrogen atom or any fluorine-containing group represented by the following formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the following formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, a is 0 or 1. When a is 0, b is 1 to 5 and c is 0 to 4. When a is 1, b is 1 to 7 and c is 0 to 6. * represents a chemical bond with other atoms.

[0025] [Chemical formula 2]

[0026]

[0027] In the formula, the dashed line represents a chemical bond with the oxygen atom in the above formula (B1), and it may also have one or two of the structures represented by the above formula (B2).

[0028] If it is such a composition for forming an organic film, an organic film with excellent in-plane uniformity and filling properties and with the formation of bulges caused by the influence of the removing agent in the EBR step being suppressed can be formed. Also, since the phenolic hydroxyl group is modified with the structure represented by the above formula (B2), the hydrophobic components concentrated on the surface of the organic film during baking when forming the hardened film will be thermally decomposed at the benzyl position to generate phenolic hydroxyl groups. As a result, the contact angle of the organic film surface can be reduced, so it will become a composition for forming an organic film on which an intermediate film such as a silicon-containing intermediate film can be formed with excellent coatability. Also, by adjusting the proportion of the structures α and β within the above range, even in a low-temperature region where thermal decomposition does not occur at the benzyl position, the contact angle can still be adjusted due to the sufficient presence of phenolic hydroxyl groups, and it will become a composition for forming an organic film on which an intermediate film such as a silicon-containing intermediate film can be formed with excellent coatability. That is, according to the composition for forming an organic film of the present invention, an organic film with excellent film-forming properties and filling properties on a substrate, excellent bulge suppression properties during the EBR step, and excellent processing margin when used as an organic film for a multilayer resist can be formed.

[0029] In the present invention, it is preferable that the aforementioned (B) aryl benzyl ether compound is a compound represented by the following general formula (B3), (B4), (B6), (B8), (B10), or (B11).

[0030] [Chemical formula 3]

[0031]

[0032] In the formula, R1 is a hydrogen atom, or one or two of the fluorine-containing groups represented by the foregoing formula (B2). Among the structures constituting the foregoing R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing groups represented by the above formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, R3 is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, a1 is 0 or 1, when a1 is 0, b1 is 1 to 5, c1 is 0 to 4, and when a1 is 1, b1 is 1 to 7, c1 is 0 to 6.

[0033] [Chemical formula 4]

[0034]

[0035] In the formula, R1 is a hydrogen atom or one or two of the fluorine-containing groups represented by the above formula (B2). Among the structures constituting the foregoing R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing groups represented by the above formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, R4 is a single bond or any one of the groups represented by the following formula (B5), R5 is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, a2 is 0 or 1, when a2 is 0, b2 is 1 to 5, c2 is 0 to 4, and when a2 is 1, b2 is 1 to 7, c2 is 0 to 6.

[0036] [Chemical formula 5]

[0037]

[0038] [Chemical formula 6]

[0039]

[0040] In the formula, R1 is a hydrogen atom or one or two of the fluorine-containing groups represented by the above formula (B2). Among the structures constituting the foregoing R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing groups represented by the above formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, R6 is any group represented by the following formula (B7), R7 is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, a3 is 0 or 1, when a3 is 0, b3 is 1 to 5, c3 is 0 to 4, and when a3 is 1, b3 is 1 to 7, c3 is 0 to 6.

[0041] [Chemical formula 7]

[0042]

[0043] [Chemical formula 8]

[0044]

[0045] In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of the hydrogen atom is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. W1 is a group represented by the following formula (B9), a4 is 0 or 1, b4 is 1 or 2, and d4 is 1 to 4.

[0046] [Chemical formula 9]

[0047]

[0048] In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of the hydrogen atom is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied.

[0049] [Chemical formula 10]

[0050]

[0051] In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of the hydrogen atom is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. W1 is a group represented by the above formula (B9), W2 is a single bond or an organic group having 1 to 50 carbon atoms, m is an integer satisfying 1 ≤ m ≤ 5, a5 is 0 or 1, b5 is 1 or 2, and d5 is 1 to 4.

[0052] [Chemical formula 11]

[0053]

[0054] In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of the hydrogen atom is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R8 is a hydrogen atom or a methyl group, and b6 is 1 to 5.

[0055] In the case of a composition for forming an organic film containing such a (B) aryl benzyl ether compound, by having an appropriate fluorine content, the film-forming property during coating can be improved, and the decomposition products generated during baking do not damage the in-plane uniformity of the film and do not cause the formation of insoluble components due to the reaction between the decomposition products. Therefore, it does not narrow the processing margin when forming the organic film, and device contamination, defects, etc. do not occur.

[0056] Furthermore, the weight average molecular weight of the aforementioned (B) aryl benzyl ether compound is preferably 1000 to 30000.

[0057] In the case of such a weight average molecular weight range, an organic film with better film-forming property and filling characteristics can be formed.

[0058] Furthermore, relative to 100 parts by mass of the content of the aforementioned (A) material for forming an organic film, the content of the aforementioned (B) aryl benzyl ether compound is preferably 0.01 parts by mass to 5 parts by mass.

[0059] In the case of a composition for forming an organic film containing the aforementioned (B) aryl benzyl ether compound in such a content, the in-plane uniformity of the formed organic film is better, which is ideal.

[0060] Furthermore, the present invention provides a method for forming an organic film, which is a method for forming an organic film used in the manufacturing process of a semiconductor device, and is characterized in that:

[0061] The composition for forming an organic film of the present invention is spin-coated on a substrate to be processed to obtain a coating film,

[0062] The aforementioned coating film is heat-treated at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds to be hardened to form an organic film.

[0063] The composition for forming an organic film of the present invention is particularly useful for filling complex-shaped patterns on a substrate to be processed by spin coating and forming an organic film with excellent in-plane uniformity, suppressing swelling in the EBR process, and removing the organic film at the ends. Therefore, according to the method for forming an organic film of the present invention, an organic film with excellent film-forming property, excellent filling characteristics, excellent swelling suppression in the EBR process, and excellent processing margin when used as an organic film for a multilayer resist can be formed.

[0064] Furthermore, the present invention provides a pattern forming method, which is characterized in that:

[0065] An organic film is formed on a workpiece using the composition for forming an organic film of the present invention,

[0066] A silicon-containing resist intermediate film is formed on the aforementioned organic film using a silicon-containing resist intermediate film material,

[0067] An upper resist film is formed using a resist upper film material composed of a photoresist composition on the aforementioned silicon-containing resist intermediate film.

[0068] A circuit pattern is formed in the aforementioned upper resist film, and the upper resist film with the formed circuit pattern is used as a mask to transfer the pattern to the aforementioned silicon-containing resist intermediate film by etching.

[0069] The silicon-containing resist intermediate film with the transferred pattern is used as a mask to transfer the pattern to the aforementioned organic film by etching.

[0070] Then, the organic film with the transferred pattern is used as a mask to form the pattern on the aforementioned workpiece by etching.

[0071] Moreover, the present invention provides a pattern forming method, characterized in that:

[0072] An organic film is formed on the workpiece using the composition for forming an organic film of the present invention.

[0073] A silicon-containing resist intermediate film is formed on the aforementioned organic film using a silicon-containing resist intermediate film material, and an organic antireflection film or a bonding film is formed on the aforementioned silicon-containing resist intermediate film.

[0074] An upper resist film is formed on the aforementioned organic antireflection film or bonding film using a resist upper film material composed of a photoresist composition, and a circuit pattern is formed in the aforementioned upper resist film.

[0075] The upper resist film with the formed circuit pattern is used as a mask to transfer the pattern to the aforementioned organic antireflection film or bonding film and the aforementioned silicon-containing resist intermediate film by etching.

[0076] The silicon-containing resist intermediate film with the transferred pattern is used as a mask to transfer the pattern to the aforementioned organic film by etching.

[0077] Then, the organic film with the transferred pattern is used as a mask to form the pattern on the aforementioned workpiece by etching.

[0078] Moreover, the present invention provides a pattern forming method, characterized in that:

[0079] An organic film is formed on the workpiece using the composition for forming an organic film of the present invention.

[0080] An inorganic hard mask selected from the group consisting of a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the aforementioned organic film.

[0081] An upper resist film is formed on the aforementioned inorganic hard mask using a resist upper film material composed of a photoresist composition.

[0082] A circuit pattern is formed on the upper resist film described above.

[0083] Using the upper resist film on which the circuit pattern has been formed as a mask, the pattern is transferred to the inorganic hard mask described above by etching.

[0084] Using the inorganic hard mask on which the pattern has been transferred as a mask, the pattern is transferred to the organic film described above by etching.

[0085] Then, using the organic film on which the pattern has been transferred as a mask, the pattern is formed on the workpiece described above by etching.

[0086] Further, the present invention provides a pattern forming method, characterized in that:

[0087] An organic film is formed on the workpiece using the composition for forming an organic film of the present invention.

[0088] An inorganic hard mask selected from the group consisting of a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the organic film described above.

[0089] An organic anti-reflection film or a bonding film is formed on the inorganic hard mask described above, and an upper resist film is formed on the organic anti-reflection film or the bonding film using a resist upper film material composed of a photoresist composition.

[0090] A circuit pattern is formed on the upper resist film described above.

[0091] Using the upper resist film on which the circuit pattern has been formed as a mask, the pattern is transferred to the organic anti-reflection film or the bonding film and the inorganic hard mask described above by etching.

[0092] Using the inorganic hard mask on which the pattern has been transferred as a mask, the pattern is transferred to the organic film described above by etching.

[0093] Then, using the organic film on which the pattern has been transferred as a mask, the pattern is formed on the workpiece described above by etching.

[0094] Thus, the composition for forming an organic film of the present invention can be ideally used in various pattern forming methods such as a three-layer resist process using a silicon-containing resist intermediate film or an inorganic hard mask, and a four-layer resist process using an organic anti-reflection film or a bonding film in addition. In such a pattern forming method of the present invention, the circuit pattern of the upper resist film can be transferred and formed on the workpiece with high precision.

[0095] Further, it is preferable to form the inorganic hard mask described above by CVD method or ALD method.

[0096] The pattern forming method of the present invention can form an inorganic hard mask by such a method, for example.

[0097] Further, in the formation of the foregoing circuit pattern, it is preferable to form the circuit pattern by lithography using light having a wavelength of 10 nm or more and 300 nm or less, direct drawing using an electron beam, nanoimprinting, or a combination thereof.

[0098] Further, in the formation of the foregoing circuit pattern, it is preferable to develop the circuit pattern using alkali development or an organic solvent.

[0099] The pattern formation method of the present invention can desirably use such means for forming a circuit pattern and means for development.

[0100] Further, it is preferable that the foregoing workpiece is a semiconductor device substrate, or any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, and a metal oxynitride film formed on the foregoing semiconductor device substrate.

[0101] In this case, as the foregoing workpiece, it is preferable to use silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof as the metal constituting the workpiece.

[0102] If it is the pattern formation method of the present invention, the foregoing workpiece can be processed to form a pattern.

[0103] Further, the present invention provides a surfactant composed of an aryl benzyl ether compound having a partial structure represented by the following general formula (B1).

[0104] [Chemical formula 12]

[0105]

[0106] In the formula, R1 is a hydrogen atom or an arbitrary fluorine-containing group represented by the following formula (B2). Among the structures constituting the foregoing R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the following formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, a is 0 or 1. When a is 0, b is 1 to 5 and c is 0 to 4. When a is 1, b is 1 to 7 and c is 0 to 6. * represents an atomic bond with other atoms.

[0107] [Chemical formula 13]

[0108]

[0109] In the formula, the dotted line represents an atomic bond with the oxygen atom in the above formula (B1), and may have one or two of the structures represented by the above formula (B2).

[0110] Such a surfactant, when combined with a fluorine substituent having a structure represented by the above formula (B2), can form an organic film with excellent in-plane uniformity and filling properties, and the formation of ridges caused by the influence of the remover in the EBR step is suppressed. Therefore, it becomes an ideal surfactant. Further, since it is a surfactant in which the phenolic hydroxyl group and the fluorine substituent having a structure represented by the above formula (B2) are adjusted to the above ranges of the ratios α and β, when the surfactant of the present invention is used as a composition for forming an organic film in the formation of an organic film, even in a low-temperature range where it does not thermally decompose at the benzyl position, the contact angle can be adjusted due to the sufficient presence of the phenolic hydroxyl group, and an organic film forming composition capable of forming an organic film on which an intermediate film such as a silicon-containing intermediate film can be formed with excellent coatability can be achieved.

[0111] Furthermore, the surfactant of the present invention is not limited to the composition for forming an organic film, and can be usefully used in the entire coating material for optical lithography. Further, as long as it is a composition containing a surfactant, various compositions of the present invention are useful, and its uses are not only industrial uses, but also extend to daily necessities such as cosmetics.

[0112] In the present invention, the aforementioned aryl benzyl ether compound is preferably a compound represented by the following general formulas (B3), (B4), (B6), (B8), (B10), or (B11).

[0113] [Chemical Formula 14]

[0114]

[0115] In the formula, R1 is a hydrogen atom, or one or two of the fluorine-containing groups represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of the hydrogen atom is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, R3 is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, a1 is 0 or 1, when a1 is 0, b1 is 1 to 5, c1 is 0 to 4, and when a1 is 1, b1 is 1 to 7, c1 is 0 to 6.

[0116] [Chemical Formula 15]

[0117]

[0118] In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, R4 is a single bond or any one of the groups represented by the following formula (B5), R5 is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, a2 is 0 or 1. When a2 is 0, b2 is 1 to 5 and c2 is 0 to 4. When a2 is 1, b2 is 1 to 7 and c2 is 0 to 6.

[0119] [Chemical formula 16]

[0120]

[0121] [Chemical formula 17]

[0122]

[0123] In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, R6 is any group represented by the following formula (B7), R7 is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, a3 is 0 or 1. When a3 is 0, b3 is 1 to 5 and c3 is 0 to 4. When a3 is 1, b3 is 1 to 7 and c3 is 0 to 6.

[0124] [Chemical formula 18]

[0125]

[0126] [Chemical formula 19]

[0127]

[0128] In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. W1 is a group represented by the following formula (B9), a4 is 0 or 1, b4 is 1 or 2, and d4 is 1 to 4.

[0129] [Chemical formula 20]

[0130]

[0131] In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of the hydrogen atom is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied.

[0132] [Chemical formula 21]

[0133]

[0134] In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of the hydrogen atom is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. W1 is a group represented by the above formula (B9), W2 is a single bond or an organic group having 1 to 50 carbon atoms, m is an integer satisfying 1 ≤ m ≤ 5, a5 is 0 or 1, b5 is 1 or 2, and d5 is 1 to 4.

[0135] [Chemical formula 22]

[0136]

[0137] In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of the hydrogen atom is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R8 is a hydrogen atom or a methyl group, and b6 is 1 to 5.

[0138] If it is a composition for forming an organic film containing such a surfactant, due to having an appropriate fluorine content, the film-forming property during coating can be further improved.

[0139] The weight-average molecular weight of the aforementioned aryl benzyl ether compound is preferably 1000 to 30000.

[0140] If it is within such a range of the weight-average molecular weight, an organic film excellent in film-forming property and filling property can be formed. Also, the weight-average molecular weight can be determined by the method described later.

[0141] (Effects of the Invention)

[0142] As described above, according to the present invention, it is possible to provide a composition for forming an organic film that has excellent film-forming properties (in-plane uniformity) and filling characteristics on a substrate (wafer), excellent film-forming properties on the organic film when used as an organic film, and excellent suppression of swelling during the EBR step. The composition for forming an organic film of the present invention has excellent film-forming properties, filling characteristics, and suppression of swelling occurring during the EBR step. For example, it is extremely useful as an organic film material used in a multi-layer resist process such as a two-layer resist process, a three-layer resist process using a silicon-containing resist intermediate film or an inorganic hard mask, or a four-layer resist process using a silicon-containing resist intermediate film or an inorganic hard mask and an organic antireflection film or a conformal film, or as an organic film-forming material for manufacturing semiconductor devices. Further, in the method for forming an organic film of the present invention, an organic film with suppressed swelling can be formed, so that semiconductor elements and the like can be efficiently manufactured. Moreover, the aryl benzyl ether compound contained in the composition for forming an organic film of the present invention has a thermally decomposable aryl benzyl ether structure and a specific fluorine substituent, and thus exhibits the above-described characteristics, and is therefore useful as a composition for forming an organic film. Furthermore, by adjusting the phenolic hydroxyl group and the fluorine substituent having the structure represented by the above formula (B2) in the above ranges of ratios α and β, even in a low-temperature range where thermal decomposition does not occur at the benzyl position, the contact angle can be adjusted due to the sufficient presence of the phenolic hydroxyl group, and thus, it becomes a composition for forming an organic film with excellent coatability for a silicon-containing intermediate film.

[0143] Further, the surfactant of the present invention is an ideal surfactant for forming an organic film with excellent in-plane uniformity and filling characteristics and with the formation of swelling inhibited due to the influence of the remover in the EBR step. Further, the surfactant of the present invention can be usefully used not only in the overall coating material for optical lithography such as for forming an organic film, but also in various industrial uses and daily necessities uses. BRIEF DESCRIPTION OF THE DRAWINGS

[0144] Figure 1 (A) to (F) are explanatory diagrams of an example of a pattern formation method using a three-layer resist process of the present invention.

[0145] Figure 2 is an example of a diagram for measuring the swelling height using a contact profilometer in Example 2.

[0146] Figure 3 is an example of a diagram for measuring the swelling height using a contact profilometer in Comparative Example 2.

[0147] Figure 4 (G) to (I) are explanatory diagrams of the filling characteristic evaluation method in the examples. DETAILED DESCRIPTION OF THE INVENTION

[0148] As described above, there is a need to develop a composition for forming an organic film that can form an organic film with excellent film-forming properties (in-plane uniformity) and filling characteristics on a substrate (wafer), and in which the swelling during the EBR step is suppressed.

[0149] In general, when forming an organic film, a resin for forming an organic film and additives are dissolved in an organic solvent to form a composition, which is coated on a substrate having a structure, wiring, etc. using a coater and a developer, and the substrate is rotated to spread the composition, and the composition at the end is removed in the EBR step, and then fired to form an organic film.

[0150] If the fluidity of the above composition is insufficient, it is considered that voids will occur when filling holes and trenches with a very high aspect ratio, and when the solubility of the resin for forming an organic film and additives in the remover used in the EBR step is poor, swelling will occur at the outer periphery of the organic film.

[0151] The inventors of the present application have made further efforts to study the above problems, and as a result, they have found that by incorporating a thermally decomposable compound having a specific repeating unit into the composition for forming an organic film, it is possible to achieve both excellent film-forming properties and a high degree of filling characteristics, and to provide a composition for forming an organic film with excellent swelling suppression during the EBR step, thus completing the present invention.

[0152] That is, the present invention is a composition for forming an organic film, which is characterized by containing:

[0153] (A) a material for forming an organic film,

[0154] (B) an aryl benzyl ether compound containing a partial structure represented by the following general formula (B1), and

[0155] (C) a solvent.

[0156] [Chemical formula 23]

[0157]

[0158] In the formula, R1 is a hydrogen atom or an arbitrary fluorine-containing group represented by the following formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the following formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, a is 0 or 1. When a is 0, b is 1 to 5 and c is 0 to 4. When a is 1, b is 1 to 7 and c is 0 to 6. * represents a chemical bond with other atoms.

[0159] [Chemical formula 24]

[0160]

[0161] In the formula, the dashed line represents the atomic bond with the oxygen atom in the above formula (B1), and may also have one or two of the structures represented by the above formula (B2).

[0162] Furthermore, the present invention is a surfactant composed of an aryl benzyl ether compound having a partial structure represented by the following general formula (B1).

[0163] [Chemical formula 25]

[0164]

[0165] In the formula, R1 is a hydrogen atom or an arbitrary fluorine-containing group represented by the following formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the following formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, a is 0 or 1. When a is 0, b is 1 to 5 and c is 0 to 4. When a is 1, b is 1 to 7 and c is 0 to 6. * represents the atomic bond with other atoms.

[0166] [Chemical formula 26]

[0167]

[0168] In the formula, the dashed line represents the atomic bond with the oxygen atom in the above formula (B1), and may also have one or two of the structures represented by the above formula (B2).

[0169] The following is a detailed description of the present invention, but the present invention is not limited thereto.

[0170] [Composition for forming organic film]

[0171] The composition for forming an organic film of the present invention contains (A) a material for forming an organic film, (B) an aryl benzyl ether compound having a partial structure represented by the following general formula (B1), and (C) a solvent.

[0172] [Chemical formula 27]

[0173]

[0174] In the formula, R1 is a hydrogen atom or an arbitrary fluorine-containing group represented by the following formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the following formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, a is 0 or 1. When a is 0, b is 1 to 5 and c is 0 to 4. When a is 1, b is 1 to 7 and c is 0 to 6. * represents the atomic bond with other atoms.

[0175] [Chemical 28]

[0176]

[0177] In the formula, the dashed line represents the atomic bond with the oxygen atom in the above formula (B1), and may also have one or two of the structures represented by the above formula (B2).

[0178] Moreover, in the composition for forming an organic film of the present invention, the aforementioned (B) aryl benzyl ether compound, (A) the material for forming an organic film, and the aforementioned (C) solvent may each be used alone or in combination of two or more.

[0179] Hereinafter, among the constituent components of the above composition for forming an organic film, first, the characteristic (B) aryl benzyl ether compound of the present invention will be described, and then the above-mentioned material for forming an organic film, solvent, and other components will be described.

[0180] [(B) Aryl benzyl ether compound]

[0181] In the composition for forming an organic film of the present invention, the component (B) is a compound having a partial structure represented by the above general formula (B1). This compound is useful for forming an organic film by being incorporated into the composition for forming an organic film.

[0182] The (B) aryl benzyl ether compound of the present invention is a compound containing an aryl benzyl ether structure with a fluorine atom. The coating film formed by the organic film-forming composition using the (A) organic film-forming material and such a (B) aryl benzyl ether compound described later is not likely to bulge during the EBR step. Also, by introducing an appropriate fluorine atom-containing substituent represented by the above formula (B2), it can have the ability to lower the surface tension and can impart the function of a surfactant that brings excellent organic film uniform coating property (leveling property). Therefore, when the (B) aryl benzyl ether compound of the present invention is used as a surfactant, it is not limited to organic films and can be used as all coating materials for optical lithography. Specifically, for example, photosensitive photoresist materials, materials for forming a topcoat formed on a resist film, etc. Also, the aryl benzyl ether structure incorporated in the (B) aryl benzyl ether compound is decomposed at the benzyl position due to heat or the like. The phenolic hydroxyl group generated at this time can reduce the contact angle on the surface of the organic film, so it will become an organic film-forming composition that can form an organic film that can improve the coating property when a middle film, for example, a silicon-containing middle film, is coated thereon. Furthermore, by adjusting the phenolic hydroxyl group and the fluorine-substituted group of the structure represented by the above formula (B2) in the above-mentioned ranges of ratios α and β, even in a low-temperature range where it does not thermally decompose at the benzyl position, due to the sufficient presence of the phenolic hydroxyl group, the contact angle can be adjusted, and it will become an organic film-forming composition that can form an organic film with improved coating property when a middle film, for example, a silicon-containing middle film, is coated thereon. Thus, the (B) aryl benzyl ether compound of the present invention has the characteristic of also acting as a surfactant.

[0183] That is, for the organic film-forming composition of the present invention containing the (A) organic film-forming material and the (B) aryl benzyl ether compound, it is possible to form an organic film with excellent film-forming property and filling property on a substrate, excellent bulge suppression property during the EBR step, and excellent process margin when used as an organic film for a multilayer resist. For example: If the organic film-forming composition of the present invention is used, an excellent organic film for a multilayer resist for microfabrication in the manufacture of semiconductor devices, etc., and an excellent organic film for planarization in the manufacture of semiconductor devices, etc., can be formed.

[0184] It is preferable that the aforementioned (B) aryl benzyl ether compound is a compound represented by the following general formula (B3), (B4), (B6), (B8), (B10), or (B11).

[0185] [Chemical formula 29]

[0186]

[0187] In the formula, R1 is a hydrogen atom or one or two of the fluorine-containing groups represented by the foregoing formula (B2). Among the structures constituting the foregoing R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing groups represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, R3 is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, a1 is 0 or 1. When a1 is 0, b1 is 1 to 5 and c1 is 0 to 4. When a1 is 1, b1 is 1 to 7 and c1 is 0 to 6.

[0188] [Chemical formula 30]

[0189]

[0190] In the formula, R1 is a hydrogen atom or one or two of the fluorine-containing groups represented by the above formula (B2). Among the structures constituting the foregoing R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing groups represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, R4 is a single bond or any one of the groups represented by the following formula (B5), R5 is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, a2 is 0 or 1. When a2 is 0, b2 is 1 to 5 and c2 is 0 to 4. When a2 is 1, b2 is 1 to 7 and c2 is 0 to 6.

[0191] [Chemical formula 31]

[0192]

[0193] [Chemical formula 32]

[0194]

[0195] In the formula, R1 is a hydrogen atom or one or two of the fluorine-containing groups represented by the above formula (B2). Among the structures constituting the foregoing R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing groups represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, R6 is any group represented by the following formula (B7), R7 is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, a3 is 0 or 1. When a3 is 0, b3 is 1 to 5 and c3 is 0 to 4. When a3 is 1, b3 is 1 to 7 and c3 is 0 to 6.

[0196] [Chemical formula 33]

[0197]

[0198] [Chemical Formula 34]

[0199]

[0200] In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. W1 is a group represented by the following formula (B9), a4 is 0 or 1, b4 is 1 or 2, and d4 is 1 to 4.

[0201] [Chemical Formula 35]

[0202]

[0203] In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied.

[0204] [Chemical Formula 36]

[0205]

[0206] In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. W1 is a group represented by the above formula (B9), W2 is a single bond or an organic group having 1 to 50 carbon atoms, m is an integer satisfying 1 ≤ m ≤ 5, a5 is 0 or 1, b5 is 1 or 2, and d5 is 1 to 4.

[0207] [Chemical Formula 37]

[0208]

[0209] In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R8 is a hydrogen atom or a methyl group, and b6 is 1 to 5.

[0210] In the case of a composition for forming an organic film containing such a compound, due to having an appropriate fluorine content, the film-forming property during coating can be improved. In addition, the decomposition products generated during baking do not damage the in-plane uniformity of the film, and furthermore, insoluble components are not formed due to the reaction between the decomposition products. Therefore, the processing margin when used as an organic film is not narrowed, and device contamination and defects do not occur.

[0211] In the above general formulas (B1), (B3), (B4), and (B6), the monovalent organic group having 1 to 30 carbon atoms represented by R2, for example: monovalent saturated hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, and tert-pentyl; monovalent unsaturated chain hydrocarbon groups such as vinyl, propenyl, butenyl, pentenyl, ethynyl, and propynyl; monocyclic saturated cyclic hydrocarbon groups such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; monovalent monocyclic unsaturated cyclic hydrocarbon groups such as cyclobutenyl, cyclopentenyl, and cyclohexenyl; monovalent polycyclic cyclic hydrocarbon groups such as norbornyl and adamantyl; and monovalent aromatic hydrocarbon groups such as phenyl, methylphenyl, naphthyl, methylnaphthyl, anthryl, and methylanthryl.

[0212] Other examples of the organic group represented by the above R2, for example, alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, and n-hexyloxy; and alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl, and n-hexyloxycarbonyl.

[0213] Part or all of the hydrogen atoms possessed by the above organic groups such as saturated hydrocarbon groups, unsaturated chain hydrocarbon groups, monocyclic saturated cyclic hydrocarbon groups, monocyclic unsaturated cyclic hydrocarbon groups, polycyclic cyclic hydrocarbon groups, aromatic hydrocarbon groups, alkoxy groups, and alkoxycarbonyl groups may also be substituted, and the substituents, for example: halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; hydroxyl group, cyano group, carboxyl group, nitro group, amino group, alkoxy group, alkoxycarbonyl group, acyl group, alkoxycarbonyloxy group, aryl group, and aliphatic heterocyclic groups such as lactone group; and aromatic heterocyclic groups such as furyl group and pyridyl group.

[0214] From the perspective of raw material availability, the organic group represented by the above R2 is preferably methyl.

[0215] In the above general formulas (B3), (B4), and (B6), the saturated or unsaturated divalent organic group having 1 to 30 carbon atoms represented by R3, R5, or R7, for example: alkylene groups such as methylene, ethanediyl, propanediyl, butanediyl, pentanediyl, hexanediyl, octanediyl, and decanediyl; monocyclic cycloalkylene groups such as cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, cyclohexanediyl, cycloheptanediyl, cyclooctanediyl, cyclodecanediyl, methylcyclohexanediyl, and ethylcyclohexanediyl; polycyclic cycloalkylene groups such as bicyclo[2.2.1]heptanediyl, bicyclo[2.2.2]octanediyl, tricyclo[5.2.1.0 2,6 decane-2,7-diyl (dicyclopentylidene), tricyclo[3.3.1.1 3，7 decane-2,6-diyl, tetracyclo[6.2.1.1 3,6 .0 2,7 dodecane-2,11-diyl, and adamantanediyl; and arene diyl groups such as phenylene and naphthylene.

[0216] The alkyldioxy group represented by R3, R5, or R7, for example: a group formed by combining the above alkyldiyl with an oxygen atom. Further, the cycloalkyldioxy group represented by R3, R5, or R7, for example: a group formed by combining the above cycloalkyldiyl with an oxygen atom.

[0217] Some or all of the hydrogen atoms possessed by the above alkyldiyl, cycloalkyldiyl, alkyldioxy group, cycloalkyldioxy group, arene diyl group, etc. may also be substituted, and the substituents are, for example, the same groups as the examples of the substituents that the organic group represented by R2 may also have.

[0218] The organic group represented by R3, R5, or R7 is, for example, a group represented by the following formula.

[0219] [Chemical Formula 38]

[0220]

[0221] In the above formula, * represents a bond.

[0222] Considering the viewpoint of raw material availability, R3, R5, or R7 is preferably, for example, methylene.

[0223] The above W2 is a single bond or an organic group having 1 to 50 carbon atoms, for example: a group represented by the following formula.

[0224] [Chemical Formula 39]

[0225]

[0226] In the above formula, * represents a bond.

[0227] The compounds represented by the above general formula (B3) are specifically exemplified as follows, but are not limited thereto. In the following examples, R1 is one or two of a hydrogen atom or the fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of the hydrogen atom is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied.

[0228] [Chemical formula 40]

[0229]

[0230] The compounds represented by the above general formula (B4) are specifically exemplified as follows, but are not limited thereto. In the following examples, R1 is one or two of a hydrogen atom or the fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of the hydrogen atom is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied.

[0231] [Chemical formula 41]

[0232]

[0233] The compounds represented by the above general formula (B6) are specifically exemplified as follows, but are not limited thereto. In the following examples, R1 is one or two of a hydrogen atom or the fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of the hydrogen atom is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied.

[0234] [Chemical formula 42]

[0235]

[0236] The compounds represented by the above general formula (B8) are specifically exemplified as follows, but are not limited thereto. In the following examples, R1 is one or two of a hydrogen atom or the fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of the hydrogen atom is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied.

[0237] [Chemical formula 43]

[0238]

[0239] [Chemical formula 44]

[0240]

[0241] [Chemical formula 45]

[0242]

[0243] Specific examples of the compound represented by the above general formula (B10) are listed below, but are not limited thereto. In the following examples, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied.

[0244] [Chemical formula 46]

[0245]

[0246] Specific examples of the compound represented by the above general formula (B11) are listed below, but are not limited thereto. In the following examples, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied.

[0247] [Chemical formula 47]

[0248]

[0249] If it has the above structure, the thermal decomposability, surface activity effect, and fluidity of the polymer can be adjusted, and it will become a compound that can more surely balance film-forming properties, landfill properties, etc.

[0250] Furthermore, in the above general formulas (B3), (B4), (B6), (B8), (B10), or (B11), among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. The relationship between α and β is preferably α + β = 1, 0.15 ≤ α ≤ 0.4, and 0.6 ≤ β ≤ 0.85. If the proportion of the structure is within the above range, it can have a more sufficient surface tension reduction ability sufficient to impart a surface activity effect, and better coating properties can be achieved. Also, even in a low-temperature range where it does not thermally decompose at the benzyl position, it can still have an appropriate contact angle, and an organic film on which an intermediate film such as a silicon-containing intermediate film can be formed with excellent coating properties can be formed.

[0251] In the (B) aryl benzyl ether compound, the proportion α of hydrogen atoms and the proportion β of the fluorine-containing group represented by the above formula (B2) in the structure constituting the aforementioned R1 can be confirmed by nuclear magnetic resonance (NMR) spectroscopy and high-performance liquid chromatography (HPLC).

[0252] The weight-average molecular weight of the aforementioned (B) aryl benzyl ether compound is preferably 1,000 to 30,000, more preferably 1,500 to 25,000. If the weight-average molecular weight is 1,000 or more, the decrease in the blending effect due to volatilization or the like can be suppressed, and a sufficient blending effect can be obtained. Also, if the weight-average molecular weight is 30,000 or less, the fluidity does not deteriorate, etc., and the landfill characteristics are excellent.

[0253] In addition, in the present invention, the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) are polystyrene conversion values obtained by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent (solvent), and the dispersity (Mw / Mn) is calculated from Mw and Mn.

[0254] [Method for producing (B) aryl benzyl ether compound]

[0255] The means for obtaining the (B) aryl benzyl ether compound of the present invention is not limited, for example, it can be synthesized by a substitution reaction of a b-valent phenol or naphthol with pentafluorobenzyl halide, 2-(trifluoromethoxy)benzyl halide, 3-(trifluoromethoxy)benzyl halide, or 4-(trifluoromethoxy)benzyl halide using an alkali catalyst as shown below. The b-valent phenol or naphthol, and pentafluorobenzyl halide, 2-(trifluoromethoxy)benzyl halide, 3-(trifluoromethoxy)benzyl halide, or 4-(trifluoromethoxy)benzyl halide used in this synthesis can be used alone or in combination of two or more. They can be appropriately selected and combined according to the required characteristics. R1, R2, a, b, and c in the following formula are as described above, and X is a Cl atom, a Br atom, or an I atom.

[0256] [Chemical formula 48]

[0257]

[0258] The alkali catalyst used at this time, for example, inorganic base compounds such as sodium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, and potassium phosphate, and organic amine compounds such as triethylamine, pyridine, and N-methylmorpholine, etc., they can be used alone or in combination of two or more. The usage amount of the catalyst is preferably 0.1 to 20 moles, more preferably 0.5 to 0.9 moles, relative to 1 mole of the hydroxyl group of the raw material b-valent phenol or naphthol.

[0259] The solvent used herein is not particularly limited as long as it is inert to the above reaction. Examples thereof include ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; aromatic solvents such as benzene, toluene, and xylene; acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, and water. These solvents can be used alone or in combination. The solvent can be used in an amount of 0 to 2000 parts by mass relative to 100 parts by mass of the reaction raw materials. The reaction temperature is preferably from -50°C to around the boiling point of the solvent, and more preferably from room temperature to 150°C. The reaction time can be appropriately selected from 0.1 to 100 hours.

[0260] As for the reaction method, there are methods such as batch-feeding phenols or naphthols and pentafluorohalotoluene, 2-(trifluoromethoxy)halotoluene, 3-(trifluoromethoxy)halotoluene, or 4-(trifluoromethoxy)halotoluene into the solvent; dispersing or dissolving phenols or naphthols and pentafluorohalotoluene, 2-(trifluoromethoxy)halotoluene, 3-(trifluoromethoxy)halotoluene, or 4-(trifluoromethoxy)halotoluene separately in individual solvents and then dropwise-feeding them; and after dispersing or dissolving any one of phenols or naphthols and pentafluorohalotoluene, 2-(trifluoromethoxy)halotoluene, 3-(trifluoromethoxy)halotoluene, or 4-(trifluoromethoxy)halotoluene in the solvent, dropwise-feeding the other one dispersed or dissolved in the solvent. Also, when there are multiple feedings of phenols or naphthols and pentafluorohalotoluene, 2-(trifluoromethoxy)halotoluene, 3-(trifluoromethoxy)halotoluene, or 4-(trifluoromethoxy)halotoluene respectively, they can be pre-mixed and reacted, or reacted separately in sequence. When using a base catalyst, for example, there are methods such as batch-feeding phenols or naphthols and pentafluorohalotoluene, 2-(trifluoromethoxy)halotoluene, 3-(trifluoromethoxy)halotoluene, or 4-(trifluoromethoxy)halotoluene, and the method of pre-dispersing or dissolving the base catalyst and then dropwise-adding it.

[0261] In order to remove unreacted raw materials, catalysts, etc. present in the system, the reaction solution obtained by the methods exemplified above can be diluted with an organic solvent, then separated and washed, and the (B) aryl benzyl ether compound can also be recovered.

[0262] The organic solvent used for liquid separation washing is not particularly limited as long as it can dissolve the compound and separate into two layers when mixed with water. For example, hydrocarbons such as hexane, heptane, benzene, toluene, and xylene, esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate, ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, and methyl isobutyl ketone, ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, and ethyl cyclopentyl methyl ether, chlorinated solvents such as dichloromethane, chloroform, dichloroethane, and trichloroethylene, and mixtures thereof. The washing water used at this time may be what is commonly referred to as deionized water or ultrapure water. The number of washing times may be 1 or more, but even if washed 10 or more times, the corresponding washing effect may not be obtained. Preferably, it is about 1 to 5 times.

[0263] When performing liquid separation washing, in order to remove unreacted raw materials or acidic components in the system, washing with an alkaline aqueous solution can also be used. Specifically, the base, for example, hydroxides of alkali metals, carbonates of alkali metals, hydroxides of alkaline earth metals, carbonates of alkaline earth metals, ammonia, and organic ammonium salts, etc.

[0264] Also, when performing liquid separation washing, in order to remove unreacted raw materials, metal impurities or basic components in the system, washing with an acidic aqueous solution can also be used. Specifically, the acid, for example, inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropolyacids, organic acids such as oxalic acid, fumaric acid, maleic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid, etc.

[0265] The liquid separation washing using the alkaline aqueous solution and the acidic aqueous solution described above can be carried out only for any one of them, or can be carried out in combination. For the view of removing metal impurities, it is more ideal to perform liquid separation washing in the order of alkaline aqueous solution and then acidic aqueous solution.

[0266] After the liquid separation washing using the alkaline aqueous solution and the acidic aqueous solution described above, washing with neutral water can also be continued. The number of washing times may be 1 or more, preferably about 1 to 5 times. The neutral water can be the above-mentioned deionized water, ultrapure water, etc. The number of washing times may be 1 or more, but sometimes the basic components and acidic components cannot be removed when the number of times is small. Even if washed 10 or more times, the corresponding washing effect may not be obtained, so preferably it is about 1 to 5 times.

[0267] Also, the reaction product after the liquid separation operation can be concentrated and dried or crystallized under reduced pressure or normal pressure to recover it in the form of a powder, but in order to improve the operability when preparing the composition for forming an organic film, it can also be made into a solution state with an appropriate concentration in advance. The concentration at this time is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass. If it is such a concentration, the viscosity is not likely to become too high, so the operability can be prevented from being damaged, and also, the amount of the solvent does not become too large, so it is economical.

[0268] The solvent at this time only needs to be able to dissolve the compound, that is, there is no special limitation. Specific examples include ketones such as cyclohexanone and methyl-2-pentanone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl 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 monoterbutyl ether acetate. They can be used alone or in combination of two or more.

[0269] In the above reaction, phenols or naphthols can be combined with pentafluorohalotoluene, 2-(trifluoromethoxy)halotoluene, 3-(trifluoromethoxy)halotoluene, or 4-(trifluoromethoxy)halotoluene according to the required performance. For example, fluorine-containing substituents that change the surface activity ability such as for controlling surface tension can be arbitrarily combined. Therefore, when the composition for forming an organic film using the said compound is used for an organic film, various properties such as film-forming property and filling property can be taken into account in a high dimension.

[0270] [(A) Material for forming organic film]

[0271] The (A) material for forming an organic film (resin or compound) used in the composition for forming an organic film of the present invention is not particularly limited as long as it is a resin or compound that conforms to spin-coating film-forming property and hardening property. From the viewpoints of etching resistance, optical properties, heat resistance, etc., a resin or compound containing an aromatic skeleton (different from (B) aryl benzyl ether compound) is more ideal.

[0272] The above aromatic skeleton includes, for example, benzene, naphthalene, anthracene, pyrene, indene, fluorene, furan, pyrrole, thiophene, phosphole, pyrazole, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, carbazole, etc. Among these, benzene, naphthalene, fluorene, and carbazole are particularly preferred.

[0273] Hereinafter, specific examples of the above (A) material for forming an organic film will be given, but they are merely simple illustrations and are not limited thereto. Also, the numbering of the formulas shown in the following examples is only applied to the description of the following formulas.

[0274] The (A) material for forming an organic film (resin or compound) used in the present invention includes, for example, resins having the following structures described in JP-A-2012-001687 and JP-A-2012-077295.

[0275] [Chemical formula 49]

[0276]

[0277] In formula (1), the ring structures Ar1 and Ar2 each independently represent a benzene ring or a naphthalene ring. X represents a single bond or an alkylene group having 1 to 20 carbon atoms. m represents 0 or 1. n represents any natural number with a molecular weight of 100,000 or less. Also, the definitions of the notations in the formula are only applied to this formula.

[0278] [Chemical formula 50]

[0279]

[0280] In formula (2), the ring structures Ar1 and Ar2 each independently represent a benzene ring or a naphthalene ring. n represents any natural number with a polystyrene-reduced weight-average molecular weight of 100,000 or less obtained by gel permeation chromatography. Also, the definitions of the notations in the formula are only applied to this formula.

[0281] The (A) organic film-forming material used in the present invention may further include resins having the following structures described in JP-A No. 2004-264710, JP-A No. 2005-043471, JP-A No. 2005-250434, JP-A No. 2007-293294, and JP-A No. 2008-065303.

[0282] [Chemical formula 51]

[0283]

[0284] In formulas (3) and (4), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or an aryl group having 1 to 3 carbon atoms, and R 3 represents an alkyl group having 1 to 3 carbon atoms, a vinyl group, an allyl group, or an optionally substituted aryl group, n represents 0 or 1, and m represents 0, 1, or 2. Also, the definitions of the notations in the formula are only applied to this formula.

[0285] [Chemical formula 52]

[0286]

[0287] In formula (5), R1 is a monovalent atom or group other than a hydrogen atom, and n is an integer of 0 to 4. However, when n is 2 to 4, multiple R1s may be the same or different. R2 and R3 are each independently a monovalent atom or group. X is a divalent group. Also, the definitions of the notations in the formula are only applied to this formula.

[0288] [Chemical formula 53]

[0289]

[0290] In formula (6), R1 is a hydrogen atom or a methyl group. R2 is any one of a single bond, a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms, and an arylene group having 6 to 10 carbon atoms, and may have any of an ether, an ester, a lactone, and an amide. R 3 and R 4 are each independently a hydrogen atom or a glycidyl group. X represents any polymer of a hydrocarbon containing an indene skeleton, a cycloolefin having 3 to 10 carbon atoms, and maleimide, and may have any of an ether, an ester, a lactone, and a carboxylic anhydride. R 5 and R 6 are each independently any one of a hydrogen atom, a fluorine atom, a methyl group, and a trifluoromethyl group. R 7 is any one of a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a hydroxyl group, and an alkoxycarbonyl group. p and q are each an integer of 1 to 4. r is an integer of 0 to 4. a, b, and c are each in the range of 0.5 ≤ a + b + c ≤ 1, 0 ≤ a ≤ 0.8, 0 ≤ b ≤ 0.8, 0.1 ≤ a + b ≤ 0.8, and 0.1 ≤ c ≤ 0.8. Also, the definitions of the notations in the formula are only applied in this formula.

[0291] [Chemical formula 54]

[0292]

[0293] In formula (7), R1 represents a hydrogen atom or a monovalent organic group, and R2 and R3 each independently represent a monovalent atom or a monovalent organic group. Also, the definitions of the notations in the formula are only applied in this formula.

[0294] The (A) material for forming an organic film used in the present invention can be more specifically exemplified by resins having the following structures described in JP-A-2004-205685, JP-A-2007-171895, and JP-A-2009-014816.

[0295] [Chemical formula 55]

[0296]

[0297] In formulas (8) and (9), R 1 to R 8 are each independently a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, an isocyanate group, or a glycidyl group. m and n are positive integers. Also, the definitions of the notations in the formula are only applied in this formula.

[0298] [Chemical formula 56]

[0299]

[0300] In formula (10), R 1 and R 6 are each independently a hydrogen atom or a methyl group. R 2 , R 3 and R 4 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a hydroxyl group, an acetoxy group or an alkoxycarbonyl group, or an aryl group having 6 to 10 carbon atoms. R 5 is a condensed polycyclic hydrocarbon group having 13 to 30 carbon atoms, -O-R 7 , -C(=O)-O-R 7 , -O-C(=O)-R 7 , or -C(=O)-NR 8 -R 7 , m is 1 or 2, n is an integer from 0 to 4, and p is an integer from 0 to 6. R 7 is an organic group having 7 to 30 carbon atoms, R 8 is a hydrogen atom, or a hydrocarbon group having 1 to 6 carbon atoms. Z is any one of a methylene group, -O-, -S-, and -NH-. a, b, c, d, and e are each in the range of 0 < a < 1.0, 0 ≤ b ≤ 0.8, 0 ≤ c ≤ 0.8, 0 ≤ d ≤ 0.8, 0 ≤ e ≤ 0.8, and 0 < b + c + d + e < 1.0. Also, the definitions of the notations in the formula are only applicable in this formula.

[0301] [Chemical 57]

[0302]

[0303] In formula (11), n represents 0 or 1. R 1 represents an optionally substituted methylene group, an optionally substituted alkylene group having 2 to 20 carbon atoms, or an optionally substituted arylene group having 6 to 20 carbon atoms. R 2 represents a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms. R 3 to R 7 are each independently a hydroxyl group, an optionally substituted alkyl group having 1 to 6 carbon atoms, an optionally substituted alkoxy group having 1 to 6 carbon atoms, an optionally substituted alkoxycarbonyl group having 2 to 10 carbon atoms, an optionally substituted aryl group having 6 to 14 carbon atoms, or an optionally substituted glycidyl ether group having 2 to 6 carbon atoms. R 9 represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Also, the definitions of the notations in the formula are only applicable in this formula.

[0304] The resin represented by formula (11), for example: the following resins.

[0305] [Chemical Formula 58]

[0306]

[0307] [Chemical Formula 59]

[0308]

[0309] The material for forming an organic film (A) used in the present invention may further include resins having the following structures described in JP-A No. 2007-199653, JP-A No. 2008-274250, and JP-A No. 2010-122656.

[0310] [Chemical Formula 60]

[0311]

[0312] In formula (12), R 1 and R 2 are each independently the same or different hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and R 3 is a single bond or an alkylene group having a linear, branched or cyclic structure and having 1 to 30 carbon atoms, and may have a bridged ring hydrocarbon group, a double bond, a hetero atom or an aromatic group having 6 to 30 carbon atoms. R 4 and R 5 are each independently a hydrogen atom or an epoxypropyl group, and n is an integer of 1 to 4. Further, the definitions of the notations in the formula are only applicable to this formula.

[0313] [Chemical Formula 61]

[0314]

[0315] In formula (13), R 1 and R 2 are each independently the same or different hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and R 3 is a single bond or an alkylene group having a linear, branched or cyclic structure and having 1 to 30 carbon atoms, and may have a bridged ring hydrocarbon group, a double bond, a hetero atom or an aromatic group having 6 to 30 carbon atoms. R 4 and R 5 are each independently a hydrogen atom or an epoxypropyl group, and R 6 is a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms. Further, the definitions of the notations in the formula are only applicable to this formula.

[0316] [Chemical Formula 62]

[0317]

[0318] In formula (14), ring Z 1 and ring Z 2 are condensed polycyclic aromatic hydrocarbon rings, and R 1a , R 1b , R 2a , and R 2b represent substituents that may be the same or different. k1 and k2 may be the same or different and represent an integer of 0 or 1 to 4, m1 and m2 each represent an integer of 0 or 1 or more, and n1 and n2 each represent an integer of 0 or 1 or more. However, n1 + n2 ≥ 1. Also, the definitions of the notations in the formula are only applied in this formula.

[0319] [Chemical formula 63]

[0320]

[0321] In formula (15), R1 and R2 are the same or different hydrogen atoms, linear, branched, or cyclic alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, or alkenyl groups having 2 to 10 carbon atoms. R 3 and R 4 are each independently a hydrogen atom or a glycidyl group, R 5 is a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, and R 6 and R 7 are each independently a benzene ring or a naphthalene ring. p and q are each 1 or 2. n is 0 < n ≤ 1. Also, the definitions of the notations in the formula are only applied in this formula.

[0322] The resin represented by formula (15), for example: the following resins.

[0323] [Chemical formula 64]

[0324]

[0325] [Chemical formula 65]

[0326]

[0327] [Chemical formula 66]

[0328]

[0329] [Chemical formula 67]

[0330]

[0331] The (A) organic film-forming material used in the present invention may further include resins having the following structures described in Japanese Patent Application Laid-Open No. 2012-214720.

[0332] [Chemical Formula 68]

[0333]

[0334] In Formula (16), the ring structures Ar1 and Ar2 each independently represent a benzene ring or a naphthalene ring. x and z each independently represent 0 or 1. Also, the definitions of the notations in the formula are only applicable to this formula.

[0335] The (A) organic film-forming material used in the present invention may further include resins and the like described in Japanese Patent Application Laid-Open No. 2014-29435.

[0336] [Chemical Formula 69]

[0337]

[0338] In Formula (17), A represents a structure having a carbazole, B represents a structure having an aromatic ring, C represents a hydrogen atom, an alkyl group, or a structure having an aromatic ring, and B and C may also form a ring with each other. The combined structure of A, B, and C has 1 to 4 carboxyl groups or their salts, or carboxylic acid ester groups. Also, the definitions of the notations in the formula are only applicable to this formula.

[0339] Also, the (A) organic film-forming material used in the present invention may further include a polymer containing a unit structure represented by the following Formula (18) and a unit structure represented by the following Formula (19) described in International Publication No. 2012 / 077640, and the ratio of the unit structure represented by Formula (18) to the unit structure represented by Formula (19) is 3 to 97:97 to 3 in terms of molar ratio.

[0340] [Chemical Formula 70]

[0341]

[0342] In Formula (18), R1 and R2 each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination of these groups that may contain an ether bond, a ketone bond, or an ester bond. R3 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination of these groups that may contain an ether bond, a ketone bond, or an ester bond. R4 represents a hydrogen atom, or an aryl group having 6 to 40 carbon atoms or a heterocyclic group that may be substituted by a halogen atom, a nitro group, an amino group, or a hydroxyl group, and R5 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a heterocyclic group that may be substituted by a halogen atom, a nitro group, an amino group, or a hydroxyl group, and R4 and R5 may also form a ring with each other. n1 and n2 each represent an integer of 1 to 3. Also, the definitions of the notations in the formula are only applicable to this formula.

[0343] [Chemical Formula 71]

[0344]

[0345] In formula (19), Ar represents an aromatic ring group having 6 to 20 carbon atoms, R6 represents a hydroxyl group, R7 represents a hydrogen atom, a halogen atom, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination of these groups which may also contain an ether bond, a ketone bond, or an ester bond. R8 represents a hydrogen atom, or an aryl group having 6 to 40 carbon atoms or a heterocyclic group which may be substituted by a halogen atom, a nitro group, an amino group, or a hydroxyl group, R9 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a heterocyclic group which may be substituted by a halogen atom, a nitro group, an amino group, or a hydroxyl group, and R8 and R9 may also form a ring with each other. n6 represents an integer of 1 to p, and n7 represents an integer of p - n6. Here, p represents the maximum number that can substitute the aromatic ring group Ar. Also, the definitions of the notations in the formula are only applicable to this formula.

[0346] The (A) organic film-forming material used in the present invention may further include a polymer containing a unit structure represented by the following formula (20) described in International Publication No. 2010 / 147155.

[0347] [Chemical Formula 72]

[0348]

[0349] In formula (20), R1 and R2 are each independently selected from the group consisting of a hydrogen atom, a halogen group, a nitro group, an amino group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, or the aryl group represents a group which may also contain an ether bond, a ketone bond, or an ester bond. R3 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, or the aryl group represents a group which may also contain an ether bond, a ketone bond, or an ester bond. R4 represents an aryl group having 6 to 40 carbon atoms or a heterocyclic group which may be substituted by a halogen group, a nitro group, an amino group, or a hydroxyl group. R5 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a heterocyclic group which may be substituted by a halogen group, a nitro group, an amino group, or a hydroxyl group, and R4 and R5 may also form a ring together with the carbon atom to which they are bonded. n1 and n2 are each an integer of 1 to 3. Also, the definitions of the notations in the formula are only applicable to this formula.

[0350] The (A) organic film-forming material used in the present invention may further include: novolak resins obtained by reacting one or more of phenols such as phenol, cresol, xylenol, catechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol (hydroxyquinol), phloroglucinol, etc. with one or more of aldehyde sources such as formaldehyde, trioxymethylene, and trioxane in the presence of an acidic catalyst, resins containing a repeating unit structure represented by the following formula (21) as described in International Publication No. 2012 / 176767, etc.

[0351] [Chemical formula 73]

[0352]

[0353] In formula (21), A represents a hydroxy-substituted phenylene group derived from a polyhydroxybenzene, and B represents a monovalent condensed aromatic hydrocarbon ring group formed by condensing 2 to 6 benzene rings. Further, the definitions of the notations in the formula are only applied to this formula.

[0354] The (A) organic film-forming material used in the present invention may further include novolak resins having a fluorene or tetrahydrospirobiindene structure as described in Japanese Patent Application Laid-Open No. 2005-128509, Japanese Patent Application Laid-Open No. 2006-259249, Japanese Patent Application Laid-Open No. 2006-259482, Japanese Patent Application Laid-Open No. 2006-293298, and Japanese Patent Application Laid-Open No. 2007-316282, resins containing a repeating unit structure represented by the following formula (22-1) or (22-2), etc.

[0355] [Chemical formula 74]

[0356]

[0357] In formula (22-1) and formula (22-2), R 1 , R 2 , R 6 and R 7 are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an allyl group or a halogen atom, and R 3 , R 4 , R 8 and R 9 are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms or a glycidyl group, and R 5 and R 14 are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. n, m, p and q are integers from 1 to 3. R 10 to R 13Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms. Further, the definitions of the notations in the formula are applied only to this formula.

[0358] The (A) organic film-forming material used in the present invention may further include a reaction product obtained by the method described in JP-A-2012-145897. More specifically, it may include a polymer obtained by condensing one or more compounds represented by the following general formula (23-1) and / or (23-2) with one or more compounds represented by the following general formula (24-1) and / or (24-2) and / or their equivalents.

[0359] [Chemical formula 75]

[0360]

[0361] In general formula (23-1) and general formula (23-2), R 1 ~R 8 Each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an isocyanato group, a glycidyloxy group, a carboxyl group, an amino group, an alkoxy group having 1 to 30 carbon atoms, an alkoxycarbonyl group having 1 to 30 carbon atoms, an alkanoyloxy group having 1 to 30 carbon atoms, or a saturated or unsaturated organic group having 1 to 30 carbon atoms which may be substituted. Further, two substituents arbitrarily selected from R 1 ~R 4 or R 5 ~R 8 may be bonded to each other to further form a cyclic substituent. Further, the definitions of the notations in the formula are applied only to this formula.

[0362] [Chemical formula 76]

[0363]

[0364] In general formula (24-1) and general formula (24-2), Q represents an organic group having 1 to 30 carbon atoms which may be substituted, and two Qs arbitrarily selected in the molecule may be bonded to each other to form a cyclic substituent. n1 to n6 are the numbers of the respective substituents, n1 to n6 are 0, 1 or 2, and formula (24-1) excludes hydroxybenzaldehyde. Further, formula (24-2) satisfies the relationships of 0 ≤ n3 + n5 ≤ 3, 0 ≤ n4 + n6 ≤ 4, and 1 ≤ n3 + n4 ≤ 4. Further, the definitions of the notations in the formula are applied only to this formula.

[0365] Further, polymers obtained by condensing one or more compounds represented by the above general formula (23-1) and / or (23-2), one or more compounds represented by the above general formula (24-1) and / or (24-2) and / or their equivalents, and one or more compounds represented by the following general formula (25) and / or their equivalents can be cited.

[0366] [Chemical formula 77]

[0367] Y-CHO (25)

[0368] In formula (25), Y is a hydrogen atom or a monovalent organic group having 30 or less carbon atoms which may have substituents, and formula (25) is different from general formula (24-1) and general formula (24-2). Further, the definitions of the notations in the formula are only applied to this formula.

[0369] The (A) organic film-forming material used in the present invention can further include compounds having the following structures described in Japanese Patent Application Laid-Open No. 2017-119671.

[0370] [Chemical formula 78]

[0371]

[0372] In formula (26-1), R is a single bond or an organic group having 1 to 50 carbon atoms, X is a group represented by the following general formula (26-2), and m1 is an integer satisfying 2 ≤ m1 ≤ 10. Further, the definitions of the notations in the formula are only applied to this formula.

[0373] [Chemical formula 79]

[0374]

[0375] In the formula, X 2 is a divalent organic group having 1 to 10 carbon atoms, n1 is 0 or 1, n2 is 1 or 2, and X 3 is a group represented by the following general formula (26-3), and n5 is 0, 1 or 2. Further, the definitions of the notations in the formula are only applied to this formula.

[0376] [Chemical formula 80]

[0377]

[0378] In the formula, R 10 is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atoms on the benzene ring in the formula may also be substituted with methyl or methoxy groups. Further, the definitions of the notations in the formula are only applied to this formula.

[0379] Compounds having the above structures include, for example, the following compounds.

[0380] [Chemical formula 81]

[0381]

[0382] The (A) organic film-forming material used in the present invention may further include polymers having repeating units represented by the following general formula (27-1) described in Japanese Patent Laid-Open No. 2019-044022 and the like.

[0383] [Chemical formula 82]

[0384]

[0385] In formula (27-1), AR1 and AR2 are benzene rings or naphthalene rings which may have substituents, and R 1 and R 2 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms. When R 1 and R 2 are organic groups, R 1 and R 2 may also form a cyclic organic group through intramolecular bonding. n is 0 or 1. When n = 0, AR1 and AR2 form a bridging structure between the aromatic rings of AR1 and AR2 without passing through Z. When n = 1, AR1 and AR2 form a bridging structure between the aromatic rings of AR1 and AR2 through Z. Z is a single bond or any of the following formula (27-2). Y is a group represented by the following formula (27-3). Also, the definitions of the symbols in the formula are only applied in this formula.

[0386] [Chemical formula 83]

[0387]

[0388] ----R 3 -C≡C-R 4 (27-3)

[0389] In formula (27-3), R 3 is a single bond or a divalent organic group having 1 to 20 carbon atoms, and R 4 is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The dashed line represents an atomic bond. Also, the definitions of the symbols in the formula are only applied in this formula.

[0390] Polymers having repeating units represented by the above general formula (27-1) include, for example, the following polymers.

[0391] [Chemical formula 84]

[0392]

[0393] [Chemical formula 85]

[0394]

[0395] (A) The material for forming the organic film can be synthesized by a known method or a commercially available product can be used.

[0396] The blending amount of the aforementioned (A) material for forming the organic film is not particularly limited as long as it can meet the spin-coating film-forming property of the composition for forming the organic film. For 100 parts by mass of the aforementioned composition for forming the organic film, the content of the aforementioned (A) material for forming the organic film is preferably 10 to 40 parts by mass, more preferably 10 to 30 parts by mass, and still more preferably 10 to 25 parts by mass. For example, when filling very high aspect ratio holes and trenches of a 3D NAND memory structure with the composition for forming the organic film, a large blending amount of the material for forming the organic film is required, and the viscosity of such a composition for forming the organic film is high, and the in-plane uniformity and filling characteristics after spin coating will deteriorate. Even with the above blending ratio of the above (A) material for forming the organic film, the composition for forming the organic film of the present invention can form an organic film with excellent in-plane uniformity and filling characteristics, so it can be appropriately used.

[0397] Furthermore, with respect to 100 parts by mass of the aforementioned (A) material for forming the organic film, the content of the aforementioned (B) aryl benzyl ether compound is preferably 0.01 part by mass to 5 parts by mass. If the composition for forming the organic film contains an aryl benzyl ether compound with such a content, the in-plane uniformity of the formed organic film is more excellent.

[0398] [(C) Solvent]

[0399] The (C) solvent that can be used in the composition for forming the organic film of the present invention is not particularly limited as long as it can dissolve the aforementioned (A) composition for forming the organic film and the aforementioned (B) aryl benzyl ether compound, and it is more desirable if it can also dissolve an acid generator, a crosslinking agent, and further a surfactant described later. Specifically, for example, solvents with a boiling point of less than 180°C such as those described in paragraphs (0091) to (0092) of Japanese Patent Application Laid-Open No. 2007-199653 can be used. Among them, it is more desirable to use propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclopentanone, cyclohexanone, and a mixture of two or more of them.

[0400] The content of the (C) solvent is preferably 200 to 10,000 parts by mass, more preferably 300 to 5,000 parts, with respect to 100 parts by mass of the (A) material for forming the organic film. By being in such a range, the concentration can be adjusted according to the desired film thickness.

[0401] Furthermore, in the material for forming an organic film of the present invention, as the organic solvent serving as the (C) solvent, a high-boiling solvent having a boiling point of 180°C or higher may be added to the solvent having a boiling point of less than 180°C (a mixture of a solvent having a boiling point of less than 180°C and a solvent having a boiling point of 180°C or higher). The high-boiling organic solvent is not particularly limited as long as it can dissolve the (A) material for forming an organic film and the (B) aryl benzyl ether compound. Examples include hydrocarbons, alcohols, ketones, esters, ethers, chlorinated solvents, etc. Specific examples are 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerol, n-nonyl acetate, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol mono-isobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol n-butyl ether, triethylene glycol butyl methyl ether, triethylene glycol diacetate, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monon-propyl ether, dipropylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monon-propyl ether, tripropylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, propylene glycol diacetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol methyl n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, γ-butyrolactone, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, dibutyl adipate, etc. They may be used alone or in combination.

[0402] The boiling point of the above-mentioned high-boiling solvent may be appropriately selected according to the temperature at which the (A) material for forming an organic film is heat-treated. The boiling point of the added high-boiling solvent is preferably 180°C to 300°C, and more preferably 200°C to 300°C. If the boiling point is such, there is no fear of excessive volatilization during baking (heat treatment) due to too low a boiling point, so sufficient thermal fluidity can be obtained. Also, if the boiling point is such, since the boiling point is high, it will not remain non-volatile in the film after baking, so there is no fear of adversely affecting film properties such as etching resistance.

[0403] When the high boiling point solvent is used, the amount of the high boiling point solvent blended is preferably 1 to 30 parts by mass relative to 100 parts by mass of the solvent having a boiling point of less than 180° C. If such an amount is blended, sufficient thermal fluidity can be imparted during baking, and there is no risk of the solvent remaining in the film and causing deterioration of film properties such as etching resistance.

[0404] If such an organic film forming composition is provided with thermal fluidity by adding a high boiling point solvent to the above-mentioned (A) organic film forming material, the organic film forming composition can achieve both high degree of filling and excellent planarization characteristics.

[0405] [Other ingredients]

[0406] In addition, an acid generator and a crosslinking agent that further promote the crosslinking reaction may be added to the organic film forming composition of the present invention. Acid generators that generate acid due to thermal decomposition and those that generate acid due to light irradiation may be added. Specifically, the acid generators include those described in paragraphs

[0061] to

[0085] of Japanese Patent Gazette No. 2007-199653. The above-mentioned acid generators may be used alone or in combination of two or more. The amount of the acid generator added is preferably 0.05 to 50 parts by mass, and more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the organic film forming material (A). If it is such an amount, the crosslinking reaction will be promoted and a dense film will be formed.

[0407] In addition, the crosslinking agent specifically includes those described in paragraphs

[0055] to

[0060] of Japanese Patent Publication No. 2007-199653. The crosslinking agent can be used alone or in combination of two or more. The amount of the crosslinking agent added is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, relative to 100 parts by mass of the organic film-forming material (A). If it is such an amount, the curability is improved, and cross-mixing with the upper film can be further suppressed.

[0408] In addition, in the composition for forming an organic film of the present invention, in order to further improve the in-plane uniformity of spin coating, other surfactants other than the (B) aryl benzyl ether compound of the present invention may also be added. Other surfactants specifically include those recorded in paragraphs

[0142] to

[0147] of Japanese Patent Publication No. 2009-269953. The above-mentioned other surfactants can be used alone or in combination of two or more. The amount added when adding other surfactants is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the organic film forming material. If it is such an amount, an organic film with excellent in-plane uniformity can be formed.

[0409] Furthermore, a basic compound for improving storage stability can be added to the composition for forming an organic film of the present invention. The basic compound functions as a quencher for acid to prevent the trace acid generated by the acid generator from promoting the crosslinking reaction. Such basic compounds are specifically described, for example, in paragraphs

[0086] to

[0090] of Japanese Patent Application Laid-Open No. 2007-199653. The above basic compounds can be used alone or in combination of two or more. When adding the basic compound, the addition amount is preferably 0.05 to 50 parts by mass, more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the (A) organic film-forming material. With such an amount, the storage stability of the composition for forming an organic film can be improved.

[0410] As described above, if it is the composition for forming an organic film of the present invention, it will become a composition for forming an organic film with excellent swelling suppression property in the EBR step. Therefore, the composition for forming an organic film of the present invention is extremely useful as an underlayer film material (organic film material) for multilayer resist processes such as a two-layer resist process, a three-layer resist process using a silicon-containing resist intermediate film or a silicon-containing inorganic hard mask intermediate film, and a four-layer resist process using a silicon-containing resist intermediate film or a silicon-containing inorganic hard mask intermediate film and an organic antireflection film or a sealing film.

[0411] [Method for forming an organic film]

[0412] The present invention provides a method for forming an organic film, which is a method for forming an organic film used in the manufacturing process of a semiconductor device, and is characterized in that: the composition for forming an organic film of the present invention is spin-coated on a substrate to be processed to obtain a coating film, and the coating film is heat-treated at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds to be hardened to form an organic film. For example: the substrate coated with the above composition for forming an organic film is heat-treated and hardened within the above temperature and time ranges to form an organic film.

[0413] In this method for forming an organic film, first, the composition for forming an organic film of the present invention is spin-coated (spin coating) on the substrate to be processed. By using the spin coating method, good filling characteristics can be obtained. After removing the end film in the EBR step, baking (heat treatment) is performed to promote the crosslinking reaction. Also, because this baking can evaporate the solvent in the composition, it is possible to prevent mixing even when forming an upper resist film or a silicon-containing resist intermediate film on the organic film.

[0414] Baking is carried out at a temperature above 100°C and below 600°C, in the range of 10 to 600 seconds, preferably at a temperature above 200°C and below 500°C, in the range of 10 to 300 seconds, and more preferably at a temperature above 250°C and below 500°C, in the range of 10 to 300 seconds. Considering device damage and the influence on wafer deformation, it is preferable that the upper limit of the heating temperature during wafer processing for lithography is 600°C or lower, and more preferably 500°C or lower. By performing heat treatment under such conditions, the crosslinking reaction can be promoted, and an organic film that does not mix with the film formed in the upper layer can be formed.

[0415] [Pattern formation method]

[0416] The following describes a pattern formation method using the composition for forming an organic film of the present invention.

[0417] [Three-layer resist process using a silicon-containing resist intermediate film]

[0418] The present invention provides a pattern formation method, characterized in that:

[0419] An organic film is formed on a workpiece using the composition for forming an organic film of the present invention,

[0420] A silicon-containing resist intermediate film is formed on the aforementioned organic film using a silicon-containing resist intermediate film material,

[0421] A resist upper layer film is formed on the aforementioned silicon-containing resist intermediate film using a resist upper layer film material composed of a photoresist composition,

[0422] A circuit pattern is formed on the aforementioned resist upper layer film, and the resist upper layer film on which the circuit pattern has been formed is used as a mask, and the pattern is transferred to the aforementioned silicon-containing resist intermediate film by etching,

[0423] The silicon-containing resist intermediate film on which the pattern has been transferred is used as a mask, and the pattern is transferred to the aforementioned organic film by etching,

[0424] The organic film on which the pattern has been transferred is used as a mask again, and the pattern is formed on the aforementioned workpiece by etching.

[0425] As the workpiece, it is preferable to use, for example, a semiconductor device substrate, or a substrate on which any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, and a metal oxynitride film has been formed on the aforementioned semiconductor device substrate. More specifically, without particular limitation, substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc., and those on which the aforementioned metal films, etc. have been formed as the processing layer on the aforementioned substrates can be used.

[0426] For the processed layer, various Low-k films such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si, etc. and their barrier films can be used, and a thickness of usually 50 to 10,000 nm, especially 100 to 5,000 nm can be formed. Also, when forming the processed layer, the substrate and the processed layer are made of different materials.

[0427] Also, as the metal constituting the workpiece, it is preferable to use a metal such as silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy containing them.

[0428] When forming an organic film on the workpiece using the composition for forming an organic film of the present invention, for example, although not limited, the above-described method for forming an organic film of the present invention can be applied.

[0429] Then, a resist intermediate film (silicon-containing resist intermediate film) is formed on the organic film using a resist intermediate film material containing a silicon atom. As the resist intermediate film material containing a silicon atom, a polysiloxane-based intermediate film material is preferably used. By making the silicon-containing resist intermediate film have an antireflection effect, reflection can be suppressed. Especially for 193 nm exposure applications, if a material containing a large amount of aromatic groups and having a high etching selectivity with respect to the substrate is used as the composition for forming an organic film, the k value increases and the substrate reflection increases. By having an absorption that becomes an appropriate k value for the silicon-containing resist intermediate film, reflection can be suppressed and the substrate reflection can be made 0.5% or less. For a silicon-containing resist intermediate film having an antireflection effect, for 248 nm or 157 nm exposure applications, it is ideal to use an anthracene group, and for 193 nm exposure applications, a polysiloxane crosslinked by an acid or heat and having a phenyl group or a light-absorbing group with a silicon-silicon bond as a suspension structure.

[0430] Then, a resist upper layer film is formed on the silicon-containing resist intermediate film using a resist upper layer film material composed of a photoresist composition. The resist upper layer film material can be either positive or negative, and the same as the commonly used photoresist composition can be used. After spin-coating the resist upper layer film material, it is preferably prebaked in the range of 60 to 180 °C for 10 to 300 seconds. Then, exposure is carried out according to the usual method, followed by post-exposure baking (PEB) and development to obtain a resist upper layer film pattern. Also, the thickness of the resist upper layer film is not particularly limited, and 30 to 500 nm is more ideal, especially 50 to 400 nm is better.

[0431] Then, a circuit pattern (resist upper layer film pattern) is formed on the resist upper layer film. The formation of the circuit pattern is preferably carried out by photolithography using light with a wavelength of 10 nm or more and 300 nm or less, direct drawing using an electron beam, nanoimprinting, or a combination thereof.

[0432] Further, exposure light, such as high-energy rays with a wavelength of 300 nm or less, specifically, far ultraviolet rays, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 laser (157 nm), Kr2 laser (146 nm), Ar2 laser (126 nm), soft X-rays (EUV) in the range of 3 to 20 nm, electron beam (EB), ion beam, and X-rays, etc. can be cited.

[0433] Further, in the formation of the circuit pattern, it is preferable to develop the circuit pattern using alkali development or an organic solvent.

[0434] Then, using the upper resist film on which the circuit pattern has been formed as a mask, the pattern is transferred by etching in the silicon-containing resist intermediate film. For the etching of the silicon-containing resist intermediate film using the upper resist film pattern as a mask, it is preferably carried out using a fluorocarbon-based gas. Thereby, the pattern (silicon-containing resist intermediate film pattern) is transferred to the silicon-containing resist intermediate film.

[0435] Then, using the silicon-containing resist intermediate film (silicon-containing resist intermediate film pattern) on which the pattern has been transferred as a mask, the pattern is transferred by etching in the organic film. The silicon-containing resist intermediate film shows resistance to etching carried out using oxygen or hydrogen, so for the etching of the organic film using the silicon-containing resist intermediate film pattern as a mask, it is preferably carried out using an etching gas with oxygen or hydrogen as the main component. Thereby, the pattern (organic film pattern) is transferred to the organic film.

[0436] Then, using the organic film (organic film pattern) on which the pattern has been transferred as a mask, a pattern is formed by etching on the workpiece.

[0437] Next, the etching of the workpiece (processed layer) can be carried out according to a conventional method. For example, if the workpiece is SiO2, SiN, or a silicon dioxide-based low dielectric constant insulating film, etching is carried out using a fluorocarbon-based gas as the main component. If it is p-Si, Al, or W, etching is carried out using a chlorine-based or bromine-based gas as the main component. When the substrate processing is carried out by etching using a fluorocarbon-based gas, the silicon-containing resist intermediate film pattern is peeled off during the processing of the workpiece. On the other hand, when the processing of the workpiece is carried out by etching using a chlorine-based or bromine-based gas, in order to peel off the silicon-containing resist intermediate film pattern, dry etching peeling using a fluorocarbon-based gas must be carried out separately after the processing of the workpiece.

[0438] As described above, the organic film obtained using the composition for forming an organic film of the present invention has excellent etching resistance during the etching of the workpiece.

[0439] [Four-layer resist process using a silicon-containing resist intermediate film and an organic antireflective film or a conformal film]

[0440] Further, the present invention provides a pattern forming method, characterized in that:

[0441] An organic film is formed on the workpiece using the composition for forming an organic film of the present invention.

[0442] A silicon-containing resist intermediate film is formed on the aforementioned organic film using a silicon-containing resist intermediate film material, and an organic anti-reflection film or a conformal film is formed on the aforementioned silicon-containing resist intermediate film.

[0443] A resist upper layer film is formed on the aforementioned organic anti-reflection film or conformal film using a resist upper layer film material composed of a photoresist composition, and a circuit pattern is formed on the aforementioned resist upper layer film.

[0444] Using the aforementioned resist upper layer film on which the circuit pattern has been formed as a mask, the pattern is transferred to the aforementioned organic anti-reflection film or conformal film and the aforementioned silicon-containing resist intermediate film by etching.

[0445] Using the aforementioned silicon-containing resist intermediate film on which the pattern has been transferred as a mask, the pattern is transferred to the aforementioned organic film by etching.

[0446] Then, using the aforementioned organic film on which the pattern has been transferred as a mask, the pattern is formed on the aforementioned workpiece by etching.

[0447] Also, in this method, an organic anti-reflection film (BARC) or a conformal film is formed between the silicon-containing resist intermediate film and the resist upper layer film, and except for this, it can be carried out in the same manner as the three-layer resist process using the silicon-containing resist intermediate film described above.

[0448] The organic anti-reflection film and the conformal film can be formed by spin coating using a known organic anti-reflection film material.

[0449] [Three-layer resist process using an inorganic hard mask intermediate film]

[0450] Furthermore, the present invention provides a pattern forming method, characterized in that:

[0451] An organic film is formed on the workpiece using the composition for forming an organic film of the present invention.

[0452] An inorganic hard mask selected from the group consisting of a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the aforementioned organic film.

[0453] A resist upper layer film is formed on the aforementioned inorganic hard mask using a resist upper layer film material composed of a photoresist composition.

[0454] A circuit pattern is formed on the aforementioned resist upper layer film.

[0455] Using the aforementioned resist upper layer film on which the circuit pattern has been formed as a mask, the pattern is transferred to the aforementioned inorganic hard mask by etching.

[0456] Using the inorganic hard mask of the previously transferred pattern as a mask, transfer the pattern to the aforementioned organic film by etching.

[0457] Then, using the organic film of the previously transferred pattern as a mask, form the pattern on the aforementioned workpiece by etching.

[0458] Also, in this method, an inorganic hard mask intermediate film is formed instead of a silicon-containing resist intermediate film on the organic film, and except for this, it can be carried out in the same manner as the three-layer resist process using the silicon-containing resist intermediate film described above.

[0459] The inorganic hard mask intermediate film selected from the group consisting of a silicon oxide film, a silicon nitride film, and a silicon oxynitride film (SiON film) can be formed, for example, by CVD method, ALD method, etc. The formation method of the silicon nitride film is described, for example, in Japanese Patent Application Laid-Open No. 2002-334869, International Publication No. 2004 / 066377, etc. The film thickness of the inorganic hard mask intermediate film is preferably 5 to 200 nm, more preferably 10 to 100 nm. It is most ideal to use the SiON film with a high anti-reflection film effect as the inorganic hard mask intermediate film.

[0460] [Four-layer resist process using an inorganic hard mask intermediate film and an organic anti-reflection film or adhesion film]

[0461] Also, the present invention provides a pattern formation method, characterized in that:

[0462] Form an organic film on the workpiece using the composition for forming the organic film of the present invention.

[0463] Form an inorganic hard mask selected from the group consisting of a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the aforementioned organic film.

[0464] Form an organic anti-reflection film or adhesion film on the aforementioned inorganic hard mask, and form an upper resist film on the aforementioned organic anti-reflection film or adhesion film using a resist upper film material composed of a photoresist composition.

[0465] Form a circuit pattern on the aforementioned upper resist film.

[0466] Using the upper resist film with the previously formed circuit pattern as a mask, transfer the pattern to the aforementioned organic anti-reflection film or adhesion film and the aforementioned inorganic hard mask by etching.

[0467] Using the inorganic hard mask of the previously transferred pattern as a mask, transfer the pattern to the aforementioned organic film by etching.

[0468] Then, using the organic film of the previously transferred pattern as a mask, form the pattern on the aforementioned workpiece by etching.

[0469] Further, an organic anti-reflection film (BARC) or a conformal film is formed between the inorganic hard mask intermediate film and the resist upper film, and other than this, it can be carried out in the same manner as the three-layer resist process using the inorganic hard mask intermediate film described above.

[0470] In particular, when using a SiON film as the inorganic hard mask intermediate film, by using the SiON film and the BARC two-layer anti-reflection film, reflection can be suppressed even in immersion exposure with a high NA exceeding 1.0. Another advantage of forming the BARC is the effect of reducing the tailing of the resist upper film pattern directly above the SiON film.

[0471] Here, an example of the pattern formation method using a three-layer resist process of the present invention is as shown in Figure 1 (A) to (F) of. During the three-layer resist process, as shown in Figure 1 (A) of, an organic film 3 is formed on a processed layer (workpiece) 2 formed on a substrate 1 using the composition for forming an organic film of the present invention, and then a silicon-containing resist intermediate film 4 is formed on the organic film 3, and a resist upper film 5 is formed thereon. Then, as shown in Figure 1 (B) of, the exposed portion 6 of the resist upper film 5 is exposed, and then PEB (post-exposure bake) is performed. Then, as shown in Figure 1 (C) of, development is performed to form a resist upper film pattern 5a. Then, as shown in Figure 1 (D) of, using the resist upper film pattern 5a as a mask, the silicon-containing resist intermediate film 4 is dry-etched using a fluorocarbon-based gas to form a silicon-containing resist intermediate film pattern 4a. Next, the resist upper film pattern 5a is removed. Next, as shown in Figure 1 (E) of, using the silicon-containing resist intermediate film pattern 4a as a mask, the organic film 3 is oxygen-plasma-etched to form an organic film pattern 3a. Again, as shown in Figure 1 (F) of, the silicon-containing resist intermediate film pattern 4a is removed, and then, using the organic film pattern 3a as a mask, the processed layer 2 is etched to form a pattern 2a.

[0472] In the pattern formation method of this example, since the swelling during the formation of the organic film 3 is suppressed, it is possible to reduce Figure 1 the defects occurring due to the swelling of the organic film during the dry etching processes of (D), (E), and (F) of.

[0473] When forming the inorganic hard mask intermediate film, it is only necessary to change the silicon-containing resist intermediate film 4 to the inorganic hard mask intermediate film. When forming the BARC or the adhesion film, it is only necessary to form the BARC or the adhesion film between the silicon-containing resist intermediate film 4 and the resist upper layer film 5. The etching of the BARC or the adhesion film can be continuously performed before the etching of the silicon-containing resist intermediate film 4, or only the etching of the BARC or the adhesion film can be performed and then the etching device, etc. can be changed to perform the etching of the silicon-containing resist intermediate film 4.

[0474] As described above, if it is the pattern forming method of the present invention, a fine pattern can be formed with high precision on the workpiece by multilayer resist processing, and the formation of the bulge of the organic film can be suppressed. Thereby, the defects caused by the bulge of the organic film can be reduced.

[0475] [Surfactant]

[0476] The surfactant of the present invention is the surfactant composed of the (B) aryl benzyl ether compound contained in the organic film forming composition of the present invention described previously.

[0477] The surfactant of the present invention can form an organic film with excellent in-plane uniformity and filling characteristics and suppress the formation of the bulge caused by the influence of the remover in the EBR step by combining the fluorine substituents having the structure represented by the formula (B2) described previously. Therefore, it becomes an ideal surfactant. Also, since it is a surfactant in which the ratios α and β of the phenolic hydroxyl group and the fluorine substituents having the structure represented by the formula (B2) are adjusted within the above range, when using the surfactant of the present invention in the formation of the organic film of the organic film forming composition, even in the low temperature range where it does not thermally decompose at the benzyl position, the contact angle can still be adjusted due to the sufficient presence of the phenolic hydroxyl group, and an organic film forming composition capable of forming an organic film on which an intermediate film such as a silicon-containing intermediate film can be formed with excellent coatability can be achieved.

[0478] In the present invention, the aryl benzyl ether compound is preferably the compound represented by the general formulas (B3), (B4), (B6), (B8), (B10), or (B11) described previously.

[0479] If it is an organic film forming composition containing such a surfactant, the film forming property during coating can be further improved by having an appropriate fluorine content.

[0480] The weight average molecular weight of the aryl benzyl ether compound is preferably 1000 to 30000.

[0481] If it is within such a weight average molecular weight range, an organic film with excellent film forming property and filling characteristics can be formed. Also, the weight average molecular weight can be determined by the method described previously.

[0482] The surfactant of the present invention is not limited to use for forming an organic film, and can also be used in the following applications, for example.

[0483] The surfactant of the present invention can be used in all coating materials for optical lithography. Specifically, for example, photosensitive photoresist materials, materials for forming a topcoat formed on a resist film, and the like.

[0484] Furthermore, although it is beyond expectation, the surfactant of the present invention can act as a wetting agent, a flow agent, or a leveling agent in various aqueous or non-aqueous coatings. Examples of aqueous coatings include latex paints and floor polishes applied to glass, wood, metal, ceramics, and polymer substrates. Examples of non-aqueous or solvent-based coatings include, generally, enamels and varnishes applied to the same substrates as above. Furthermore, various fluorinated polar polymers are useful wetting agents, flow agents, or leveling agents in various powder and radiation-curable coatings. The above-mentioned fluorinated polar polymers exert their functions by making the surface tension of the coating smaller than the surface tension of the substrate on which it is used.

[0485] Furthermore, various fluorinated polar polymers can also be used as additives in various consumer products, such as detergents, shampoos, and cosmetics, as well as cleaning agents for furniture and glass, automotive polishes, and the like.

[0486] Furthermore, since the fluorinated polar polymer of the present invention forms a laminate, it can be used in coatings on various substrates.

[0487] The end uses are not limited, and can be classified as follows, for example.

[0488] (1) For paints and coatings, to improve wetting, leveling property, and gloss, to improve stain resistance as a flow modifier, and as a Teflon (registered trademark) wetting aid.

[0489] (2) For waxes and polishes, to improve leveling property and gloss, to improve wetting, and as a Teflon (registered trademark) wetting aid.

[0490] (3) For aqueous adhesives, to improve wetting and leveling property, and as a semi-peelable adhesive. The same also applies to non-aqueous adhesives.

[0491] (4) For various photographic art applications, to improve leveling property, reduce ink capillary action, wet photo emulsions, and improve shelf life.

[0492] (5) For various polymer technology applications, such as mold release spraying, emulsion polymerization, anti-fog agents, external lubricants, internal lubricants, coupling agents, Teflon (registered trademark) wetting aids, wetting agents for olefins and acrylates, and CaSO4 scale removers.

[0493] (6) For electronic applications, such as a scale inhibitor for zinc batteries and an additive for plating baths.

[0494] (7) As a caulking material for improving leveling property and stain resistance.

[0495] (8) For metal technology applications, such as for corrosion resistance, wetting of etching baths, cleaning and scale removal, and for degreasing.

[0496] (9) For various cleaning applications, such as for hair conditioners and rinses, alkaline cleaners, glass cleaners and antifogging agents, shampoos, and for solvent degreasing.

[0497] Further applications, such as floor polish emulsions; electrolytic formation coatings; photo processing; fluoropolymer emulsions; specialty inks; aqueous coatings; solvent-based coatings; electro-etching baths; corrosion inhibitors; solder systems; alkaline systems; pre-etching agents for plastic plating.

[0498] That is, the surfactant of the present invention is useful not only in industrial applications but also in daily commodity applications.

[0499] [Examples]

[0500] The following provides further specific descriptions of the present invention with synthesis examples, comparative synthesis examples, examples, and comparative examples, but the present invention is not limited thereto. Also, the method for measuring the molecular weight is specifically carried out according to the following method. The weight-average molecular weight (Mw), number-average molecular weight (Mn) in terms of polystyrene, and the dispersity (Mw / Mn) are determined by gel permeation chromatography (GPC) using tetrahydrofuran as the eluent (solvent).

[0501] [Synthesis of Aryl Benzyl Ether Compounds (B-1) to (B-18)]

[0502] For the synthesis of compounds (B-1) to (B-18) used in the preparation of the organic film-forming compositions (UDL-1 to 113) of the examples, the following phenolic compounds (a1) to (a14) and bromine compounds (b1) to (b4) were used.

[0503] (Phenolic Compounds)

[0504] [Chemical Formula 86]

[0505]

[0506] (Bromine Compounds)

[0507] [Chemical Formula 87]

[0508]

[0509] [Synthesis Example 1] Synthesis of Aryl Benzyl Ether Compound (B-1)

[0510] [Chemical Formula 88]

[0511]

[0512] To 2.12 g of a phenol-based compound (a1) and 1.93 g of potassium carbonate, 60.0 g of DMF (N,N-dimethylformamide) was added, and the mixture was stirred into a homogeneous solution at an internal temperature of 60 °C under a nitrogen atmosphere. Then, 3.65 g of a bromine compound (b1) was added dropwise to the homogeneous solution over 5 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. Then, the organic layer was washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (B-1).

[0513] The weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0514] (B-1): Mw = 3870, Mw / Mn = 2.74

[0515] [Synthesis Example 2] Synthesis of Aryl Benzyl Ether Compound (B-2)

[0516] [Chemical Formula 89]

[0517]

[0518] To 2.12 g of a phenol-based compound (a1) and 1.38 g of potassium carbonate, 60.0 g of DMF (N,N-dimethylformamide) was added, and the mixture was stirred into a homogeneous solution at an internal temperature of 60 °C under a nitrogen atmosphere. Then, 2.61 g of a bromine compound (b1) was added dropwise to the homogeneous solution over 5 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. Then, the organic layer was washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (B-2).

[0519] The weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0520] (B-2): Mw = 3720, Mw / Mn = 2.79

[0521] [Synthesis Example 3] Synthesis of Aryl Benzyl Ether Compound (B-3)

[0522] [Chemical Formula 90]

[0523]

[0524] To 2.12 g of a phenol-based compound (a1) and 2.49 g of potassium carbonate, 60.0 g of DMF (N,N-dimethylformamide) was added, and the mixture was stirred into a homogeneous solution at an internal temperature of 60 °C under a nitrogen atmosphere. Then, 4.70 g of a bromine compound (b1) was added dropwise to the homogeneous solution over 5 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. Then, the organic layer was washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (B-3).

[0525] The weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0526] (B-3): Mw = 3950, Mw / Mn = 2.67

[0527] [Synthesis Example 4] Synthesis of aryl benzyl ether compound (B-4)

[0528] [Chemical Formula 91]

[0529]

[0530] To 2.67 g of a phenol-based compound (a2) and 1.93 g of potassium carbonate, 60.0 g of DMF (N,N-dimethylformamide) was added, and the mixture was stirred into a homogeneous solution at an internal temperature of 60 °C under a nitrogen atmosphere. Then, 3.57 g of a bromine compound (b2) was added dropwise to the homogeneous solution over 5 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. Then, the organic layer was washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (B-4).

[0531] The weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0532] (B-4): Mw = 7430, Mw / Mn = 5.34

[0533] [Synthesis Example 5] Synthesis of aryl benzyl ether compound (B-5)

[0534] [Chemical Formula 92]

[0535]

[0536] To 2.67 g of the phenol-based compound (a2) and 1.38 g of potassium carbonate, 60.0 g of DMF (N,N-dimethylformamide) was added, and the mixture was stirred into a homogeneous solution at an internal temperature of 60°C under a nitrogen atmosphere. Then, 2.55 g of the bromine compound (b2) was added dropwise to the homogeneous solution over 5 minutes, and the reaction was carried out at an internal temperature of 60°C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. Then, the organic layer was washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain the aryl benzyl ether compound (B-5).

[0537] The weight-average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0538] (B-5): Mw = 7250, Mw / Mn = 5.45

[0539] [Synthesis Example 6] Synthesis of aryl benzyl ether compound (B-6)

[0540] [Chemical Formula 93]

[0541]

[0542] To 2.67 g of the phenol-based compound (a2) and 2.49 g of potassium carbonate, 60.0 g of DMF (N,N-dimethylformamide) was added, and the mixture was stirred into a homogeneous solution at an internal temperature of 60°C under a nitrogen atmosphere. Then, 4.59 g of the bromine compound (b2) was added dropwise to the homogeneous solution over 5 minutes, and the reaction was carried out at an internal temperature of 60°C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. Then, the organic layer was washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain the aryl benzyl ether compound (B-6).

[0543] The weight-average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0544] (B-6): Mw = 7690, Mw / Mn = 5.22

[0545] [Synthesis Example 7] Synthesis of aryl benzyl ether compound (B-7)

[0546] [Chemical Formula 94]

[0547]

[0548] To 2.90 g of the phenol-based compound (a3) and 1.66 g of potassium carbonate, 60.0 g of DMF (N,N-dimethylformamide) was added, and the mixture was stirred into a homogeneous solution at an internal temperature of 60 °C under a nitrogen atmosphere. Then, 3.13 g of the bromine compound (b1) was added dropwise to the homogeneous solution over 5 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. The organic layer was then washed twice with 100 ml of 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain the aryl benzyl ether compound (B-7).

[0549] The weight-average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0550] (B-7): Mw = 5060, Mw / Mn = 2.82

[0551] [Synthesis Example 8] Synthesis of aryl benzyl ether compound (B-8)

[0552] [Chemical Formula 95]

[0553]

[0554] To 6.30 g of the phenol-based compound (a4) and 4.22 g of potassium carbonate, 60.0 g of DMF (N,N-dimethylformamide) was added, and the mixture was stirred into a homogeneous solution at an internal temperature of 60 °C under a nitrogen atmosphere. Then, 8.16 g of the bromine compound (b2) was added dropwise to the homogeneous solution over 10 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. The organic layer was then washed twice with 100 ml of 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain the aryl benzyl ether compound (B-8).

[0555] The weight-average molecular weight (Mw) and the dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0556] (B-8): Mw = 4610, Mw / Mn = 2.49

[0557] [Synthesis Example 9] Synthesis of aryl benzyl ether compound (B-9)

[0558] [Chemical Formula 96]

[0559]

[0560] To 5.07 g of a phenol-based compound (a5) and 3.87 g of potassium carbonate, 60.0 g of DMF (N,N-dimethylformamide) was added, and the mixture was stirred into a homogeneous solution at an internal temperature of 60 °C under a nitrogen atmosphere. Then, 7.31 g of a bromine compound (b1) was added dropwise to the homogeneous solution over 10 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. The organic layer was washed twice with 100 ml of a 3% nitric acid aqueous solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (B-9).

[0561] The weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0562] (B-9): Mw = 3690, Mw / Mn = 2.89

[0563] [Synthesis Example 10] Synthesis of aryl benzyl ether compound (B-10)

[0564] [Chemical Formula 97]

[0565]

[0566] To 7.52 g of a phenol-based compound (a6) and 3.87 g of potassium carbonate, 60.0 g of DMF (N,N-dimethylformamide) was added, and the mixture was stirred into a homogeneous solution at an internal temperature of 60 °C under a nitrogen atmosphere. Then, 7.14 g of a bromine compound (b3) was added dropwise to the homogeneous solution over 10 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. The organic layer was washed twice with 100 ml of a 3% nitric acid aqueous solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (B-10).

[0567] The weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0568] (B-10): Mw = 4020, Mw / Mn = 3.30

[0569] [Synthesis Example 11] Synthesis of aryl benzyl ether compound (B-11)

[0570] [Chemical Formula 98]

[0571]

[0572] 6.35 g of a phenol-based compound (a7) and 6.63 g of potassium carbonate were added to 60.0 g of DMF (N,N-dimethylformamide), and the mixture was stirred into a homogeneous solution at an internal temperature of 60 °C under a nitrogen atmosphere. Then, 12.53 g of a bromine compound (b1) was added dropwise to the homogeneous solution over 20 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. The organic layer was then washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (B-11).

[0573] The weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0574] (B-11): Mw = 11790, Mw / Mn = 6.51

[0575] [Synthesis Example 12] Synthesis of aryl benzyl ether compound (B-12)

[0576] [Chemical Formula 99]

[0577]

[0578] 9.63 g of a phenol-based compound (a8) and 4.98 g of potassium carbonate were added to 60.0 g of DMF (N,N-dimethylformamide), and the mixture was stirred into a homogeneous solution at an internal temperature of 60 °C under a nitrogen atmosphere. Then, 9.18 g of a bromine compound (b2) was added dropwise to the homogeneous solution over 20 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. The organic layer was then washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (B-12).

[0579] The weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0580] (B-12): Mw = 2580, Mw / Mn = 1.81

[0581] [Synthesis Example 13] Synthesis of aryl benzyl ether compound (B-13)

[0582] [Chemical Formula 100]

[0583]

[0584] To 11.69 g of a phenol-based compound (a9) and 11.61 g of potassium carbonate, 60.0 g of DMF (N,N-dimethylformamide) was added, and the mixture was stirred into a homogeneous solution at an internal temperature of 60 °C under a nitrogen atmosphere. Then, 21.92 g of a bromine compound (b1) was added dropwise to the homogeneous solution over 30 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. Then, the organic layer was washed twice with 100 ml of a 3% nitric acid aqueous solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (B-13).

[0585] The weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0586] (B-13): Mw = 1930, Mw / Mn = 1.29

[0587] [Synthesis Example 14] Synthesis of aryl benzyl ether compound (B-14)

[0588] [Chemical Formula 101]

[0589]

[0590] To 11.69 g of a phenol-based compound (a10) and 11.61 g of potassium carbonate, 60.0 g of DMF (N,N-dimethylformamide) was added, and the mixture was stirred into a homogeneous solution at an internal temperature of 60 °C under a nitrogen atmosphere. Then, 21.42 g of a bromine compound (b2) was added dropwise to the homogeneous solution over 30 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. Then, the organic layer was washed twice with 100 ml of a 3% nitric acid aqueous solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (B-14).

[0591] The weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0592] (B-14): Mw = 2140, Mw / Mn = 1.22

[0593] [Synthesis Example 15] Synthesis of aryl benzyl ether compound (B-15)

[0594] [Chemical Formula 102]

[0595]

[0596] To 17.50 g of a phenol-based compound (a11) and 11.61 g of potassium carbonate, 60.0 g of DMF (N,N-dimethylformamide) was added, and the mixture was stirred into a homogeneous solution at an internal temperature of 60 °C under a nitrogen atmosphere. Then, 21.92 g of a bromine compound (b1) was added dropwise to the homogeneous solution over 30 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. The organic layer was then washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (B-15).

[0597] The weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0598] (B-15): Mw = 3610, Mw / Mn = 1.53

[0599] [Synthesis Example 16] Synthesis of aryl benzyl ether compound (B-16)

[0600] [Chemical Formula 103]

[0601]

[0602] To 15.50 g of a phenol-based compound (a12) and 11.61 g of potassium carbonate, 60.0 g of DMF (N,N-dimethylformamide) was added, and the mixture was stirred into a homogeneous solution at an internal temperature of 60 °C under a nitrogen atmosphere. Then, 21.42 g of a bromine compound (b4) was added dropwise to the homogeneous solution over 30 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. The organic layer was then washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (B-16).

[0603] The weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0604] (B-16): Mw = 3050, Mw / Mn = 2.38

[0605] [Synthesis Example 17] Synthesis of aryl benzyl ether compound (B-17)

[0606] [Chemical Formula 104]

[0607]

[0608] 2.40 g of a phenol-based compound (a13) and 1.93 g of potassium carbonate were added to 60.0 g of DMF (N,N-dimethylformamide), and the mixture was stirred into a homogeneous solution at an internal temperature of 60 °C under a nitrogen atmosphere. Then, 3.65 g of a bromine compound (b1) was added dropwise to the homogeneous solution over 5 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. The organic layer was then washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (B-17).

[0609] The weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0610] (B-17): Mw = 23220, Mw / Mn = 1.17

[0611] [Synthesis Example 18] Synthesis of aryl benzyl ether compound (B-18)

[0612] [Chemical Formula 105]

[0613]

[0614] 2.40 g of a phenol-based compound (a14) and 1.93 g of potassium carbonate were added to 60.0 g of DMF (N,N-dimethylformamide), and the mixture was stirred into a homogeneous solution at an internal temperature of 60 °C under a nitrogen atmosphere. Then, 3.57 g of a bromine compound (b2) was added dropwise to the homogeneous solution over 5 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. The organic layer was then washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (B-18).

[0615] The weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0616] (B-18): Mw = 20490, Mw / Mn = 1.14

[0617] [Synthesis of Comparative Compounds (R1) to (R6)]

[0618] The comparative compounds (R1) to (R6) used for the preparation of the composition for forming an organic film in the comparative examples (Comparative UDL-7 to 17) were synthesized using the following monomers (r1) to (r3) and bromine compounds (r4) and (r5).

[0619] [Chemical Formula 106]

[0620]

[0621] [Comparative Synthesis Example 1] Synthesis of Comparative Compound (R1)

[0622] [Chemical Formula 107]

[0623]

[0624] Under a nitrogen atmosphere, 7.45 g of monomer (r1) was added to 40.0 g of PGME (propylene glycol monomethyl ether), and the mixture was stirred at an internal temperature of 110 °C to form a homogeneous solution. Then, 1.14 g of p-toluenesulfonic acid was added to the homogeneous solution, and the reaction was carried out at an internal temperature of 110 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. After washing 5 times with 100 ml of pure water, the organic layer was dried under reduced pressure to obtain the target compound (R1).

[0625] The weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0626] (R1): Mw = 5020, Mw / Mn = 3.11

[0627] [Comparative Synthesis Example 2] Synthesis of Comparative Compound (R2)

[0628] [Chemical Formula 108]

[0629]

[0630] Under a nitrogen atmosphere, 2.16 g of monomer (r2) and 0.54 g of monomer (r3) were added to 40.0 g of PGME (propylene glycol monomethyl ether), and the mixture was stirred at an internal temperature of 110 °C to form a homogeneous solution. Then, 0.38 g of p-toluenesulfonic acid was added to the homogeneous solution, and the reaction was carried out at an internal temperature of 110 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. After washing 5 times with 100 ml of pure water, the organic layer was dried under reduced pressure to obtain the target compound (R2).

[0631] The weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0632] (R2): Mw = 5700, Mw / Mn = 3.55

[0633] [Comparative Synthesis Example 3] Synthesis of Comparative Compound (R3)

[0634] [Chemical 109]

[0635]

[0636] To 2.12 g of a phenol-based compound (R1) and 1.24 g of potassium carbonate, 60.0 g of DMF (N,N-dimethylformamide) was added, and the mixture was stirred into a homogeneous solution at an internal temperature of 60 °C under a nitrogen atmosphere. Then, 2.35 g of a bromine compound (r4) was added dropwise to the homogeneous solution over 5 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. Then, the organic layer was washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (R3).

[0637] The weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0638] (R3): Mw = 3700, Mw / Mn = 2.80

[0639] [Comparative Synthesis Example 4] Synthesis of Comparative Compound (R4)

[0640] [Chemical 110]

[0641]

[0642] To 2.67 g of a phenol-based compound (R2) and 1.24 g of potassium carbonate, 60.0 g of DMF (N,N-dimethylformamide) was added, and the mixture was stirred into a homogeneous solution at an internal temperature of 60 °C under a nitrogen atmosphere. Then, 2.30 g of a bromine compound (r5) was added dropwise to the homogeneous solution over 5 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. Then, the organic layer was washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (R4).

[0643] The weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0644] (R4): Mw = 7230, Mw / Mn = 5.46

[0645] [Comparative Synthesis Example 5] Synthesis of Comparative Compound (R5)

[0646] [Chemical 111]

[0647]

[0648] To 2.12 g of a phenol-based compound (R1) and 2.63 g of potassium carbonate, 60.0 g of DMF (N,N-dimethylformamide) was added, and the mixture was stirred into a homogeneous solution at an internal temperature of 60 °C under a nitrogen atmosphere. Then, 4.96 g of a bromine compound (r4) was added dropwise to the homogeneous solution over 5 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. Then, the organic layer was washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (R5).

[0649] The weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0650] (R5): Mw = 3960, Mw / Mn = 2.65

[0651] [Comparative Synthesis Example 6] Synthesis of Comparative Compound (R6)

[0652] [Chemical Formula 112]

[0653]

[0654] To 2.67 g of a phenol-based compound (R2) and 2.63 g of potassium carbonate, 60.0 g of DMF (N,N-dimethylformamide) was added, and the mixture was stirred into a homogeneous solution at an internal temperature of 60 °C under a nitrogen atmosphere. Then, 4.84 g of a bromine compound (r5) was added dropwise to the homogeneous solution over 5 minutes, and the reaction was carried out at an internal temperature of 60 °C for 24 hours. After the reaction solution was cooled to room temperature, 100 ml of methyl isobutyl ketone and 100 ml of pure water were added to the reaction solution to homogenize it, and then the separated aqueous layer was removed. Then, the organic layer was washed twice with 100 ml of a 3% aqueous nitric acid solution and five times with 100 ml of pure water, and then the organic layer was dried under reduced pressure to obtain an aryl benzyl ether compound (R6).

[0655] The weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the results were as follows.

[0656] (R6): Mw = 7700, Mw / Mn = 5.21

[0657] [(A) Material for forming an organic film (resin or compound)]

[0658] Preparation of the composition for forming an organic film (UDL-1 to 113 and Comparative UDL-1 to 17) of Examples and Comparative Examples was carried out using the following resins or compounds as (A) the material for forming an organic film.

[0659] M1: Resin represented by the following formula (M1)

[0660] M2: Resin represented by the following formula (M2)

[0661] M3: Compound represented by the following formula (M3)

[0662] M4: Compound represented by the following formula (M4)

[0663] M5: Resin represented by the following formula (M5)

[0664] M6: Resin represented by the following formula (M6)

[0665] [Chemical formula 113]

[0666]

[0667] [(C) Solvent]

[0668] For the preparation of the composition for forming an organic film (UDL-1 to 113 and Comparative UDL-1 to 17) of Examples and Comparative Examples, the following solvents were used as (C) solvents, respectively.

[0669] (S1): Propylene glycol monomethyl ether acetate

[0670] (S2): Propylene glycol monoethyl ether

[0671] [Preparation of the composition for forming an organic film (UDL-1 to 113, Comparative UDL-1 to 17)]

[0672] Any one of the above compounds (B-1) to (B-18) and (R1) to (R6), and any one of the above materials (M1) to (M6) for forming an organic film were dissolved in one or both of the above solvents at the ratios shown in Tables 1 to 4. The mixture thus obtained was filtered through a 0.1-μm fluororesin filter to prepare the composition for forming an organic film (anti-reflective coating material: UDL-1 to 113, Comparative UDL-7 to 17), respectively. Further, any one of the above materials (M1) to (M6) for forming an organic film and the above solvent (S1) were dissolved at the ratio shown in Table 4. The mixture thus obtained was filtered through a 0.1-μm fluororesin filter to prepare the composition for forming an organic film (anti-reflective coating material: Comparative UDL-1 to 6), respectively.

[0673] [Table 1]

[0674]

[0675]

[0676] [Table 2]

[0677]

[0678]

[0679] [Table 3]

[0680]

[0681] [Table 4]

[0682]

[0683]

[0684] [Fabrication of Silicon Wafers with Organic Hard Films Formed Using Organic Film-Forming Compositions (UDL-1 to 113, Comparative UDL-1 to 17)]

[0685] Using the coater / developer "CLEAN TRACK LITHIUS Pro AP" from Tokyo Electron Limited, 2 ml of each of the above-prepared organic film-forming compositions (UDL-1 to 113, Comparative UDL-1 to 17) was sprayed onto the center of a silicon wafer, and the wafer was rotated at the rotation speed to achieve the average film thickness recorded in Tables 5 to 8. After spreading, it was baked at 350 °C to form a coating film of the organic film-forming composition. While rotating the silicon wafer at a speed of 1000 rpm, the remover liquid was discharged from the discharge nozzle at a discharge rate of 2 mL / s (a mixed liquid of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether (30:70, mass ratio)), and at the same time, it was moved from the outer peripheral part of the silicon wafer toward the center part at a speed of 5 mm / s until it reached a position of 3 mm. At this position, the remover liquid was discharged at a discharge rate of 2 mL / s for 5 seconds. After that, the discharge of the liquid was stopped, and the silicon wafer was rotated at a speed of 1000 rpm for 30 seconds. Then, the silicon wafer was heated at 350 °C for 60 seconds, thereby obtaining silicon wafers with organic films (organic hard films) formed in each example.

[0686] [Solvent Resistance Evaluation: Examples 1-1 to 1-113, Comparative Examples 1-1 to 1-17]

[0687] Using the respective organic film forming compositions (UDL-1 to 113, Comparative UDL-1 to 17) on a silicon wafer according to the above method, the organic film was formed and the film thickness was measured. Then, PGMEA solvent was dropped on each organic film, left for 30 seconds and spun dry, and baked at 100 °C for 60 seconds to evaporate PGMEA, and the film thickness was measured. Let the film thickness before dropping PGMEA solvent be X and the film thickness after dropping PGMEA solvent be X1, and define the absolute value of the value obtained by (X1 - X) / X × 100 as the film thickness change rate (%). When the film thickness change rate is less than 0.5%, it is rated as good, and when it is 0.5% or more, it is rated as bad. The results are shown in Tables 5 to 8 below.

[0688] [In-plane uniformity evaluation: Examples 1-1 to 1-113, Comparative Examples 1-1 to 1-17]

[0689] Using the respective organic film forming compositions (UDL-1 to 113, Comparative UDL-1 to 17) on a silicon wafer according to the above method, the organic film was formed, and the film thickness within a radius of 145 mm from the center of the organic film was measured. Let the maximum film thickness be Xmax, the minimum film thickness be Xmin, and the average film thickness be X average , and define the value obtained by (X max -X min ) / X average as the in-plane uniformity (%). When the in-plane uniformity is less than 2%, it is rated as A (good), when it is 2% or more and less than 3%, it is rated as B, and when it is 3% or more, it is rated as C (bad). The results are shown in Tables 5 to 8.

[0690] [Table 5]

[0691]

[0692]

[0693] [Table 6]

[0694]

[0695]

[0696] [Table 7]

[0697]

[0698]

[0699] [Table 8]

[0700] Composition for forming organic film Average film thickness Solvent resistance In-plane uniformity Example 1-109 UDL-109 500 nm Good A Example 1-110 UDL-110 500 nm Good A Example 1-111 UDL-111 500 nm Good A Example 1-112 UDL-112 500 nm Good A Example 1-113 UDL-113 500 nm Good A Comparative Example 1-1 Comparative UDL-1 500 nm Good C Comparative Example 1-2 Comparative UDL-2 500 nm Good C Comparative Example 1-3 Comparative UDL-3 500 nm Good C Comparative Example 1-4 Comparative UDL-4 500 nm Good C Comparative Example 1-5 Comparative UDL-5 500 nm Good C Comparative Example 1-6 Comparative UDL-6 500 nm Good C Comparative Example 1-7 Comparative UDL-7 500 nm Good C Comparative Example 1-8 Comparative UDL-8 500 nm Good C Comparative Example 1-9 Comparative UDL-9 500 nm Good C Comparative Example 1-10 Comparative UDL-10 500 nm Good C Comparative Example 1-11 Comparative UDL-11 500 nm Good C Comparative Example 1-12 Comparative UDL-12 500 nm Good C Comparative Example 1-13 Comparative UDL-13 500 nm Good C Comparative Example 1-14 Comparative UDL-14 500 nm Good C Comparative Example 1-15 Comparative UDL-15 500 nm Good C Comparative Example 1-16 Comparative UDL-16 500 nm Good A Comparative Example 1-17 Comparative UDL-17 500 nm Good A

[0701] As shown in Tables 5 to 8, in Examples 1-1 to 1-113 using the organic film-forming composition of the present invention, an organic film with good solvent resistance and in-plane uniformity was obtained. However, in Comparative Examples 1-1 to 1-15 (Comparative UDL-1 to 15) among Comparative Examples 1-1 to 1-17 using a composition that does not contain the aryl benzyl ether compound contained in the organic film-forming composition of the present invention, the in-plane uniformity was poor. The following evaluation will be discussed for UDL-1 to 113 with good solvent resistance and in-plane uniformity and Comparative UDL-16 to 17.

[0702] [Evaluation of bulge suppression: Examples 2-1 to 2-113, Comparative Examples 2-1 to 2-2]

[0703] Using each organic film-forming composition (UDL-1 to 113, Comparative UDL-16 to 17), an organic film was formed on a silicon wafer according to the above method, and the height change of the outer peripheral end of the organic film in the direction of the center of the silicon wafer up to a position of 1000 μm was measured using an Alpha-Step D-600 (contact profilometer) manufactured by KLA-TENCOR Corporation. When the height of the silicon wafer is 0, as Figure 2 shown, when the maximum height is less than 110% of the film thickness, it is rated as A (good), when the maximum height is 110% or more and less than 150%, it is rated as B, and as Figure 3 shown, when a region with a height of 150% or more occurs, it is rated as C (bad). The results are shown in Tables 9 to 12.

[0704] [Filling evaluation: Examples 2-1 to 2-113, Comparative Examples 2-1 to 2-2]

[0705] As Figure 4 shown, on a SiO2 wafer substrate having a dense hole pattern (hole diameter 0.2 μm, hole depth 1.0 μm, distance between the centers of two adjacent holes 0.4 μm), each organic film-forming composition (UDL-1 to 113, Comparative UDL-16 to 17) was used to form a film according to the above method, and an organic film 8 was formed. The substrate used was a base substrate (SiO2 wafer substrate) 7 having a dense hole pattern as shown in Figure 4 (G) (top view) and (H) (cross-sectional view). The cross-sectional shape of each obtained wafer substrate was observed using a scanning electron microscope (SEM) to confirm whether there were no voids inside the holes and they were filled with the organic film. When using an organic film-forming composition with poor filling characteristics, voids appeared inside the holes. When using an organic film-forming composition with good filling characteristics, in this evaluation, as Figure 4 shown in (I), there were no voids inside the holes and they were filled with the organic film. When no voids occurred, it was rated as good, and when voids occurred, it was rated as bad. The results are shown in Tables 9 to 12.

[0706] [Evaluation of Coating Property of Silicon-Containing Resist Intermediate Film: Examples 2-1 to 2-113, Comparative Examples 2-1 to 2-2]

[0707] Using each organic film-forming composition (UDL-1 to 113, Comparative UDL-16 to 17), an organic film was formed on a silicon wafer substrate according to the above method. The following silicon-containing resist intermediate film material (SOG1) was coated thereon and baked at 200 °C for 60 seconds to form a silicon-containing resist intermediate film. And the state of the coating film of the silicon-containing resist intermediate film was visually observed and evaluated.

[0708] When the state of the coating film of the silicon-containing resist intermediate film was good, it was rated as good; when dewetting occurred, it was rated as bad.

[0709] Also, in this evaluation, in order to evaluate the superiority and inferiority of the coating property of the silicon-containing resist intermediate film, the evaluation condition was a strict evaluation condition with the film thickness of the silicon-containing resist intermediate film set to 10 nm. The results are shown in Tables 9 to 12.

[0710] A propylene glycol ethyl ether solution of the following polymer was prepared as the silicon-containing resist intermediate film material (SOG1). The polymer solution used for the evaluation of the coating property of the silicon-containing resist intermediate film was 0.5% by weight.

[0711] [Chemical Formula 114]

[0712]

[0713] [Contact Angle Evaluation: Examples 2-1 to 2-113, Comparative Examples 2-1 to 2-2]

[0714] Using each organic film-forming composition (UDL-1 to 113, Comparative UDL-16 to 17), an organic film was formed on a silicon wafer substrate according to the above method, and the contact angle with pure water was measured. The results are shown in Tables 9 to 12.

[0715] [Table 9]

[0716]

[0717]

[0718] [Table 10]

[0719]

[0720]

[0721] [Table 11]

[0722]

[0723]

[0724] [Table 12]

[0725]

[0726] As shown in Tables 9 to 12, it was confirmed that the solvent resistance, in-plane uniformity, bulge suppression property, filling property, and coatability of the silicon-containing resist intermediate film of the composition for forming an organic film (UDL-1 to 113) of the present invention were excellent. Also, the contact angle was between 55 and 66 degrees.

[0727] [Contact Angle Evaluation Comparison for Baking at 250°C and 350°C: Examples 3-1 to 3-54 and Comparative Examples 3-1 to 3-2]

[0728] The silicon wafers coated with the composition for forming an organic film were heated at 250°C for 60 seconds, and then organic films were formed on the silicon wafer substrates using each composition for forming an organic film (UDL-24 to 77 and Comparative UDL-16 to 17) in the same manner as the above method. The contact angle with pure water was measured. The results are shown in Tables 13 to 14.

[0729] Also, for the composition for forming an organic film, a resin for forming an organic film that was baked at 250°C and had a good solvent resistance evaluation result in the same manner as the above method was selected. The results are shown in Tables 13 to 14.

[0730] Also, each result of the contact angle evaluation for baking at 350°C was obtained in Example 2.

[0731] [Silicon Intermediate Film Coatability Evaluation Comparison for Baking at 250°C and 350°C: Examples 3-1 to 3-54 and Comparative Examples 3-1 to 3-2]

[0732] The silicon wafers coated with the composition for forming an organic film were heated at 250°C for 60 seconds, and then organic films were formed on the silicon wafer substrates using the composition for forming an organic film (UDL-24 to 77 and Comparative UDL-16 to 17) in the same manner as the above method. Then, the following silicon-containing resist intermediate film material (SOG1) was coated thereon, baked at 200°C for 60 seconds, and a silicon-containing resist intermediate film was formed. The coating state of the silicon-containing resist intermediate film was visually observed and evaluated.

[0733] When the coating state was good, it was rated as good; when dewetting occurred, it was rated as bad.

[0734] Also, in this evaluation, in order to evaluate the superiority or inferiority of the coatability of the silicon-containing resist intermediate film, the evaluation condition was a strict evaluation condition with the film thickness of the silicon-containing resist intermediate film set to 10 nm. The results are shown in Tables 13 to 14.

[0735] Further, the evaluation results of the coating properties of the silicon intermediate film baked at 350°C shown in Tables 13 to 14 were obtained in Example 2.

[0736] Regarding the silicon-containing resist intermediate film material (SOG1), a propylene glycol monoethyl ether solution of the same polymer as that used in Example 2 was prepared. The polymer solution used for evaluating the coating properties of the silicon-containing resist intermediate film was 0.5% by weight.

[0737] [Table 13]

[0738]

[0739]

[0740] [Table 14]

[0741]

[0742]

[0743] As shown in Tables 13 to 14, it was confirmed that the silicon-containing resist intermediate film formed by baking the composition for forming an organic film (UDL-24 to 77) of the present invention at 250°C had excellent coating properties. Further, the contact angle at 250°C was 68 degrees or more and less than 80 degrees. On the other hand, in Comparative Examples 3-1 to 3-2 having a structure outside the above range, in the low-temperature range where thermal decomposition did not occur at the benzyl position, due to the high contact angle, the coating properties of the silicon-containing resist intermediate film deteriorated. For the above reasons, it was confirmed that by adjusting the ratio β of the fluorine-substituted group and the ratio α of the phenolic hydroxyl group of the structure represented by the above formula (B2) to the above range, even in the low-temperature range where thermal decomposition did not occur at the benzyl position, the contact angle could be adjusted due to the sufficient presence of the phenolic hydroxyl group, and a composition for forming an organic film having excellent coating properties for an intermediate film such as a silicon-containing resist intermediate film was obtained.

[0744] [Pattern formation test: Examples 4-1 to 4-113]

[0745] An organic film was formed on a SiO2 wafer substrate using each composition for forming an organic film (UDL-1 to 113) by the above method (baking at 350°C). The following silicon-containing resist intermediate film material (SOG1) was coated thereon, baked at 200°C for 60 seconds, and a silicon-containing resist intermediate film with a film thickness of 35 nm was formed. The following ArF single-layer resist was coated thereon as a resist upper film material, baked at 105°C for 60 seconds, and a photoresist film with a film thickness of 100 nm was formed. The following wetting protective film material (TC-1) was coated on the photoresist film, baked at 90°C for 60 seconds, and a protective film with a film thickness of 50 nm was formed.

[0746] Prepare a 2% solution of propylene glycol ethyl ether of the following polymer as a silicon-containing resist intermediate film material (SOG1).

[0747] [Chemical formula 115]

[0748]

[0749] For the resist upper layer film material (single-layer resist for ArF), dissolve the polymer (RP1), acid generator (PAG1), and basic compound (Amine1) in a solvent (PGMEA) containing 0.1 mass% of FC-430 (manufactured by Sumitomo 3M Co., Ltd.) according to the ratio in Table 15, and filter through a 0.1-μm fluororesin filter to prepare it.

[0750] [Table 15]

[0751]

[0752] The polymer (RP1), acid generator (PAG1), and basic compound (Amine1) are as follows.

[0753] [Chemical formula 116]

[0754]

[0755] For the wetting protective film material (TC-1), dissolve the polymer (PP1) in an organic solvent according to the ratio in Table 16, and filter through a 0.1-μm fluororesin filter to prepare it.

[0756] [Table 16]

[0757]

[0758] The polymer (PP1) is as follows.

[0759] [Chemical formula 117]

[0760]

[0761] Next, perform exposure using an ArF immersion exposure apparatus (manufactured by Nikon Corporation; NSR-S610C, NA 1.30, σ 0.98 / 0.65, 35-degree dipole s-polarized illumination, 6% half-tone phase shift mask), bake at 100 °C for 60 seconds (PEB), and develop for 30 seconds with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) to obtain a 55-nm 1:1 positive line-and-space pattern (resist upper layer film pattern).

[0762] Next, using the etching device Telius manufactured by Tokyo Electron Limited, dry etching (pattern transfer) is performed on the silicon-containing resist intermediate film using the upper resist film pattern as a mask to obtain a silicon-containing resist intermediate film pattern. Using the obtained silicon-containing resist intermediate film pattern as a mask, dry etching (pattern transfer) is performed on the organic film to obtain an organic film pattern. Using the obtained organic film pattern as a mask, dry etching (pattern transfer) is performed on the SiO2 wafer substrate (SiO2 film). The etching conditions are as follows.

[0763] (Transfer conditions of the upper resist film pattern to the silicon-containing resist intermediate film)

[0764]

[0765] (Transfer conditions of the silicon-containing resist intermediate film pattern to the organic film)

[0766]

[0767] (Transfer conditions of the organic film pattern to the SiO2 wafer substrate)

[0768]

[0769] The cross-section of the obtained pattern was observed with an electron microscope (S-4700) manufactured by Hitachi, Ltd., and the results are shown in Tables 17 to 20.

[0770] [Table 17]

[0771] Composition for forming organic film Shape of substrate after transfer etching Example 4-1 UDL-1 Good Example 4-2 UDL-2 Good Example 4-3 UDL-3 Good Example 4-4 UDL-4 Good Example 4-5 UDL-5 Good Example 4-6 UDL-6 Good Example 4-7 UDL-7 Good Example 4-8 UDL-8 Good Example 4-9 UDL-9 Good Example 4-10 UDL-10 Good Example 4-11 UDL-11 Good Example 4-12 UDL-12 Good Example 4-13 UDL-13 Good Example 4-14 UDL-14 Good Example 4-15 UDL-15 Good Example 4-16 UDL-16 Good Example 4-17 UDL-17 Good Example 4-18 UDL-18 Good Example 4-19 UDL-19 Good Example 4-20 UDL-20 Good Example 4-21 UDL-21 Good Example 4-22 UDL-22 Good Example 4-23 UDL-23 Good Example 4-24 UDL-24 Good Example 4-25 UDL-25 Good Example 4-26 UDL-26 Good Example 4-27 UDL-27 Good Example 4-28 UDL-28 Good Example 4-29 UDL-29 Good Example 4-30 UDL-30 Good Example 4-31 UDL-31 Good Example 4-32 UDL-32 Good Example 4-33 UDL-33 Good Example 4-34 UDL-34 Good Example 4-35 UDL-35 Good Example 4-36 UDL-36 Good

[0772] [Table 18]

[0773]

[0774]

[0775] [Table 19]

[0776]

[0777]

[0778] [Table 20]

[0779] Composition for forming organic film Shape of substrate after transfer etching Example 4-109 UDL-109 Good Example 4-110 UDL-110 Good Example 4-111 UDL-111 Good Example 4-112 UDL-112 Good Example 4-113 UDL-113 Good

[0780] As shown in Tables 17 to 20, in Examples 4-1 to 4-113 using the composition for forming an organic film (UDL-1 to 113) of the embodiments of the present invention, the resist upper layer film patterns were finally transferred well onto the SiO2 wafer substrate, and it was confirmed that the composition for forming an organic film of the embodiments of the present invention is suitable for use in fine processing using the multilayer resist method.

[0781] From the above, it can be seen that if it is the composition for forming an organic film of the present invention, it has excellent film-forming properties, a high degree of filling properties, and excellent swelling suppression properties. The coating property of the silicon-containing resist intermediate film is excellent, so it is extremely useful as an organic film material for multilayer resist processing. Also, it can be seen that if it is the pattern forming method of the present invention using the composition for forming an organic film of the present invention, an organic film can be formed that fills holes and trenches with a very high aspect ratio without voids, and can form fine patterns with high precision, and the swelling can be suppressed. Therefore, semiconductor elements and the like can be manufactured with good efficiency.

[0782] Also, from the results of the above-described examples, it can be seen that the surfactant of the present invention becomes an ideal surfactant for forming an organic film with excellent in-plane uniformity and filling properties, and in which the formation of swelling due to the influence of the remover in the EBR step is suppressed. Also, it can be seen that if the surfactant of the present invention is used, a composition for forming an organic film can be achieved that can form an intermediate film, for example, a silicon-containing intermediate film, on which an organic film can be formed with excellent coating properties.

[0783] This specification includes the following aspects.

[0784] [1] A composition for forming an organic film, characterized by comprising:

[0785] (A) A material for forming an organic film,

[0786] (B) An aryl benzyl ether compound having a partial structure represented by the following general formula (B1), and

[0787] (C) A solvent,

[0788] [Chemical formula 118]

[0789]

[0790] In the formula, R1 is a hydrogen atom or any fluorine-containing group represented by the following formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the following formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, a is 0 or 1. When a is 0, b is 1 to 5 and c is 0 to 4. When a is 1, b is 1 to 7 and c is 0 to 6. * represents a chemical bond with other atoms.

[0791] [Chemical formula 119]

[0792]

[0793] In the formula, the dashed line represents a chemical bond with the oxygen atom in the above formula (B1), and may also have one or two of the structures represented by the above formula (B2).

[0794] [2] The composition for forming an organic film as in [1], wherein the aforementioned (B) aryl benzyl ether compound is a compound represented by the following general formula (B3), (B4), (B6), (B8), (B10), or (B11).

[0795] [Chemical formula 120]

[0796]

[0797] In the formula, R1 is a hydrogen atom or one or two of the fluorine-containing groups represented by the aforementioned formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, R3 is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, a1 is 0 or 1. When a1 is 0, b1 is 1 to 5 and c1 is 0 to 4. When a1 is 1, b1 is 1 to 7 and c1 is 0 to 6.

[0798] [Chemical formula 121]

[0799]

[0800] In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, R4 is a single bond or any one of the groups represented by the following formula (B5), R5 is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, a2 is 0 or 1. When a2 is 0, b2 is 1 to 5 and c2 is 0 to 4. When a2 is 1, b2 is 1 to 7 and c2 is 0 to 6.

[0801] [Chemical formula 122]

[0802]

[0803] [Chemical formula 123]

[0804]

[0805] In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, R6 is any group represented by the following formula (B7), R7 is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, a3 is 0 or 1. When a3 is 0, b3 is 1 to 5 and c3 is 0 to 4. When a3 is 1, b3 is 1 to 7 and c3 is 0 to 6.

[0806] [Chemical formula 124]

[0807]

[0808] [Chemical formula 125]

[0809]

[0810] In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. W1 is a group represented by the following formula (B9), a4 is 0 or 1, b4 is 1 or 2, and d4 is 1 to 4.

[0811] [Chemical formula 126]

[0812]

[0813] In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied.

[0814] [Chemical 127]

[0815]

[0816] In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. W1 is a group represented by the above formula (B9), W2 is a single bond or an organic group having 1 to 50 carbon atoms, m is an integer satisfying 1 ≤ m ≤ 5, a5 is 0 or 1, b5 is 1 or 2, and d5 is 1 to 4.

[0817] [Chemical 128]

[0818]

[0819] In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R8 is a hydrogen atom or a methyl group, and b6 is 1 to 5.

[0820] [3] The composition for forming an organic film according to [1] or [2], wherein the weight average molecular weight of the aforementioned (B) aryl benzyl ether compound is 1000 to 30000.

[0821] [4] The composition for forming an organic film according to any one of [1] to [3], wherein the content of the aforementioned (B) aryl benzyl ether compound is 0.01 to 5 parts by mass with respect to 100 parts by mass of the content of the aforementioned (A) material for forming an organic film.

[0822] [5] An organic film forming method, which is a method for forming an organic film used in the manufacturing process of a semiconductor device, characterized in that:

[0823] A coating film is obtained by spin-coating the composition for forming an organic film according to any one of [1] to [4] on a substrate to be processed,

[0824] The aforementioned coating film is heat-treated at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds to be hardened to form an organic film.

[0825] [6] A pattern forming method, characterized in that:

[0826] An organic film is formed on a workpiece using the composition for forming an organic film according to any one of [1] to [4],

[0827] A silicon-containing resist intermediate film is formed on the aforementioned organic film using a silicon-containing resist intermediate film material,

[0828] A resist upper layer film is formed on the aforementioned silicon-containing resist intermediate film using a resist upper layer film material composed of a photoresist composition,

[0829] A circuit pattern is formed on the aforementioned resist upper layer film, and the resist upper layer film on which the circuit pattern has been formed is used as a mask to transfer the pattern by etching onto the aforementioned silicon-containing resist intermediate film,

[0830] The silicon-containing resist intermediate film on which the pattern has been transferred is used as a mask to transfer the pattern by etching onto the aforementioned organic film,

[0831] Then, the organic film on which the pattern has been transferred is used as a mask to form a pattern by etching on the aforementioned workpiece.

[0832] [7] A pattern forming method, characterized in that:

[0833] An organic film is formed on a workpiece using the composition for forming an organic film according to any one of [1] to [4],

[0834] A silicon-containing resist intermediate film is formed on the aforementioned organic film using a silicon-containing resist intermediate film material, and an organic antireflection film or a bonding film is formed on the aforementioned silicon-containing resist intermediate film,

[0835] A resist upper layer film is formed on the aforementioned organic antireflection film or bonding film using a resist upper layer film material composed of a photoresist composition, and a circuit pattern is formed on the aforementioned resist upper layer film,

[0836] The resist upper layer film on which the circuit pattern has been formed is used as a mask to transfer the pattern by etching onto the aforementioned organic antireflection film or bonding film and the aforementioned silicon-containing resist intermediate film,

[0837] The silicon-containing resist intermediate film on which the pattern has been transferred is used as a mask to transfer the pattern by etching onto the aforementioned organic film,

[0838] Then, the organic film on which the pattern has been transferred is used as a mask to form a pattern by etching on the aforementioned workpiece.

[0839] [8] A pattern forming method, characterized in that:

[0840] An organic film is formed on a workpiece using the composition for forming an organic film according to any one of [1] to [4].

[0841] An inorganic hard mask selected from the group consisting of a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the aforementioned organic film.

[0842] An upper resist film is formed on the aforementioned inorganic hard mask using a resist upper film material composed of a photoresist composition.

[0843] A circuit pattern is formed on the aforementioned upper resist film.

[0844] Using the upper resist film on which the circuit pattern has been formed as a mask, the pattern is transferred by etching to the aforementioned inorganic hard mask.

[0845] Using the inorganic hard mask on which the pattern has been transferred as a mask, the pattern is transferred by etching to the aforementioned organic film.

[0846] Using the organic film on which the pattern has been transferred as a mask, the pattern is formed by etching on the aforementioned workpiece.

[0847] [9] A pattern forming method, characterized in that:

[0848] An organic film is formed on a workpiece using the composition for forming an organic film according to any one of [1] to [4].

[0849] An inorganic hard mask selected from the group consisting of a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the organic film.

[0850] An organic antireflection film or a bonding film is formed on the inorganic hard mask, and an upper resist film is formed on the organic antireflection film or the bonding film using a resist upper film material composed of a photoresist composition.

[0851] A circuit pattern is formed on the upper resist film.

[0852] Using the upper resist film on which the circuit pattern has been formed as a mask, the pattern is transferred by etching to the organic antireflection film or the bonding film and the inorganic hard mask.

[0853] Using the inorganic hard mask on which the pattern has been transferred as a mask, the pattern is transferred by etching to the organic film.

[0854] Using the organic film on which the pattern has been transferred as a mask, the pattern is formed by etching on the workpiece.

[0855]

[10] The pattern forming method according to [8] or [9], wherein the inorganic hard mask is formed by CVD method or ALD method.

[0856]

[11] The pattern formation method according to any one of [6] to

[10] , wherein in the formation of the circuit pattern, photolithography using light with a wavelength of 10 nm or more and 300 nm or less, direct drawing using an electron beam, nanoimprinting, or a combination thereof is used to form the circuit pattern.

[0857]

[12] The pattern formation method according to any one of [6] to

[11] , wherein in the formation of the circuit pattern, the circuit pattern is developed using alkali development or an organic solvent.

[0858]

[13] The pattern formation method according to any one of [6] to

[12] , wherein the object to be processed is a semiconductor device substrate, or any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, and a metal oxynitride film is formed on the semiconductor device substrate.

[0859]

[14] The pattern formation method according to

[13] , wherein for the object to be processed, the metal constituting the object to be processed is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof.

[0860]

[15] A surfactant composed of an aryl benzyl ether compound having a partial structure represented by the following general formula (B1),

[0861] [Chemical formula 129]

[0862]

[0863] In the formula, R1 is a hydrogen atom or an arbitrary fluorine-containing group represented by the following formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the following formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, a is 0 or 1. When a is 0, b is 1 to 5 and c is 0 to 4. When a is 1, b is 1 to 7 and c is 0 to 6. * represents an atomic bond with other atoms.

[0864] [Chemical formula 130]

[0865]

[0866] In the formula, the dotted line represents an atomic bond with the oxygen atom in the above formula (B1), and may have one or two of the structures represented by the above formula (B2).

[0867]

[16] The surfactant as described in

[15] , wherein the aryl benzyl ether compound is a compound represented by the following general formula (B3), (B4), (B6), (B8), (B10), or (B11).

[0868] [Chemical formula 131]

[0869]

[0870] In the formula, R1 is a hydrogen atom or one or two of the fluorine-containing groups represented by the foregoing formula (B2). Among the structures constituting the foregoing R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the foregoing formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, R3 is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, a1 is 0 or 1. When a1 is 0, b1 is 1 to 5 and c1 is 0 to 4. When a1 is 1, b1 is 1 to 7 and c1 is 0 to 6.

[0871] [Chemical formula 132]

[0872]

[0873] In the formula, R1 is a hydrogen atom or one or two of the fluorine-containing groups represented by the foregoing formula (B2). Among the structures constituting the foregoing R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the foregoing formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, R4 is a single bond or any one of the groups represented by the following formula (B5), R5 is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, a2 is 0 or 1. When a2 is 0, b2 is 1 to 5 and c2 is 0 to 4. When a2 is 1, b2 is 1 to 7 and c2 is 0 to 6.

[0874] [Chemical formula 133]

[0875]

[0876] [Chemical formula 134]

[0877]

[0878] In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, R6 is any group represented by the following formula (B7), R7 is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, a3 is 0 or 1. When a3 is 0, b3 is 1 to 5 and c3 is 0 to 4. When a3 is 1, b3 is 1 to 7 and c3 is 0 to 6.

[0879] [Chemical formula 135]

[0880]

[0881] [Chemical formula 136]

[0882]

[0883] In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. W1 is a group represented by the following formula (B9), a4 is 0 or 1, b4 is 1 or 2, and d4 is 1 to 4.

[0884] [Chemical formula 137]

[0885]

[0886] In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied.

[0887] [Chemical formula 138]

[0888]

[0889] In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. W1 is a group represented by the above formula (B9), W2 is a single bond or an organic group having 1 to 50 carbon atoms, m is an integer satisfying 1 ≤ m ≤ 5, a5 is 0 or 1, b5 is 1 or 2, and d5 is 1 to 4.

[0890] [Chemical 139]

[0891]

[0892] In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). Among the structures constituting the aforementioned R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R8 is a hydrogen atom or a methyl group, and b6 is 1 to 5.

[0893]

[17] A surfactant as in

[15] or

[16] , wherein the weight average molecular weight of the aforementioned aryl benzyl ether compound is 1000 to 30000.

[0894] Furthermore, the present invention is not limited to the above embodiments. The above embodiments are illustrative, and those having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effects are all included within the technical scope of the present invention.

[0895] Explanation of reference numerals

[0896] 1: Substrate

[0897] 2: Layer to be processed

[0898] 2a: Pattern (pattern formed on the layer to be processed)

[0899] 3: Organic film

[0900] 3a: Organic film pattern

[0901] 4: Silicon-containing resist intermediate film

[0902] 4a: Silicon-containing resist intermediate film pattern

[0903] 5: Resist upper layer film

[0904] 5a: Resist upper layer film pattern

[0905] 6: Exposed part

[0906] 7: Base substrate

[0907] 8: Organic film

Claims

1. A composition for forming an organic film, characterized by containing: (A) A material for forming an organic film, (B) An aryl benzyl ether compound having a partial structure represented by the following general formula (B1), and (C) A solvent, In the formula, R1 is a hydrogen atom or an arbitrary fluorine-containing group represented by the following formula (B2). Among the structures constituting R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the following formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, a is 0 or 1. When a is 0, b is 1 to 5 and c is 0 to 4. When a is 1, b is 1 to 7 and c is 0 to 6. * represents a chemical bond with other atoms. In the formula, the dashed line represents a chemical bond with the oxygen atom in the above formula (B1), and may also have one or two of the structures represented by the above formula (B2).

2. The composition for forming an organic film according to claim 1, wherein The (B) aryl benzyl ether compound is a compound represented by the following general formula (B3), (B4), (B6), (B8), (B10), or (B11). In the formula, R1 is a hydrogen atom or one or two of the fluorine-containing groups represented by the formula (B2). Among the structures constituting R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, R3 is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, a1 is 0 or 1. When a1 is 0, b1 is 1 to 5 and c1 is 0 to 4. When a1 is 1, b1 is 1 to 7 and c1 is 0 to 6. In the formula, R1 is a hydrogen atom or one or two of the fluorine-containing groups represented by the above formula (B2). Among the structures constituting R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, R4 is a single bond or any one of the groups represented by the following formula (B5), R5 is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, a2 is 0 or 1. When a2 is 0, b2 is 1 to 5 and c2 is 0 to 4. When a2 is 1, b2 is 1 to 7 and c2 is 0 to 6. In the formula, R1 is a hydrogen atom or one or two of the fluorine-containing groups represented by the above formula (B2). Among the structures constituting R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, R6 is an arbitrary group represented by the following formula (B7), R7 is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms, a3 is 0 or 1. When a3 is 0, b3 is 1 to 5 and c3 is 0 to 4. When a3 is 1, b3 is 1 to 7 and c3 is 0 to 6. In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). In the structure constituting R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. W1 is a group represented by the following formula (B9), a4 is 0 or 1, b4 is 1 or 2, and d4 is 1 to 4. In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). In the structure constituting R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). In the structure constituting R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. W1 is a group represented by the above formula (B9), W2 is a single bond or an organic group having 1 to 50 carbon atoms, m is an integer satisfying 1 ≤ m ≤ 5, a5 is 0 or 1, b5 is 1 or 2, and d5 is 1 to 4. In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). In the structure constituting R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R8 is a hydrogen atom or a methyl group, and b6 is 1 to 5.

3. The composition for forming an organic film according to claim 1, wherein, The weight average molecular weight of the (B) aryl benzyl ether compound is 1000 to 30000.

4. The composition for forming an organic film according to claim 1, wherein, With respect to 100 parts by mass of the content of the (A) material for forming an organic film, the content of the (B) aryl benzyl ether compound is 0.01 part by mass to 5 parts by mass.

5. An organic film forming method, which is an organic film forming method used in the manufacturing process of a semiconductor device, characterized in that: A coating film is obtained by spin-coating the organic film forming composition according to any one of claims 1 to 4 on a substrate to be processed. The coating film is heat-treated at a temperature of 100 °C or higher and 600 °C or lower for 10 to 600 seconds to be hardened to form an organic film.

6. A pattern forming method, characterized in that: An organic film is formed on a workpiece using the organic film forming composition according to any one of claims 1 to 4. A silicon-containing resist intermediate film is formed on the organic film using a silicon-containing resist intermediate film material. A resist upper layer film is formed on the silicon-containing resist intermediate film using a resist upper layer film material composed of a photoresist composition. A circuit pattern is formed on the resist upper layer film, and the resist upper layer film having the formed circuit pattern is used as a mask, and the pattern is transferred by etching to the silicon-containing resist intermediate film. The silicon-containing resist intermediate film having the transferred pattern is used as a mask, and the pattern is transferred by etching to the organic film. Then, the organic film having the transferred pattern is used as a mask, and the pattern is formed by etching on the workpiece.

7. A pattern forming method, characterized in that: An organic film is formed on a workpiece using the composition for forming an organic film according to any one of claims 1 to 4, A silicon-containing resist intermediate film is formed on the organic film using a silicon-containing resist intermediate film material, and an organic antireflection film or a conformal film is formed on the silicon-containing resist intermediate film, A resist upper film is formed on the organic antireflection film or the conformal film using a resist upper film material composed of a photoresist composition, and a circuit pattern is formed in the resist upper film, The resist upper film having the circuit pattern formed thereon is used as a mask, and the pattern is etched and transferred to the organic antireflection film or the conformal film and the silicon-containing resist intermediate film, The silicon-containing resist intermediate film having the transferred pattern is used as a mask, and the pattern is etched and transferred to the organic film, The organic film having the transferred pattern is further used as a mask, and the pattern is etched on the workpiece to form a pattern.

8. A pattern forming method, characterized in that: An organic film is formed on a workpiece using the composition for forming an organic film according to any one of claims 1 to 4, An inorganic hard mask selected from the group consisting of a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the organic film, A resist upper film is formed on the inorganic hard mask using a resist upper film material composed of a photoresist composition, A circuit pattern is formed in the resist upper film, The resist upper film having the circuit pattern formed thereon is used as a mask, and the pattern is etched and transferred to the inorganic hard mask, The inorganic hard mask having the transferred pattern is used as a mask, and the pattern is etched and transferred to the organic film, The organic film having the transferred pattern is further used as a mask, and the pattern is etched on the workpiece to form a pattern.

9. A pattern forming method, characterized in that: An organic film is formed on a workpiece using the composition for forming an organic film according to any one of claims 1 to 4, An inorganic hard mask selected from the group consisting of a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the organic film, An organic antireflection film or a conformal film is formed on the inorganic hard mask, and a resist upper film is formed on the organic antireflection film or the conformal film using a resist upper film material composed of a photoresist composition, A circuit pattern is formed in the resist upper film, The resist upper film having the circuit pattern formed thereon is used as a mask, and the pattern is etched and transferred to the organic antireflection film or the conformal film and the inorganic hard mask, The inorganic hard mask having the transferred pattern is used as a mask, and the pattern is etched and transferred to the organic film, Furthermore, the organic film having the transferred pattern is used as a mask, and the pattern is etched on the workpiece.

10. The pattern forming method according to claim 8, wherein, The inorganic hard mask is formed by CVD method or ALD method.

11. The pattern forming method according to claim 6, wherein, In the formation of the circuit pattern, lithography using light with a wavelength of 10 nm or more and 300 nm or less, direct drawing using an electron beam, nanoimprinting, or a combination thereof is used to form the circuit pattern.

12. The pattern forming method according to claim 6, wherein, In the formation of the circuit pattern, the circuit pattern is developed using alkali development or an organic solvent.

13. The pattern forming method according to claim 6, wherein, The object to be processed is a semiconductor device substrate, or any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, and a metal oxynitride film formed on the semiconductor device substrate.

14. The pattern forming method according to claim 13, wherein, Regarding the object to be processed, the metal constituting the object to be processed is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof.

15. A surfactant composed of an aryl benzyl ether compound having a partial structure represented by the following general formula (B1). In the formula, R1 is a hydrogen atom or any fluorine-containing group represented by the following formula (B2). Among the structures constituting R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the following formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms. a is 0 or 1. When a is 0, b is 1 to 5 and c is 0 to 4. When a is 1, b is 1 to 7 and c is 0 to 6. * represents a chemical bond with other atoms. In the formula, the dashed line represents a chemical bond with the oxygen atom in the above formula (B1), and may have one or two of the structures represented by the above formula (B2).

16. The surfactant according to claim 15, wherein The aryl benzyl ether compound is a compound represented by the following general formula (B3), (B4), (B6), (B8), (B10), or (B11). In the formula, R1 is a hydrogen atom or one or two of the fluorine-containing groups represented by the formula (B2). Among the structures constituting R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms. R3 is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms. a1 is 0 or 1. When a1 is 0, b1 is 1 to 5 and c1 is 0 to 4. When a1 is 1, b1 is 1 to 7 and c1 is 0 to 6. In the formula, R1 is a hydrogen atom or one or two of the fluorine-containing groups represented by the above formula (B2). Among the structures constituting R1, when the proportion of hydrogen atoms is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms. R4 is a single bond or any one of the groups represented by the following formula (B5). R5 is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms. a2 is 0 or 1. When a2 is 0, b2 is 1 to 5 and c2 is 0 to 4. When a2 is 1, b2 is 1 to 7 and c2 is 0 to 6. In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). In the structure constituting the R1, when the proportion of the hydrogen atom is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R2 is a saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms. R6 is any group represented by the following formula (B7). R7 is a saturated or unsaturated divalent organic group having 1 to 30 carbon atoms. a3 is 0 or 1. When a3 is 0, b3 is 1 to 5 and c3 is 0 to 4. When a3 is 1, b3 is 1 to 7 and c3 is 0 to 6. In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). In the structure constituting the R1, when the proportion of the hydrogen atom is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. W1 is a group represented by the following formula (B9). a4 is 0 or 1. b4 is 1 or 2. d4 is 1 to 4. In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). In the structure constituting the R1, when the proportion of the hydrogen atom is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). In the structure constituting the R1, when the proportion of the hydrogen atom is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. W1 is a group represented by the above formula (B9). W2 is a single bond or an organic group having 1 to 50 carbon atoms. m is an integer satisfying 1 ≤ m ≤ 5. a5 is 0 or 1. b5 is 1 or 2. d5 is 1 to 4. In the formula, R1 is one or two of a hydrogen atom or a fluorine-containing group represented by the above formula (B2). In the structure constituting the R1, when the proportion of the hydrogen atom is α and the proportion of the fluorine-containing group represented by the above formula (B2) is β, the relationship of α + β = 1, 0.1 ≤ α ≤ 0.5, and 0.5 ≤ β ≤ 0.9 is satisfied. R8 is a hydrogen atom or a methyl group. b6 is 1 to 5.

17. The surfactant according to claim 15 or claim 16, wherein, The weight-average molecular weight of the aryl benzyl ether compound is 1000 to 30000.

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