Composition for organic film formation, pattern formation method, and compound

Abstract

The present invention relates to a composition for forming an organic film, a pattern forming method, and a compound. The present invention provides a composition for forming an organic film which exhibits high etching resistance, excellent twist resistance, film formability, and which has a small amount of sublimation components of a fugitive gas, a pattern forming method using the composition, and a compound suitable for the composition. A composition for forming an organic film contains a compound represented by the following general formula (1) and an organic solvent. In the above general formula (1), X is any one of X1 to X3 represented by the following general formulae (2), (3), and (5), and two or more kinds of X can be used in combination. In the above general formula (3), W represents a carbon atom or a nitrogen atom, n1 represents 0 or 1, n2 represents an integer of 1 to 3, and R1 is independently any group represented by the following general formula (4). In the above general formula (5), R2 is a hydrogen atom or an alkyl group having a carbon number of 1 to 4, and R3 is any group.

Description

TECHNICAL FIELD

[0001] The present application relates to a composition for forming an organic film, a pattern forming method using the same, and a polymer contained in the composition. BACKGROUND

[0002] In recent years, with the high integration and high speed of semiconductor devices, the miniaturization of pattern rules is required, and photolithography using light exposure, which is now used as a general technique, has been developed for more miniaturization and high precision pattern processing using light sources.

[0003] As for the light source for photolithography used in the formation of a resist pattern, light exposure using g-rays (436 nm) or i-rays (365 nm) of a mercury lamp is widely used in a low density portion. On the other hand, in a high density portion requiring miniaturization, photolithography using a shorter wavelength of KrF excimer laser (248 nm) or ArF excimer laser (193 nm) has been put into practical use, and in the most advanced era requiring further miniaturization, photolithography using extreme ultraviolet rays (EUV, 13.5 nm) has also been approaching practical use.

[0004] As the miniaturization of resist patterns continues to progress as described above, it is known that in a single-layer resist method, which is a typical photoresist pattern forming method, the ratio of the height of a pattern to the line width of the pattern (aspect ratio) increases, and pattern collapse occurs due to the surface tension of a developer at the time of development. It is also known that when a pattern of a high aspect ratio is formed on a high-low difference substrate, a multi-layer resist method in which a pattern is formed by laminating films having different dry etching characteristics is excellent, and a two-layer resist method in which 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, are combined (Patent Document 1, etc.), and a three-layer resist method in which a photoresist layer made of an organic photosensitive polymer used in a 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 are combined (Patent Document 2, etc.) have been developed.

[0005] This three-layer resist method first uses fluorocarbon-based dry etching gas to transfer a pattern of a photoresist upper layer film to a silicon-containing resist intermediate film, and then uses the pattern as a mask to transfer the pattern to an organic film (organic lower layer film) having carbon and hydrogen as main constituent elements by dry etching with an oxygen-containing gas. Then, the organic film is used as a mask to form a pattern on a processed object by dry etching. However, in the manufacture of semiconductor devices in the 20 nm era and beyond, if the pattern of the organic film is used as a hard mask to transfer the pattern to a processed object by dry etching, the organic film pattern will show a phenomenon of distortion and bending.

[0006] A carbon hard mask formed directly above a substrate to be processed is generally an amorphous carbon (hereinafter referred to as CVD-C) film formed by a CVD method using methane gas, ethane gas, acetylene gas, or the like as a raw material. This CVD-C film has very few hydrogen atoms in the film and is known to be very effective against distortion and bending of a pattern as described above, but when the substrate to be processed has a difference in level, it is known that due to the characteristics of the CVD process, it is difficult to fill in the difference in level flatly. Therefore, if the substrate to be processed having a difference in level is filled in with the CVD-C film and then patterned with a photoresist, a difference in level occurs on the coating surface of the photoresist due to the influence of the difference in level of the substrate to be processed, and thus the film thickness of the photoresist becomes uneven, resulting in degradation of the focus margin and the pattern shape during photolithography.

[0007] On the other hand, when an organic film is formed as a carbon hard mask formed directly above a substrate to be processed by a spin coating method, it is known that there is an advantage that the difference in level of a substrate having a difference in level can be filled in flatly. If the substrate is planarized with this organic film material, the film thickness variation of a silicon-containing resist intermediate film and a photoresist upper film formed thereon can be suppressed, the focus margin of photolithography can be enlarged, and a normal pattern can be formed.

[0008] Therefore, an organic film material capable of forming an organic film having high planarity on a substrate to be processed and a method for forming an organic film are sought, which have high etching resistance when dry etching processing of the substrate to be processed is performed.

[0009] In the past, as an organic film forming material for a multi-layer resist method, a condensed resin obtained by using a carbonyl compound such as a ketone, an aldehyde, or an aromatic alcohol as a condensing agent for a phenol-based or naphthol-based compound has been known in such an organic film material. For example, a fluorene bisphenol novolak resin described in Patent Document 2, a bisphenol compound and a novolak resin thereof described in Patent Document 3, a novolak resin of an adamantane phenol compound described in Patent Document 4, a bisnaphthol compound and a novolak resin thereof described in Patent Document 5, and the like. The resin used in such a material is composed of naphthalene, fluorene, adamantane, or the like having a high carbon density as a main skeleton, but it cannot be avoided that the etching resistance is degraded due to the oxygen atom from the phenolic hydroxyl group in the constituting unit.

[0010] Further, as a resin for an organic film material not containing a hetero atom such as oxygen in order not to impair the etching resistance, a resin having a fluorene structure described in Patent Document 6 has been cited, but the resin itself does not contribute to thermal hardening, and in order to form a hardened film, a composition to which a crosslinking agent such as a methylol compound is added is used to form a hardened film, so even if the carbon content of the resin is increased, there is a problem that the etching resistance of the resin originally made high-carbon is impaired due to the presence of the crosslinking agent having a low carbon content.

[0011] As an organic film material not containing an additive such as a crosslinking agent which is a deterioration factor of etching resistance and not containing a hetero atom such as oxygen for the purpose of improving etching resistance, an organic film material using a monomolecular compound described in Patent Literature 7 can be exemplified, but since a monomolecular compound is used, there are problems such as coatability on a substrate with a complex shape, sublimate caused by a low molecule at the time of baking, and the like, and there are issues in each characteristic of heat resistance and etching resistance of the hardened organic film.

[0012] In order to improve the carbon density as much as possible, various fullerene derivatives are investigated in Patent Literatures 8 and 9 and the like, but the fullerene itself does not have hardenability, and there is a difficulty in film formation due to a problem of solvent solubility. Therefore, when the fullerene is used, it is necessary to add a resin and a crosslinking agent, and in order to improve the solvent solubility, it is necessary to introduce various substituents and the like, and due to the decrease in carbon density and the deterioration of heat resistance caused by the introduction of substituents, it becomes a major issue for an organic film material.

[0013] Prior Art Documents

[0014] Patent Literature

[0015] [Patent Literature 1] Japanese Patent Application Laid-Open (JP-A) No. 6-118651

[0016] [Patent Literature 2] Japanese Patent Application Laid-Open (JP-A) No. 2005-128509

[0017] [Patent Literature 3] Japanese Patent Application Laid-Open (JP-A) No. 2006-293298

[0018] [Patent Literature 4] Japanese Patent Application Laid-Open (JP-A) No. 2006-285095

[0019] [Patent Literature 5] Japanese Patent Application Laid-Open (JP-A) No. 2010-122656

[0020] [Patent Literature 6] International Publication No. 2013 / 047106

[0021] [Patent Literature 7] Japanese Patent Application Laid-Open (JP-A) No. 2008-164806

[0022] [Patent Literature 8] International Publication No. 2008 / 126804

[0023] [Patent Literature 9] International Publication No. 2016 / 143436 SUMMARY

[0024] [Problems to be Solved by the Invention]

[0025] The present invention has an object to provide an organic film forming composition which exhibits high etching resistance, excellent twist resistance, and excellent film formability without impairing the carbon content of the resin as it is, and which has a small amount of sublimation components which become diffused gas, a pattern forming method using the same, and a compound suitable for the organic film forming composition, by using a compound having a high carbon content and having thermal curing properties.

[0026] [Means for solving the problem]

[0027] To achieve the above object, the present invention provides an organic film forming composition characterized by containing a compound represented by the following general formula (1) and an organic solvent.

[0028] [Chemical Formula 1]

[0029]

[0030] In the above general formula (1), X is any one of X1 to X3 represented by the following general formulae (2), (3), and (5), and two or more kinds of X can be used in combination.

[0031] [Chemical Formula 2]

[0032]

[0033] [Chemical Formula 3]

[0034]

[0035] In the above general formula (3), W represents a carbon atom or a nitrogen atom, n1 represents 0 or 1, n2 represents an integer of 1 to 3, and R1 is independently any one of the groups represented by the following general formula (4).

[0036] [Chemical Formula 4]

[0037]

[0038] [Chemical Formula 5]

[0039]

[0040] In the above general formula (5), R2 is a hydrogen atom or an alkyl group having a carbon number of 1 to 4, and R3 is any one of the following groups.

[0041] [Chemical Formula 6]

[0042]

[0043] If the organic film-forming composition is such, an organic film-forming composition can be provided which has a high carbon content, exhibits high etching resistance, excellent twist resistance, and excellent film-forming properties without impairing the carbon content of the resin as it is, and has a small amount of sublimation components of a dispersion gas.

[0044] Further, the compound represented by the aforementioned general formula (1) preferably has a ratio Mw / Mn of a weight average molecular weight Mw to a number average molecular weight Mn, as determined by gel permeation chromatography, of 1.00 ≤ Mw / Mn ≤ 1.15.

[0045] If the organic film-forming composition is such, an organic film having excellent burying properties and planarity can be formed.

[0046] Further, the aforementioned organic solvent preferably is a mixture of one or more organic solvents having a boiling point of less than 180 degrees and one or more organic solvents having a boiling point of 180 degrees or more.

[0047] If the organic film-forming composition is such, the heat flowability of the organic film is imparted by adding a high-boiling organic solvent to the compound represented by the aforementioned general formula (1), and the organic film-forming composition can have high-degree burying / planarization properties.

[0048] Further, the aforementioned organic film-forming composition preferably further contains one or more of a surfactant and a plasticizer.

[0049] If the organic film-forming composition is such, the coating properties and burying / planarization properties are more excellent.

[0050] Further, the present application provides a pattern forming method,

[0051] An organic film is formed on a processed object using the aforementioned organic film-forming composition, 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 photoresist composition, a circuit pattern is formed on the resist upper layer film, the pattern-formed resist upper layer film is used as a mask to transfer the pattern on the aforementioned silicon-containing resist intermediate film by etching, the pattern-transferred silicon-containing resist intermediate film is used as a mask to transfer the pattern on the aforementioned organic film by etching, and a pattern is formed on the aforementioned processed object by etching using the pattern-transferred organic film as a mask.

[0052] By the pattern forming method using the aforementioned three-layer resist process, a fine pattern can be formed on a processed object with high precision.

[0053] Further, the present application provides a pattern forming method,

[0054] An organic film is formed on a processed body using the above-mentioned composition for forming an organic film, a silicon-containing resist intermediate film is formed on the organic film using a silicon-containing resist intermediate film material, an organic anti-reflective film (BARC) is formed on the silicon-containing resist intermediate film, a resist upper layer film is formed on the BARC using a photoresist composition and becomes a 4-layer film structure, a circuit pattern is formed on the resist upper layer film, the patterned resist upper layer film is used as a mask to transfer the pattern on the BARC film and the silicon-containing resist intermediate film by etching, the pattern-transferred silicon-containing resist intermediate film is used as a mask to transfer the pattern on the organic film by etching, and the processed body is etched using the pattern-transferred organic film as a mask to form a pattern on the processed body.

[0055] By using the pattern forming method of the 4-layer resist treatment, a fine pattern can be formed on a processed body with higher precision.

[0056] Further, the present application provides a pattern forming method characterized in that

[0057] An organic film is formed on a processed body using the above-mentioned composition for forming an organic film, an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the organic film, a resist upper layer film is formed on the inorganic hard mask using a photoresist composition, a circuit pattern is formed on the resist upper layer film, the patterned resist upper layer film is used as a mask to transfer the pattern on the inorganic hard mask by etching, the pattern-transferred inorganic hard mask is used as a mask to transfer the pattern on the organic film by etching, and the processed body is etched using the pattern-transferred organic film as a mask to form a pattern on the processed body.

[0058] By using the pattern forming method of the 3-layer resist treatment, a fine pattern can be formed on a processed body with high precision.

[0059] Further, the present application provides a pattern forming method characterized in that

[0060] An organic film is formed on a workpiece using the above-mentioned composition for forming an organic film, an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, a silicon oxynitride film is formed on the organic film, an organic bottom anti-reflective coating (BARC) is formed on the inorganic hard mask, an upper resist film is formed on the BARC using a photoresist composition and becomes a 4-layer film structure, a circuit pattern is formed on the upper resist film, the patterned upper resist film is used as a mask to transfer the pattern to the BARC film and the inorganic hard mask by etching, the pattern-transferred inorganic hard mask is used as a mask to transfer the pattern to the organic film by etching, and the workpiece is etched using the pattern-transferred organic film as a mask to form a pattern on the workpiece.

[0061] By using the above-mentioned 4-layer resist processing method, a fine pattern can be formed on a workpiece with higher precision.

[0062] Further, the above-mentioned inorganic hard mask is preferably formed by a CVD method or an ALD method.

[0063] The above-mentioned inorganic hard mask, if formed by a CVD method or an ALD method, can form a fine pattern on a workpiece with higher precision.

[0064] Further, as the method for forming a circuit pattern, it is preferable to use optical lithography with a wavelength of 10 nm or more and 300 nm or less, direct drawing with an electron beam, nano-imprinting, or a combination thereof.

[0065] If the above-mentioned circuit pattern forming method is used, a fine pattern can be formed on a workpiece with higher precision.

[0066] Further, in the formation of the above-mentioned circuit pattern, it is preferable to develop the circuit pattern using an alkali developer or an organic solvent.

[0067] If the above-mentioned pattern forming method is used, a fine pattern can be formed on a workpiece with higher precision.

[0068] Further, in the formation of the above-mentioned circuit pattern, the above-mentioned workpiece is preferably a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, or a metal oxynitride film.

[0069] If the above-mentioned workpiece is used, a better pattern can be formed.

[0070] Further, in the formation of the above-mentioned circuit pattern, the above-mentioned metal is preferably silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof.

[0071] If such a metal is used as a workpiece, a better pattern can be formed.

[0072] Further, the present application provides a compound represented by the following general formula (1).

[0073] [Chemical 7]

[0074]

[0075] In the above general formula (1), X is any one of X1 to X3 represented by the following general formulae (2), (3), and (5), and two or more kinds of X can be used in combination.

[0076] [Chemical 8]

[0077]

[0078] [Chemical 9]

[0079]

[0080] In the above general formula (3), W represents a carbon atom or a nitrogen atom, n1 represents 0 or 1, n2 represents an integer of 1 to 3, and R1 is independently any one of the groups represented by the following general formula (4).

[0081] [Chemical 10]

[0082]

[0083] [Chemical 11]

[0084]

[0085] In the above general formula (5), R2 is a hydrogen atom or an alkyl group having a carbon number of 1 to 4, and R3 is any one of the groups represented by the following.

[0086] [Chemical 12]

[0087]

[0088] If such a compound is used, a compound suitable for forming an organic film having a high carbon content, a high etching resistance, a high twist resistance, a high film formability, and a low amount of sublimation components of a dispersing gas can be provided without damaging the original carbon content of the resin.

[0089] [Effects of the Invention]

[0090] Generally, a sumanene derivative, which corresponds to a cap structure of a fullerene or a nanotube, has a property that 2-dimensional molecular assemblies are easily formed because of the curved structure possessed by the sumanene structure, in which the sumanene molecules overlap each other. The organic film-forming composition containing the sumanene derivative represented by the aforementioned general formula (1) can form a carbon film having high density and high strength, due to the property of easily forming molecular assemblies and the solubility to an organic solvent and the thermal curability imparted by the substituent represented by X. Therefore, the organic film formed from the organic film-forming composition of the present application, when used as an organic film for a resist, has excellent dry etching resistance and twist resistance.

[0091] The sumanene derivative of the present application has thermal curability and is composed of a condensed aromatic ring structure having a high carbon content, which corresponds to a partial structure of a fullerene, and thus becomes a component of an organic film-forming composition that imparts an organic film having both high twist resistance and dry etching resistance. Also, such a sumanene derivative is not limited to use as a compound for a resist organic film material, and use in next-generation materials such as molecular semiconductors is expected based on the property of easily forming molecular assemblies.

[0092] As described above, the compound of the present application, which is a high-density carbon compound composed of a sumanene structure as a main skeleton, becomes a useful compound for forming an organic film having excellent etching resistance and twist resistance. Also, the organic film-forming composition of the present application containing this compound becomes a useful material for forming an organic film having not only excellent etching resistance and twist resistance but also many properties such as heat resistance, filling / plane characteristics, and the like. Therefore, it is extremely useful as a resist organic film material for multilayer resist processing such as 2-layer resist processing, 3-layer resist processing using a silicon-containing resist intermediate film, or 4-layer resist processing using a silicon-containing resist intermediate film and an organic bottom anti-reflective coating (BARC). Also, if the pattern forming method of the present application is used, a fine pattern can be formed on a processed substrate with high precision in multilayer resist processing. BRIEF DESCRIPTION OF DRAWINGS

[0093] Figure 1 (A) to (F) of FIG. 1 are process diagrams illustrating an example of the pattern forming method of the present application.

[0094] Figure 2 is a cross-sectional view of an example of an organic film formed by applying the organic film-forming composition of the present application to a SiO2 wafer substrate having a trench pattern. DETAILED DESCRIPTION

[0095] As described above, a composition for forming an organic film having high etching resistance and excellent twist resistance, and excellent filling and planarization properties of a substrate, a pattern forming method using the same, and a compound suitable for the composition for forming an organic film are sought to be developed.

[0096] The present inventors have intensively studied in order to solve the above problems, and as a result, have found that by introducing a specific partial structure into suemycin, heat hardenability and solubility in an organic solvent can be imparted. Also, an organic film forming composition containing the aforementioned compound and an organic solvent has been found to form an organic film that has excellent etching resistance, twist resistance, and heat resistance, filling / planarization properties, film formation properties, and a small amount of sublimation components, and the like, and the present invention has been completed.

[0097] That is, the present invention is a composition for forming an organic film, characterized by

[0098] The aforementioned composition for forming an organic film contains a compound represented by the following general formula (1) and an organic solvent.

[0099] [Chemical Formula 13]

[0100]

[0101] In the aforementioned general formula (1), X is any one of X1 to X3 represented by the following general formulae (2), (3), and (5), and two or more kinds of X can be used in combination.

[0102] [Chemical Formula 14]

[0103]

[0104] [Chemical Formula 15]

[0105]

[0106] In the aforementioned general formula (3), W represents a carbon atom or a nitrogen atom, n1 represents 0 or 1, n2 represents an integer of 1 to 3, and R1 is independently any one of the groups represented by the following general formula (4).

[0107] [Chemical Formula 16]

[0108]

[0109] [Chemical Formula 17]

[0110]

[0111] In the aforementioned general formula (5), R2 is a hydrogen atom or an alkyl group having a carbon number of 1 to 4, and R3 is any one of the following groups.

[0112] [Chemical Formula 18]

[0113]

[0114] The present application is explained in detail below, but the present application is not limited thereto.

[0115] [Compound]

[0116] The organic film-forming composition of the present application contains a compound represented by the following general formula (1).

[0117] [Chemical 19]

[0118]

[0119] In the above general formula (1), X is any one of X1 to X3 represented by the following general formulae (2), (3), and (5), and two or more kinds of X can be used in combination.

[0120] [Chemical 20]

[0121]

[0122] [Chemical 21]

[0123]

[0124] In the above general formula (3), W represents a carbon atom or a nitrogen atom, n1 represents 0 or 1, n2 represents an integer of 1 to 3, and R1 is independently any one of the groups represented by the following general formula (4).

[0125] [Chemical 22]

[0126]

[0127] [Chemical 23]

[0128]

[0129] In the above general formula (5), R2 is a hydrogen atom or an alkyl group having a carbon number of 1 to 4, and R3 is any one of the following groups.

[0130] [Chemical 24]

[0131]

[0132] When the partial structure represented by X in the above general formula (1) is X1, it is a structure represented by the following formula (2), which is more desirable from the viewpoint of imparting hardness, solvent solubility, and etching resistance.

[0133] [Chemical 25]

[0134]

[0135] In the partial structure represented by X in the aforementioned general formula (1), X2 represented by the aforementioned general formula (3) can be specifically exemplified as follows. Substituents on the aromatic rings constituting them can also have substituents, and examples include hydroxy group, methyl group, methoxy group, nitro group, halogen group, trifluoromethyl group, and the like. Among the following X2, it is preferable that n1 = 1 and the substituent represented by R1 is an ethynyl group or an ethynylphenyl group from the viewpoint of etching resistance.

[0136] [Chemical Formula 26]

[0137]

[0138] [Chemical Formula 27]

[0139]

[0140] In the partial structure represented by X in the aforementioned general formula (1), X3 represented by the aforementioned general formula (5) can be specifically exemplified as follows. When the constituent elements constituting them have an aromatic ring, the aromatic ring can also have substituents, and examples include hydroxy group, methyl group, methoxy group, nitro group, halogen group, trifluoromethyl group, and the like. Among the following X3, it is preferable that R2 is a hydrogen atom from the viewpoint of thermal curing property, and it is preferable that R3 is a naphthyl group or a diphenylacetylene group from the viewpoint of etching resistance and thermal curing property.

[0141] [Chemical Formula 28]

[0142]

[0143] [Chemical Formula 29]

[0144]

[0145] [Chemical Formula 30]

[0146]

[0147] [Chemical Formula 31]

[0148]

[0149] In the partial structure represented by X in the aforementioned general formula (1), the compound of X3 not only has thermal curing property as the role of the substituent R3, but also can cause intermolecular dehydration or condensation reaction with alcohol elimination by the action of heat or acid and form a dense film as shown below.

[0150] [Chemical Formula 32]

[0151]

[0152] Further, the compound represented by the general formula (1) preferably has a ratio Mw / Mn of a weight average molecular weight Mw to a number average molecular weight Mn obtained by gel permeation chromatography in a range of 1.00 ≤ Mw / Mn ≤ 1.15. By definition, if it is a monomolecular compound, Mw / Mn becomes 1.00, but due to the separation property of the gel permeation chromatography, the measured value can exceed 1.00 at times. In general, it is extremely difficult to approach Mw / Mn = 1.00 for a polymer having a repeating unit without using a special polymerization method, and it has a distribution of Mw and Mw / Mn becomes a value exceeding 1. In the present application, in order to distinguish a monomolecular compound from a polymer, 1.00 ≤ Mw / Mn ≤ 1.15 is defined as an index showing monomolecularity.

[0153] By controlling the Mw / Mn of the compound for the organic film forming composition described above in such a range, the organic film forming composition can form an organic film excellent in burying properties and planarization properties.

[0154] Further, the compound for the organic film forming composition represented by the general formula (1) described above is preferably added in a range of 1 to 20 parts by mass, more preferably 5 to 15 parts by mass, with respect to 100 parts by mass of the organic film forming composition.

[0155] [Method for producing compound]

[0156] The compound represented by the general formula (1) of the present application can be synthesized using sumaresene or an oxide of sumaresene as a raw material. The following describes a method for production for each case where X is X1, X2, and X3.

[0157] In the case where X is X1, for example, a substitution reaction using the following sumaresene and a halide, a tosylate, or a mesylate of propargyl, and a base catalyst is used. X4 in the following formula is a halogen, a tosyl group, or a mesyl group.

[0158] [Compound 33]

[0159]

[0160] The base catalyst used in the substitution reaction can include inorganic base compounds such as sodium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, and potassium phosphate, organic amine compounds such as triethylamine, pyridine, and N-methylmorpholine, and the like, and they can be used alone or in combination of two or more. The amount of the catalyst used is in a range of 0.1 to 20 moles, preferably 0.2 to 10 moles, with respect to the number of moles of the raw material sumaresene.

[0161] The solvent used at this time is not particularly limited as long as it is a solvent that is inert to the above reaction, and examples include diethyl ether, tetrahydrofuran, dioxane, benzene, toluene, xylene, acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, water, and the like, which can be used alone or in combination. These solvents can be used in a range of 0 to 2000 parts by mass relative to 100 parts by mass of the raw material of the reaction, and the reaction temperature is preferably -50°C to the boiling point of the solvent, and more preferably room temperature to 150°C. The reaction time can be appropriately selected from 0.1 to 100 hours.

[0162] As the reaction method, the following methods can be used: a method in which the sumaresene and the propargyl-type halide, tosylate or mesylate, and the catalyst base catalyst are added in batches; a method in which the sumaresene, halide or tosylate, mesylate is dispersed or dissolved, and the catalyst is added in batches or in portions; a method in which the catalyst is diluted with a solvent and added dropwise; a method in which the sumaresene, halide or tosylate, mesylate is added in batches or in portions after the catalyst is dispersed or dissolved; and a method in which the catalyst is diluted with a solvent and added dropwise. At this time, the amount of the propargyl-type halide, tosylate or mesylate used is preferably 2 moles or more per 1 mole of the sumaresene, although this depends on the reactivity of the aromatic compound. After the reaction is completed, the catalyst used in the reaction can be removed by diluting with an organic solvent, separating, and washing to recover the desired product.

[0163] In addition to the propargyl-type halide, tosylate, and mesylate described above, an alkyl-type halide and tosylate, mesylate, or an allyl-type halide and tosylate, mesylate, or the like can also be used in combination. Furthermore, by controlling the reaction rate of the substitution reaction, the introduction rate of the propargyl group can also be controlled. By combining a plurality of substituents or controlling the introduction rate, the film formability and the adhesion to the substrate can be controlled.

[0164] The organic solvent used in the separation and washing is not particularly limited as long as it can dissolve the desired product and can be separated into two layers even when mixed with water, and examples include hexane, heptane, benzene, toluene, xylene, esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate, ketones such as methyl ethyl ketone, methyl amyl ketone, and cyclohexanone, ethers such as diethyl ether, diisopropyl ether, and methyl-tert-butyl ether, ethyl cyclopentyl methyl ether, chlorine-based solvents such as dichloromethane, chloroform, and dichloroethane, and mixtures thereof. The washing water used at this time can be, for example, deionized water or ultrapure water. The number of times of washing is one or more, but the effect of the number of times of washing is not necessarily obtained even when the number of times of washing is 10 or more, and thus the number of times of washing is preferably 1 to 5.

[0165] For the purpose of removing acidic components in the system, the washing with an aqueous alkaline solution can also be performed. Specific examples of the base include hydroxides of alkali metals, carbonates of alkali metals, hydroxides of alkaline earth metals, carbonates of alkaline earth metals, ammonia, and organic ammonium.

[0166] Further, for the purpose of removing metal impurities or basic components in the system, the washing with an aqueous acidic solution can also be performed. Specific examples of the acid include hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, inorganic acids such as heteropoly acids, oxalic acid, fumaric acid, maleic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, and organic acids.

[0167] The washing with an aqueous alkaline solution or an aqueous acidic solution can be performed alone or in combination. The washing is preferably performed in the order of the aqueous alkaline solution and the aqueous acidic solution from the viewpoint of removal of metal impurities.

[0168] After the washing with an aqueous alkaline solution or an aqueous acidic solution, the washing with neutral water can also be performed. The number of times of washing is preferably 1 to 5. The neutral water is not particularly limited and can be deionized water or ultrapure water. The number of times of washing is preferably 1 to 5.

[0169] Further, the reaction product after the liquid separation operation can be concentrated and dried or subjected to a crystallization operation under reduced pressure or under normal pressure to be recovered as a powder. However, in order to improve the handling properties in the production of the composition for forming an organic film, the solution can be previously prepared to have a moderate concentration. The concentration is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass. If the concentration is within this range, the viscosity does not easily increase, and thus the handling properties can be prevented from deteriorating. Further, the amount of solvent does not become excessively large, and thus the production cost can be reduced.

[0170] The solvent is not particularly limited as long as it can dissolve the compound, and specific examples thereof 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; and 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 mono-tert-butyl ether acetate. These solvents can be used alone or in combination.

[0171] When X is X2, the manufacturing method differs depending on whether W is a carbon atom or a nitrogen atom. When W is a carbon atom, it can be obtained by condensation reaction of suisenene with aromatic aldehydes or the like (reaction method 1). When W is a nitrogen atom, it can be obtained by condensation reaction of suisenene oxide with aromatic amines or the like (reaction method 2). In the following formulae, nl, n2, and R1 are as described above.

[0172] Reaction method 1: case where W is a carbon atom

[0173] [Chemical Formula 34]

[0174]

[0175] Reaction method 2: case where W is a nitrogen atom

[0176] [Chemical Formula 35]

[0177]

[0178] The base catalyst used in the condensation reaction of suisenene with aromatic aldehydes shown in reaction method 1 is, for example, inorganic base compounds such as sodium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, potassium phosphate, or the like, organic amine compounds such as triethylamine, pyridine, N-methylmorpholine, or the like, and the like, and they can be used alone or in combination of two or more. The amount of use of these catalysts is in the range of 0.1 to 20 moles, preferably 0.2 to 10 moles, relative to the moles of the starting material suisenene.

[0179] The solvent used in reaction method 1 is not particularly limited as long as it is a solvent that is inert to the above reaction, and for example, ether-based solvents such as diethyl ether, tetrahydrofuran, dioxane, or the like, aromatic solvents such as benzene, toluene, xylene, or the like, acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, water, or the like, and the like can be used alone or in combination. These solvents can be used in the range of 0 to 2000 parts by mass relative to 100 parts by mass of the reaction starting material, and the reaction temperature is preferably around the boiling point of the solvent, and more desirably room temperature to 150°C. The reaction time can be appropriately selected from 0.1 to 100 hours.

[0180] The reaction method and the recovery method of reaction method 1 can be used as the method that can be used in the case of X1.

[0181] The preparation of the compound used in the organic film material obtained by reaction method 1 can be performed in combination with the desired properties, and aromatic aldehydes having a substituent other than R1 can be used alone or in combination. For example, aromatic aldehydes having a substituent that contributes to planarization properties and film formation properties, and a substituent that contributes to etching resistance and heat resistance can be combined in any ratio.

[0182] As the acid catalyst used in the condensation reaction of sumaresene oxide with aromatic amines shown in Reaction Method 2, there can be used inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, heteropoly acid, and the like, organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, and the like, Lewis acids such as aluminum chloride, ethoxyaluminum, isopropoxyaluminum, boron trifluoride, boron trichloride, boron tribromide, tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dimethoxydibutyltin, dibutyltin oxide, titanium tetrachloride, titanium tetrabromide, methoxytitanium (IV), ethoxytitanium (IV), isopropoxytitanium (IV), titanium (IV) oxide, and the like. The amount of use of this catalyst is in the range of 0.1 to 20 moles, preferably 0.2 to 10 moles, relative to the moles of the intermediate, bis(indol-2,3-dione).

[0183] The solvent used in Reaction Method 2 is not particularly limited, and there can be used alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and the like, ethers such as diethyl ether, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, 1,4-dioxane, and the like, chlorine-based solvents such as dichloromethane, chloroform, dichloroethane, trichloroethylene, and the like, hydrocarbons such as hexane, heptane, benzene, toluene, xylene, cumene, and the like, nitriles such as acetonitrile, and the like, ketones such as acetone, ethyl methyl ketone, isobutyl methyl ketone, and the like, esters such as ethyl acetate, n-butyl acetate, propylene glycol methyl ether acetate, and the like, aprotic polar solvents such as dimethyl sulfoxide, N,N-dimethylformamide, hexamethylphosphoric triamide, and the like, which can be used alone or in combination of two or more. These solvents can be used in the range of 0 to 2000 parts by mass relative to 100 parts by mass of the reaction raw material, and the reaction temperature is preferably in the range of -50°C to the boiling point of the solvent, more preferably in the range of room temperature to 150°C. The reaction time can be appropriately selected from the range of 0.1 to 100 hours.

[0184] The reaction method and the recovery method of Reaction Method 2 can use the above-described methods as the methods that can be used in the case of X1.

[0185] The preparation of the compound used in the organic film-forming composition obtained by Reaction Method 2 can use, in combination with the required properties, various aromatic amines having a substituent other than R1, either alone or in combination. For example, it is possible to combine, in any ratio, aromatic amines having a substituent that contributes to the planarization characteristics and the film-forming property, and aromatic amines having a substituent that contributes to the etching resistance and the heat resistance.

[0186] When X is X3, the production method differs depending on whether R2is a hydrogen atom or an alkyl group. When R2is a hydrogen atom, it can be obtained by, for example, a reaction of sumaresenone oxide with an organometallic reagent represented by R3-M (Step 1). When R2is an alkyl group, it can be obtained by, for example, a condensation reaction of the sumaresenone derivative obtained in Step 1 with an alcohol represented by R2-OH (Step 2). R2and R3in the formulae below are as described above, and M is Li or MgX5, and X5is a halogen atom.

[0187] [Chem. 36]

[0188]

[0189] The organometallic reagent used in Step 1 can include Grignard reagents, organolithium reagents, organozinc reagents, organotitanium reagents, and the like, with Grignard reagents and organolithium reagents being particularly preferable. Grignard reagents and organolithium reagents can be prepared by direct metallation of the corresponding halide with metallic magnesium or lithium, or by metal-halogen exchange reactions with aliphatic organometallic compounds such as isopropylmagnesium halide, methyllithium, butyllithium, and the like.

[0190] Alternatively, organozinc reagents and organotitanium reagents can be prepared by reaction of the corresponding Grignard reagents or organolithium reagents with zinc halide, titanium (IV) halide, titanium (IV) alkoxide, or the like. When preparing the above organometallic reagents, or when reacting the above organometallic reagents with sumaresenone oxide, a metal salt compound can also be present. In this case, the reaction proceeds in the presence of a transition metal catalyst such as palladium or nickel.

[0191] The above metal salt compound can include cyanide, halide, and perhalogen acid salts, and lithium salts such as lithium chloride, lithium bromide, lithium iodide, and lithium perchlorate, and copper salts such as copper (I) cyanide, copper (II) cyanide, copper (I) chloride, copper (II) chloride, and dilithium tetrachlorocuprate can be mentioned as preferable metal salt compounds.

[0192] The above metal salt compound can be added in an amount of 0.01 to 5.0 equivalents, and preferably in an amount of 0.2 to 2.0 equivalents, relative to the organometallic reagent, to increase the solubility of the organometallic reagent, to make the preparation easier, or to adjust the nucleophilicity or Lewis acidity of the reagent.

[0193] As the solvent used in the preparation of the above organometallic reagent and in the reaction with sumaresenone oxide, ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, and cyclopentyl methyl ether, hydrocarbons such as benzene, toluene, xylene, mesitylene, hexane, heptane, octane, and isooctane, and aprotic polar solvents such as N,N,N',N'-tetramethylethylenediamine, hexamethylphosphoric triamide, and N,N-dimethylformamide can be used alone or in combination.

[0194] The reaction temperature, depending on the sumaresene oxide, the kind of the organometallic reagent, the reaction conditions, is preferably -70 to 150°C, for example, in the case of the organometallic reagent being an organozinc reagent, a Grignard reagent, the reaction can be carried out at room temperature to the boiling point of the solvent under reflux, etc., and can be variously selected depending on the reaction. The reaction time is usually carried out for 30 minutes to 48 hours, preferably.

[0195] The reaction method of Step 1 and the recovery method after quenching the reaction with the organometallic reagent with water, etc., can use the above-mentioned methods as the methods which can be used in the case of X1.

[0196] The acid catalyst and the solvent used in the condensation reaction with the alcohol represented by R2-OH in Step 2 can use the same acid catalyst and the solvent as those used in the condensation reaction of sumaresene oxide with aromatic amines in (Reaction Method 2). Also, the reaction method and the recovery method can use the above-mentioned methods as the methods which can be used in the case of X1.

[0197] As described above, the compound represented by the above-mentioned general formula (1) of the present application can give the composition for forming an organic film which can exhibit high etching resistance and excellent twist resistance.

[0198] <Composition for forming an organic film>

[0199] Also, the present application provides the composition for forming an organic film containing the compound represented by the above-mentioned general formula (1) and an organic solvent. Also, in the composition for forming an organic film of the present application, the compound represented by the above-mentioned general formula (1) of the present application can be used alone or in combination with a plurality of kinds.

[0200] In the composition for forming an organic film of the present application, a blending compound, other polymer, etc., a modifier can be further blended. The above-mentioned modifier, when mixed with the composition for forming an organic film of the present application, plays a role of improving the film-forming property of spin coating, the filling property on a substrate having a step difference.

[0201] Such modifiers can be exemplified by phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 3,5-diphenylphenol, 2-naphthylphenol, 3-naphthylphenol, 4-naphthylphenol, 4-tritylphenol, resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, catechol, 4-tert-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 2-methoxy-5-methylphenol, 2-tert-butyl-5-methylphenol, gallic acid, thymol, isothymol, 4,4'-(9H-fluoren-9-ylidene)bisphenol, 2,2'dimethyl-4,4'-(9H-fluoren-9-ylidene)bisphenol, 2,2'diallyl-4,4'-(9H-fluoren-9-ylidene)bisphenol, 2,2'difluoro-4,4'-(9H-fluoren-9-ylidene)bisphenol, 2,2'diphenyl-4,4'-(9H-fluoren-9-ylidene)bisphenol, 2,2'dimethoxy-4,4'-(9H-fluoren-9-ylidene)bisphenol, 2,3,2',3'-tetrahydro-(1,1')-spirobiindene-6,6'-diol, 3,3,3',3'-tetramethyl-2,3,2',3'-tetrahydro-(1,1')-spirobiindene-6,6'-diol, 3,3,3',3',4,4'-hexamethyl-2,3,2',3'-tetrahydro-(1,1')-spirobiindene-6,6'-diol, 2,3,2',3'-tetrahydro-(1,1')-spirobiindene-5,5'-diol, 5,5'-dimethyl-3,3,3',3'-tetramethyl-2,3,2',3'-tetrahydro-(1,1')-spirobiindene-6,6'-diol, 1-naphthol, 2-naphthol, 2-methyl-1-naphthol, 4-methoxy-1-naphthol, 7-methoxy-2-naphthol, and 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 3-hydroxynaphthalene-2-carboxylic acid methyl, indene, hydroxyindene, benzofuran, hydroxyanthracene, vinylnaphthalene, biphenyl, bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinyl-norborn-2-ene, α-pinene, β-pinene, limonene, novolak resins, polyhydroxystyrene, polystyrene, polyvinyl naphthalene, polyvinyl anthracene, polyvinyl carbazole, polyindene, polyvinylnaphthalene, polynorbornene, polycyclodecene, polytetracyclododecene, polytricyclo[2.2.1.0(2,6)]heptane (poly-nortricyclene), poly(meth)acrylate, and copolymers thereof.

[0202] Further, the naphthol dicyclopentadiene copolymer described in Japanese Patent Application Laid-Open No. 2004-205685, the fluorene bisphenol novolak resin described in Japanese Patent Application Laid-Open No. 2005-128509, the ethylene-naphthalene copolymer described in Japanese Patent Application Laid-Open No. 2005-250434, the fullerene having a phenol group described in Japanese Patent Application Laid-Open No. 2006-227391, the bisphenol compound and the novolak resin thereof described in Japanese Patent Application Laid-Open No. 2006-293298, the novolak resin of the adamantane phenol compound described in Japanese Patent Application Laid-Open No. 2006-285095, the bisnaphthol compound and the novolak resin thereof described in Japanese Patent Application Laid-Open No. 2010-122656, the fullerene resin compound described in Japanese Patent Application Laid-Open No. 2008-158002, and the like can also be blended.

[0203] The blending amount of the aforementioned modifier is preferably 0 to 1,000 parts by mass, more preferably 0 to 500 parts by mass, relative to 100 parts by mass of the compound represented by General Formula (1) of the present application.

[0204] [Organic solvent] The organic solvent that can be used in the organic film-forming composition of the present application is not particularly limited as long as the aforementioned compound represented by General Formula (1), acid generator, crosslinking agent, other additive, and the like are dissolved. Specifically, a solvent having a boiling point of not more than 180°C, such as the solvents described in paragraphs (0091) to (0092) of Japanese Patent Application Laid-Open No. 2007-199653, can be used.

[0205] Among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether, 2-heptanone, cyclopentanone, cyclohexanone (CyHO), and a mixture of two or more of these are preferable.

[0206] If the composition contains the aforementioned organic solvent, the composition can be coated by spin coating, and contains the aforementioned compound represented by General Formula (1) of the present application, so that an organic film-forming composition having good dry etching resistance, and also having heat resistance and high degree of filling / plane characteristics can be obtained.

[0207] Further, in the organic film-forming composition of the present application, a high-boiling-point organic solvent having a boiling point of not less than 180°C can be added to an organic solvent having a boiling point of not more than 180°C as the organic solvent (a mixture of an organic solvent having a boiling point of not more than 180°C and an organic solvent having a boiling point of not less than 180°C).

[0208] The high-boiling organic solvent is not particularly limited as long as it can dissolve the compound represented by General Formula (1), and examples thereof include hydrocarbons, alcohols, ketones, esters, ethers, chlorine-based solvents, and the like. Specific examples thereof include 1,6-diacetoxyhexane, 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 mononormal butyl ether, diethylene glycol monoisobutyl 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 normal butyl ether, triethylene glycol butyl methyl ether, triethylene glycol diacetate, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mononormal propyl ether, dipropylene glycol mononormal butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mononormal propyl ether, tripropylene glycol mononormal butyl 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 normal propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, triethylene glycol diacetate, γ-butyrolactone, dimethyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, dibutyl adipate, and the like. These can be used alone or in combination.

[0209] The boiling point of the aforementioned high-boiling organic solvent is appropriately selected in accordance with the temperature at which the composition for forming an organic film is heat-treated, and the boiling point of the added high-boiling organic solvent is preferably 180°C to 300°C, and more preferably 200°C to 300°C. If the aforementioned boiling point is 180°C or higher, there is no risk of rapid volatilization during baking (heat treatment) due to a too low boiling point, and sufficient thermal fluidity can be obtained. Also, if the aforementioned boiling point is 300°C or lower, the boiling point is not excessively high, and the aforementioned high-boiling solvent is not left remaining in the organic film after baking, and thus the physical properties of the organic film, such as etching resistance, are not adversely affected.

[0210] Further, when the aforementioned high-boiling-point organic solvent is used, the blending amount of the high-boiling-point organic solvent 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 the blending amount is so, there is no concern that sufficient thermal fluidity cannot be imparted at the time of baking or that the film properties such as etching resistance are deteriorated due to the residual organic film.

[0211] If the organic film-forming composition is so, by adding a high-boiling-point organic solvent to the compound represented by the aforementioned general formula (1) to impart thermal fluidity, an organic film-forming composition that gives a high degree of filling / plane- tizing properties can be obtained.

[0212] Further, the amount of the organic solvent as a whole is preferably 70 to 95% by mass, and more preferably 80 to 90% by mass, in the organic film-forming composition.

[0213] [Other additives]

[0214] In the organic film-forming composition of the present application, an acid generator can be added in order to more promote the hardening reaction. The acid generator can be either an acid generator that generates an acid due to thermal decomposition or an acid generator that generates an acid due to light irradiation, and either can be added. Specifically, the material described in paragraphs (0061) to (0085) of Japanese Patent Application Publication No. 2007-199653 can be added, but the present application is not limited thereto.

[0215] The aforementioned acid generator can be used alone or in combination with two or more. The addition amount of the acid generator, relative to 100 parts by mass of the compound represented by general formula (1), is preferably 0.05 to 50 parts by mass, and more preferably 0.1 to 10 parts by mass.

[0216] In the organic film-forming composition of the present application, a surfactant can be added in order to improve the coatability of spin coating. The surfactant, for example, can be the surfactant described in (0142) to (0147) of Japanese Patent Application Publication No. 2009-269953.

[0217] The addition amount of the surfactant, relative to 100 parts by mass of the aforementioned compound represented by general formula (1), is preferably 0.001 to 20 parts by mass, and more preferably 0.01 to 10 parts by mass.

[0218] Further, in the organic film-forming composition of the present application, a crosslinking agent can also be added in order to improve the hardening property and more inhibit cross mixing with the upper layer film. The crosslinking agent is not particularly limited, and various crosslinking agents of known systems can be widely used. As an example, a melamine-based crosslinking agent, a glycoluril-based crosslinking agent, a benzoguanamine-based crosslinking agent, a urea-based crosslinking agent, a β-hydroxyalkylamide-based crosslinking agent, an isocyanurate-based crosslinking agent, an aziridine-based crosslinking agent, an oxazoline-based crosslinking agent, and an epoxy-based crosslinking agent can be listed.

[0219] The amount of the crosslinking agent added is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the compound represented by the aforementioned general formula (1).

[0220] A melamine-based crosslinking agent, specifically, hexamethoxymethylated melamine, hexabutoxymethylated melamine, their alkoxy and / or hydroxy substituted bodies, and their partial self-condensates can be exemplified.

[0221] A glycoluril-based crosslinking agent, specifically, tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, their alkoxy and / or hydroxy substituted bodies, and their partial self-condensates can be exemplified.

[0222] A benzoguanamine-based crosslinking agent, specifically, tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, their alkoxy and / or hydroxy substituted bodies, and their partial self-condensates can be exemplified.

[0223] A urea-based crosslinking agent, specifically, dimethoxymethylated dimethoxyethyl urea, its alkoxy and / or hydroxy substituted bodies, and their partial self-condensates can be exemplified.

[0224] A β-hydroxyalkylamide-based crosslinking agent, specifically, N,N,N',N'-tetra(2-hydroxyethyl)adipamide can be exemplified.

[0225] An isocyanurate-based crosslinking agent, specifically, isocyanuric acid triepoxypropyl ester, isocyanuric acid triallyl ester can be exemplified.

[0226] An aziridine-based crosslinking agent, specifically, 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane, 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate] can be exemplified.

[0227] An oxazoline-based crosslinking agent, specifically, 2,2'-isopropylidenebis(4-benzyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), 2,2'-methylenebis 4,5-diphenyl-2-oxazoline, 2,2'-methylenebis-4-phenyl-2-oxazoline, 2,2'-methylenebis-4-tert-butyl-2-oxazoline, 2,2'-bis(2-oxazoline), 1,3-phenylenebis(2-oxazoline), 1,4-phenylenebis(2-oxazoline), 2-isopropenyl oxazoline copolymer can be exemplified.

[0228] An epoxy-based crosslinking agent, specifically, diepoxypropyl ether, ethylene glycol diepoxypropyl ether, 1,4-butanediol diepoxypropyl ether, 1,4-cyclohexanedimethanol diepoxypropyl ether, poly(epoxypropyl methacrylate), trimethylolethane triepoxypropyl ether, trimethylolpropane triepoxypropyl ether, neopentatetrol tetraepoxypropyl ether can be exemplified.

[0229] Further, in the composition for forming an organic film of the present application, a plasticizer can be added in order to further improve the planarization / leveling properties. The plasticizer is not particularly limited, and various known plasticizers of various systems can be used. Examples of the plasticizer include low molecular compounds such as phthalate esters, adipate esters, phosphate esters, trimellitate esters, citrate esters, polyether-based plasticizers, polyester-based plasticizers, and polyoxymethylene-based polymers described in Japanese Patent Application Publication No. 2013-253227.

[0230] The amount of the plasticizer to be added is preferably 5 to 500 parts by mass, and more preferably 10 to 200 parts by mass, relative to 100 parts by mass of the compound represented by the general formula (1).

[0231] Further, in the composition for forming an organic film of the present application, as an additive that imparts the same level of level / planarization properties as the plasticizer, for example, a liquid additive having a polyethylene glycol or polypropylene glycol structure, or a thermally decomposable polymer having a weight reduction rate of 40% by mass or more at 30°C to 250°C and a weight average molecular weight of 300 to 200,000 is preferably used. The thermally decomposable polymer preferably contains repeating units having an acetal structure represented by the following general formula (DP1) or (DP2).

[0232] [Chemical Formula 37]

[0233]

[0234] In the formula, R4 is a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms that can be substituted. Y is a divalent organic group having 2 to 30 carbon atoms that can be saturated or unsaturated.

[0235] [Chemical Formula 38]

[0236]

[0237] In the formula, R5 is an alkyl group having 1 to 4 carbon atoms. Z is a divalent hydrocarbon group having 4 to 10 carbon atoms that can be saturated or unsaturated, and can have an ether bond. n represents the average number of repeating units, and is 3 to 500.

[0238] Further, the composition for forming an organic film of the present application can be used alone or in combination of two or more. The composition for forming an organic film can be used for resist organic film materials or planarization materials for semiconductor device manufacturing.

[0239] Further, the composition for forming an organic film of the present application is extremely useful as an organic film material for a two-layer resist process, a three-layer resist process using a silicon-containing resist intermediate film, a four-layer resist process using a silicon-containing resist intermediate film, a silicon-containing inorganic hard mask, and an organic bottom anti-reflective coating (BARC), and the like.

[0240] <Method for forming organic film>

[0241] The present application can form an organic underlayer film for a multilayer resist film used for photolithography or an organic film for a planarization film for semiconductor manufacturing using the aforementioned composition for forming an organic film.

[0242] In the present application, the aforementioned composition for forming an organic film is coated on a substrate to be processed by a spin coating method or the like. By using a spin coating method or the like, good filling properties can be obtained. After spin coating, the solvent is evaporated, and in order to prevent mixing with an upper resist film and a silicon-containing resist intermediate film, and to promote crosslinking reaction, baking (heat treatment) is performed. Baking is preferably performed at 100°C or higher and 600°C or lower for 10 to 600 seconds, more preferably at 200°C or higher and 500°C or lower for 10 to 300 seconds. If the upper limit of the heating temperature in the wafer processing of photolithography is 600°C or lower, and more preferably 500°C or lower, in view of device damage and the influence on wafer distortion, this is ideal.

[0243] Further, in the present application, the aforementioned composition for forming an organic film of the present application can also be coated on a substrate to be processed by a spin coating method or the like, and the composition for forming an organic film is calcined in a gas environment having an oxygen concentration of 0.1% or higher and 21% or lower to harden the composition for forming an organic film to form an organic film.

[0244] The composition for forming an organic film of the present application, by being calcined in such an oxygen gas environment, can obtain an organic film that is sufficiently hardened. The gas environment in baking can also be air, and it is not a problem, and in order to reduce oxygen, it is ideal to previously seal a noble gas such as N2, Ar, He, or the like, in order to prevent oxidation of the organic film. In order to prevent oxidation, the oxygen concentration needs to be controlled, and it is preferable to be 1000 ppm or lower, and more preferably 100 ppm or lower. If oxidation of the organic film during baking is prevented, there is no case of increased absorption or decreased etching resistance, and thus it is ideal.

[0245] The composition for forming an organic film of the present application, by its excellent filling / planarization properties, can obtain a planar organic film regardless of the concave-convex of the substrate to be processed, and thus it is extremely useful when forming a planar organic film on a substrate to be processed having a structure with a height of 30 nm or higher or a difference in level.

[0246] Further, the thickness of the organic underlayer film or the planarization film for semiconductor devices, or the like, can be appropriately selected, and it is preferable to be 30 to 20,000 nm, and more preferably 50 to 15,000 nm.

[0247] (Pattern forming method)

[0248] The present application can provide a pattern forming method, as a pattern forming method using a three-layer resist process of an organic film forming composition, which forms a pattern on a processed object, comprising at least the following steps: forming an organic film on a processed object using the organic film forming composition of the present application; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material; forming a resist upper layer film on the silicon-containing resist intermediate film using a photoresist composition; forming a circuit pattern on the resist upper layer film; etching to transfer the pattern on the silicon-containing resist intermediate film using the resist upper layer film having the formed circuit pattern as a mask; etching to transfer the pattern on the organic film using the silicon-containing resist intermediate film having the transferred pattern as a mask; and etching to form a pattern on the processed object using the organic film having the transferred pattern as a mask.

[0249] The silicon-containing resist intermediate film of the three-layer resist process is resistant to etching by oxygen or hydrogen, and therefore, in the three-layer resist process, dry etching of the organic film using the silicon-containing resist intermediate film as a mask is preferably performed using an etching gas mainly comprising oxygen or hydrogen.

[0250] The silicon-containing resist intermediate film of the three-layer resist process is preferably a polysiloxane-based intermediate film. By imparting an antireflection effect to the silicon-containing resist intermediate film, reflection can be suppressed. In particular, for 193 nm exposure applications, if a material having a high etching selectivity with respect to a substrate and containing a large amount of aromatic groups is used, the k value increases and the reflection from the substrate increases, but by imparting an absorption that becomes an appropriate k value for the silicon-containing resist intermediate film, reflection can be suppressed and the reflection from the substrate can be reduced to 0.5% or less. For 248 nm and 157 nm exposure applications, a polysiloxane having a pendant anthracene group and crosslinked by acid or heat, which has an antireflection effect, is preferably used. For 193 nm exposure applications, a polysiloxane having a pendant phenyl group or a light-absorbing group having a silicon-silicon bond and crosslinked by acid or heat, which has an antireflection effect, is preferably used.

[0251] An organic antireflection film (BARC) can also be formed on the aforementioned silicon-containing resist intermediate film, in which case, an organic film is formed on a substrate to be processed using the composition for forming an organic film of the present application, a silicon-containing resist intermediate film is formed on the aforementioned organic film using a silicon-containing resist intermediate film material, a BARC is formed on the aforementioned silicon-containing resist intermediate film, a resist upper layer film is formed on the aforementioned BARC using a photoresist composition, a circuit pattern is formed on the aforementioned resist upper layer film, a pattern is transferred to the aforementioned BARC and the aforementioned silicon-containing resist intermediate film in order by etching using the aforementioned resist upper layer film on which the circuit pattern has been formed as a mask, a pattern is transferred to the aforementioned organic film by etching using the aforementioned silicon-containing resist intermediate film on which the pattern has been transferred as a mask, the aforementioned substrate to be processed is etched using the aforementioned organic film on which the pattern has been transferred as a mask, and a pattern is formed on the aforementioned substrate to be processed, whereby a pattern can be formed on the aforementioned substrate to be processed.

[0252] Alternatively, an inorganic hard mask can also be formed as a resist intermediate film, in which case, an organic film is formed on a substrate to be processed using the composition for forming an organic film of the present application, an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the aforementioned organic film, a resist upper layer film is formed on the aforementioned inorganic hard mask using a photoresist composition, a circuit pattern is formed on the aforementioned resist upper layer film, a pattern is transferred to the aforementioned inorganic hard mask by etching using the aforementioned resist upper layer film on which the circuit pattern has been formed as a mask, a pattern is transferred to the aforementioned organic film by etching using the aforementioned inorganic hard mask on which the pattern has been formed as a mask, and the aforementioned substrate to be processed is etched using the aforementioned organic film on which the pattern has been formed as a mask, whereby a pattern can be formed on the aforementioned substrate to be processed.

[0253] As described above, when an inorganic hard mask is formed on an organic film, a silicon oxide film, a silicon nitride film, and a silicon oxynitride film (SiON film) can be formed by a CVD method, an ALD method, or the like. For example, with respect to a method for forming a silicon nitride film, Japanese Patent Application Publication No. 2002-334869 and International Publication No. 2004 / 066377 are described. The film thickness of the inorganic hard mask is preferably 5 to 200 nm, and more preferably 10 to 100 nm. Further, it is most preferable that the inorganic hard mask be a SiON film, which has a high effect as an antireflection film. The substrate temperature when forming the SiON film is 300 to 500°C, and thus the organic film positioned on the lower layer needs to withstand a temperature of 300 to 500°C. The composition for forming an organic film used in the present application has high heat resistance and can withstand a high temperature of 300 to 500°C, and thus can be combined with an inorganic hard mask formed by a CVD method or an ALD method and an organic film formed by a spin coating method.

[0254] Also, a 4-layer resist treatment using an organic anti-reflective film (BARC) is also desirable, in which case, an organic film is formed on a substrate to be processed using the organic film-forming composition of the present application, an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the organic film, a BARC is formed on the inorganic hard mask, a resist upper layer film is formed on the BARC using a photoresist composition, a circuit pattern is formed on the resist upper layer film, the resist upper layer film on which the circuit pattern has been formed is used as a mask, and a pattern is transferred to the BARC and the inorganic hard mask in order by etching, the inorganic hard mask on which the pattern has been transferred is used as a mask, a pattern is transferred to the organic film by etching, and the substrate to be processed is etched using the organic film on which the pattern has been transferred as a mask to form a pattern on the substrate to be processed, by these steps, a pattern can be formed on the substrate to be processed.

[0255] As described above, a photoresist film is formed as a resist upper layer film on an inorganic hard mask, but a BARC can also be formed on the inorganic hard mask by spin coating, and a photoresist film is formed thereon. In particular, when a SiON film is used as the inorganic hard mask, reflection can be suppressed even in immersion exposure at a high NA exceeding 1.0 by using a 2-layer anti-reflective film of the SiON film and the BARC. Another advantage of forming a BARC is that it has the effect of reducing the tailing of a photoresist pattern formed directly on the SiON film.

[0256] The resist upper layer film of the 3-layer resist treatment described above can be either a positive type or a negative type, and a photoresist composition that is the same as and generally used can be used. After the photoresist composition is spin coated, pre-baking is performed, but it is preferable to be in the range of 60 to 180°C for 10 to 300 seconds. Thereafter, exposure is performed in the usual manner, and post-exposure baking (PEB) and development are performed to obtain a resist pattern. Also, the thickness of the resist upper layer film is not particularly limited, and it is desirable to be in the range of 30 to 500 nm, and more desirably in the range of 50 to 400 nm.

[0257] Also, the exposure light can be high-energy rays having a wavelength of 300 nm or less, and specific examples include an excimer laser such as 248 nm, 193 nm, and 157 nm, soft X-rays having a wavelength of 3 to 20 nm, an electron beam, and X-rays.

[0258] In the pattern forming method of the present application, the method of forming a circuit pattern on the resist upper layer film is preferably optical lithography using light having a wavelength of 10 nm or more and 300 nm or less, direct drawing using an electron beam, nano-imprinting, or a combination thereof.

[0259] Also, in the pattern forming method of the present application, the development method is preferably alkali development or development using an organic solvent.

[0260] Then, the obtained resist pattern is used as a mask to perform etching. The etching of the silicon-containing resist intermediate film and the inorganic hard mask in the 3-layer resist processing is performed using a fluorocarbon gas with the upper resist pattern as a mask. By this, the silicon-containing resist intermediate film pattern and the inorganic hard mask pattern are formed.

[0261] Next, the obtained silicon-containing resist intermediate film pattern and inorganic hard mask pattern are used as a mask to perform etching processing of the organic film.

[0262] The etching of the processed substrate and the like can be performed by a conventional method. For example, if the processed substrate is SiO2, SiN, a silicon dioxide low dielectric constant insulating film, etching is performed mainly using a fluorine gas. If the processed substrate is p-Si, Al, W, etching is performed mainly using a chlorine gas or a bromine gas. When the substrate is etched using a fluorine gas, the silicon-containing resist intermediate film pattern in the 3-layer resist processing is peeled off at the same time as the substrate processing. When the substrate is etched using a chlorine gas or a bromine gas, the silicon-containing resist intermediate film pattern is peeled off separately after the substrate processing by dry etching using a fluorine gas.

[0263] The organic film obtained using the composition for forming an organic film according to the present application has excellent etching resistance when the processed substrate is etched.

[0264] In the pattern forming method according to the present application, the processed substrate is preferably a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, or a metal oxynitride film.

[0265] Further, the metal is preferably silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof.

[0266] The processed substrate is not particularly limited and can be a substrate such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, and the like, and a substrate on which a processed layer has been formed. The processed layer is formed using various Low-k films such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, Al-Si, and a barrier film thereof, and is preferably formed to have a thickness of 50 to 10,000 nm, more preferably 100 to 5,000 nm. The substrate and the processed layer can be formed using different materials.

[0267] The processed substrate preferably has a structure having a height of 30 nm or more or a processed substrate having a difference in height.

[0268] An example of the 3-layer resist processing is described below. Figure 1 A specific example is described below.

[0269] 3-layer resist processing, as Figure 1 (A) of FIG. 1, an organic film 3 is formed on the processed object 2 stacked on the substrate 1 using the composition for forming an organic film of the present application, and then a silicon-containing resist intermediate film 4 is formed thereon, and a resist upper layer film 5 is formed thereon.

[0270] Then, as shown in (B) of FIG. 1, a specific portion 6 of the resist upper layer film is exposed, PEB and development are performed, and a resist pattern 5a (C) of FIG. 1 is formed. This obtained resist pattern 5a is used as a mask, and the silicon-containing resist intermediate film 4 is etched using a CF-based gas, and a silicon-containing resist intermediate film pattern 4a (D) of FIG. 1 is formed. After the resist pattern 5a is removed, this obtained silicon-containing resist intermediate film pattern 4a is used as a mask, and the organic film 3 is subjected to oxygen plasma etching, and an organic film pattern 3a (E) of FIG. 1 is formed. After the silicon-containing resist intermediate film pattern 4a is further removed, the organic film pattern 3a is used as a mask, and the processed object 2 is etched, and a pattern 2a (F) of FIG. 1 is formed. Figure 1 Figure 1 Figure 1 Figure 1 Figure 1

[0271] When an inorganic hard mask is used, the silicon-containing resist intermediate film 4 is an inorganic hard mask, and when a BARC is coated, a BARC layer is provided between the silicon-containing resist intermediate film 4 or the inorganic hard mask and the resist upper layer film 5. Etching of the BARC is sometimes performed continuously before etching of the silicon-containing resist intermediate film 4, or the etching of the BARC can be performed, and then the etching apparatus or the like is changed, and the silicon-containing resist intermediate film 4 is etched.

[0272] Thus, if the pattern forming method of the present application is used, a fine pattern can be formed on a processed substrate with high precision in a multi-layer resist processing.

[0273] [Examples]

[0274] The following examples, comparative examples, examples, and comparative examples are more specifically described for the present application, but the present application is not limited by these. Also, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the dispersity (Mw / Mn) were obtained by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent.

[0275] ​​​​​The synthesis of compounds (Al) to (A8) contained in the composition for forming an organic film was performed using the following sumaresene (Bl) to (B2), aromatic aldehyde (Cl) to (C3), propargyl bromide (C4), aromatic Grignard reagent (C5) to (C6), and aromatic amine (C7). Also, the aromatic Grignard reagent (C6) and sumaresene oxide (B2) were synthesized by the methods described in Synthesis Example 1 and Synthesis Example 2, respectively.

[0276] Sumaresene:

[0277] [Chemical Formula 39]

[0278]

[0279] Aromatic aldehyde (Cl) to (C3), propargyl bromide (C4), aromatic Grignard reagent (C5) to (C6), and aromatic amine (C7)

[0280] [Chemical Formula 40]

[0281]

[0282] (Synthesis Example 1) Synthesis of aromatic Grignard reagent (C6)

[0283] [Chemical Formula 41]

[0284]

[0285] A flask was charged with magnesium 1.2 g, and degassed and dehydrated by heating with a hot air gun under reduced pressure. Under a nitrogen atmosphere, dehydrated THF 20 g and iodine 2.0 g were added and stirred. A solution of 2-bromonaphthalene 5.0 g in THF 10 g was added, and stirred at 40°C for 3 hours to obtain a THF solution of (C6).

[0286] (Synthesis Example 2) Synthesis of sumaresene (B2)

[0287] [Chemical Formula 42]

[0288]

[0289] Sumaresene (Bl) 10.0 g, dichloromethane 200 ml, pyridine 30.0 g, ruthenium (III) chloride hydrate 17.0 g, and t-butyl hydroperoxide 70% aqueous solution 100 g were added, and stirred at 40°C for 100 hours. After that, a small amount of silica gel was added, and dried under reduced pressure with an evaporator, and purified by column chromatography on silica gel to remove impurities. After dissolving in methyl isobutyl ketone (MIBK) and crystallizing with hexane, (B2) 8.1 g (70%) was recovered and dried at 70°C under vacuum to obtain (B2) 8.1 g (70%). The instrumental analysis data of this compound are described below.

[0290] (Synthesis Example 3) Synthesis of compound (Al)

[0291] [Chem. 43]

[0292]

[0293] Under nitrogen atmosphere, sumaresene (B1) 1.0 g, n-tetrabutylammonium bromide 5.5 g, 30 wt% sodium hydroxide aqueous solution 100 ml degassed by bubbling nitrogen, THF 50 ml were added. After that, 4-ethynylbenzaldehyde (C1) 3.5 g was added, and stirred at room temperature for 15 hours. MIBK 150 ml was added, and washed with deionized water until neutral. The obtained organic layer was concentrated, dissolved in MIBK, methanol was added and crystallized, filtered, washed and recovered, vacuum dried at 70°C to obtain (A1) 1.7 g (74%). The following shows the instrumental analysis data of this compound.

[0294] IR (ATR method): 3443, 3289, 3036, 2957, 2870, 2106, 1698, 1661, 1505, 1403, 1367, 1308, 1224, 1163, 1110, 1016, 887, 827, 653, 544 cm ―1

[0295] 1 H―NMR (600 MHz, in CDC13): 7.89-7.80 (6H, m), 7.64-7.50 (7H, m), 7.43-7.16 (8H, m), 3.24-3.20 (3H, m) ppm

[0296] 13 C―NMR (150 MHz, in CDC13): 162.512, 147.825, 147.458, 147.368, 145.807, 145.511, 145.339, 141.318, 141.219, 141.092, 132.853, 132.757, 132.559, 132.500, 130.751, 129.725, 129.663, 128.223, 127.869, 127.631, 127.571, 127.329, 125.727, 125.622, 123.884, 123.751, 123.662, 123.511, 122.454, 121.162, 121.060, 120.964, 120.964, 115.423, 115.323, 115.216, 76.496, 56.092 ppm GPC: Mw / Mn = 1.08

[0297] MS (for C 48 H24 +H + Calcd): 601.195

[0298] MS (LC-MS): 601.194

[0299] (Synthetic Example 4) Synthesis of Compound (A2)

[0300] [Synthesis Example 4] Synthesis of Compound (A2)

[0301]

[0302] 4-ethynylbenzaldehyde (C1) was changed to 4-ethynylphenylbenzaldehyde (C2), and the same procedure as for Compound (Al) was carried out except for this, to obtain Compound (A2) 2.2 g (69%). The instrumental analysis data of this compound are disclosed below.

[0303] IR (ATR method): 3290, 3054, 2960, 2873, 2738, 2213, 2121, 1693, 1598, 1507, 1487, 1442, 1394, 1311, 1223, 1180, 1159, 1107, 1069, 1018, 910, 887, 824, 754, 689 cm -1

[0304] 1 H―NMR (600 MHz in CDC13): 7.90 (2H, m), 7.83 (2H, m), 7.66 (3H, m), 7.57 (10H, m), 7.47 (2H, m), 7.38 (15H, m), 7.24-7.16 (2H, m) ppm

[0305] 13C―NMR (150 MHz, in CDC13): 162.513, 147.535, 147.453, 147.403, 146.084, 145.787, 145.733, 145.495, 143.406, 143.159, 141.578, 141.125, 141.008, 136.370, 136.288, 136.218, 136.132, 132.213, 132.134, 132.047, 132.014, 131.914, 131.827, 131.751, 130.755, 130.207, 129.989, 129.837, 129.775, 128.573, 128.531, 128.334, 128.058, 127.815, 127.757, 127.516, 126.978, 125.776, 123.898, 123.765, 123.717, 123.512, 123.273, 121.209, 121.135, 121.010, 120.924, 115.325, 91.22, 89.57 ppm.

[0306] GPC: Mw / Mn = 1.02

[0307] MS (for C 66 H 36 +H + Calculated): 829.289

[0308] MS (LC-MS): 829.288

[0309] (Synthetic Example 5) Synthesis of Compound (A3)

[0310] [Synthesis 45]

[0311]

[0312] 4-ethynylbenzaldehyde (C1) was replaced with 4-(propargyloxy)benzaldehyde (C3), and the same procedure as for Compound (Al) was followed, except that, to obtain Compound (A3), 2.0 g (75%) was obtained. The instrumental analysis data of this compound are disclosed below.

[0313] IR (ATR method): 3287, 3041, 2923, 2120, 1686, 1600, 1507, 1445, 1394, 1370, 1304, 1224, 1173, 1113, 1020, 978, 826, 681, 630 cm -1

[0314] 1H―NMR (600 MHz in CDC13): 7.92-7.83 (8H, m), 7.49-7.27 (5H, m), 7.19-7.05 (8H, m), 4.83-4.77 (6H, m), 2.63-2.59 (3H, m) ppm

[0315] 13 C―NMR (150 MHz in CDC13): 158.139, 147.871, 147.547, 146.013, 145.667, 145.517, 145.237, 145.074, 143.373, 143.321, 139.383, 139.296, 132.048, 132.045, 131.347, 131.324, 131.298, 131.275, 130.171, 129.887, 129.847, 129.728, 128.270, 128.119, 127.902, 127.822, 127.608, 123.491, 123.343, 120.801, 120.707, 120.628, 120.506, 115.330, 115.171, 115.126, 78.85, 76.006, 56.052, 29.844 ppm

[0316] GPC: Mw / Mn = 1.06

[0317] MS (for C 51 H 30 O3+H + Calculated): 691.227

[0318] MS (LC-MS): 691.226

[0319] (Synthetic Example 6) Synthesis of Compound (A4)

[0320] [Chemical Formula 46]

[0321]

[0322] To sumaresene (Bl) 1.0 g, n-butyl ammonium bromide 5.5 g, 30 wt% sodium hydroxide aqueous solution 100 ml degassed by bubbling with nitrogen, THF 50 ml were added under nitrogen atmosphere. Thereafter, propargyl bromide 80 wt% toluene solution (C4) 10.0 g was added, and stirred at room temperature for 100 hours. MIBK 150 ml was added, and washed with deionized water until neutral. The obtained organic layer was concentrated, dissolved in MIBK, hexane was added and crystallized, filtered, washed, and vacuum dried at 70°C to obtain (A4) 1.5 g (80%). The following shows the instrumental analysis data of this compound.

[0323] IR (ATR method): 3433, 3296, 2929, 2118, 1723, 1426, 1366, 1257, 1086, 825, 643cm -1

[0324] 1 H-NMR (600MHz, in CDCl3): 7.34 (6H, s), 3.47 (6H, d), 2.53 (6H, d), 2.26 (3H, t), 2.09 (3H, t)

[0325] 13 C-NMR (150MHz, at CDCl3): 154.911, 146.056, 122.961, 81.228, 71.604, 59.549, 24.629ppm

[0326] GPC: Mw / Mn = 1.07

[0327] MS (as for C) 39 H 24 +H + (Calculated): 493.195

[0328] MS (LC-MS): 493.195

[0329] (Synthesis Example 7) Synthesis of Compound (A5)

[0330] [Chemistry 47]

[0331]

[0332] 1.0 g of trioxane (B2) and 30 ml of THF were added under nitrogen atmosphere. 30 ml of a 1 M THF solution of magnesium phenyl bromide (C5) was added while stirring at room temperature, and the mixture was stirred overnight. 50 g of ammonium chloride aqueous solution was added to stop the reaction, and the mixture was extracted with 150 ml of MIBK. The organic layer was then washed with deionized water until neutral. The mixture was dried under reduced pressure using an evaporator, and impurities were removed by silica gel column chromatography. The solution was dissolved in MIBK, crystallized with hexane, filtered, washed, and dried under vacuum at 70 °C to obtain 1.4 g (80%) of (A5). The following describes the apparatus analysis data for this compound.

[0333] IR (ATR method): 3533, 3381, 3051, 3001, 1611, 1510, 1476, 1451, 1359 cm -1

[0334] 1H―NMR (600 MHz in CDC13): 7.28 (15H, m), 7.02 (6H, s), 5.72 (3H, s) ppm

[0335] 13 C―NMR (150 MHz in CDC13): 160.321, 158.2, 146.223, 130.211, 122.415, 122.511, 116.283, 83.728 ppm

[0336] GPC: Mw / Mn = 1.03

[0337] (Synthetic Example 8) Synthesis of Compound (A6)

[0338] [Chemical Formula 48]

[0339]

[0340] Instead of phenylmagnesium bromide (C5), 2-naphthylmagnesium bromide (C6) prepared in Synthetic Example 1 was used, and the same procedure as for Compound (A5) was carried out to obtain 2.4 g (71%) of (A6). The yield and instrumental analysis data of this compound are shown below.

[0341] IR (ATR method): 3531, 3394, 3053, 3019, 1601, 1505, 1474, 1448, 1357 cm -1

[0342] 1 H―NMR (600 MHz in CDC13): 8.03-7.09 (21H, m), 7.04 (6H, s), 5.78 (3H, s) ppm

[0343] 13 C―NMR (150 MHz in CDC13): 161.312, 150.343, 146.273, 140.442, 139.686, 133.223, 132.639, 128.148, 127.497, 126.004, 125.774, 124.146, 121.122, 83.712 ppm

[0344] GPC: Mw / Mn = 1.05

[0345] (Synthetic Example 9) Synthesis of Compound (A7)

[0346] [Chemical Formula 49]

[0347]

[0348] To the compound (A6) 1.0 g, methanol 20.0 g under nitrogen atmosphere, add methanesulfonic acid 2.0 g, and stir for 3 hours under reflux. Add toluene 150 ml, and wash with deionized water until neutral. Concentrate the obtained organic layer, dissolve in MIBK, add hexane and crystallize, filter, wash, and obtain (A7) 0.93 g (88%). The following shows the instrumental analysis data of this compound.

[0349] IR (ATR method): 3051, 2927, 2826, 1603, 1446, 1160, 1082 cm -1

[0350] 1 H―NMR (600 MHz in CDCl3): 8.03-7.09 (21H, m), 7.04 (6H, s), 3.06 (9H, s)

[0351] 13 C―NMR (150 MHz in CDCl3): 161.293, 146.877, 146.221, 141.017, 140.778, 133.271, 132.649, 127.727, 126.384, 125.659, 124.357, 123.945, 120.913, 89.189, 51.445 ppm

[0352] GPC: Mw / Mn = 1.04

[0353] (Synthetic Example 10) Synthesis of compound (A8)

[0354] [Chemical 50]

[0355]

[0356] To trioxosumulene (B2) 1.5 g, 4-ethynylaniline (C7) 5.3 g, activated molecular sieve (MS4A) 5.0 g, and dehydrated toluene 20 ml under nitrogen atmosphere, and react for 6 hours at 120°C. Add 4-ethynylaniline (C7) 5.3 g, activated molecular sieve (MS4A) 5.0 g, and continue the reaction for 24 hours. Dry the reaction solution by evaporation under reduced pressure, and purify by column chromatography on silica gel. Dissolve in MIBK, crystallize with hexane, filter, wash, and dry under vacuum at 70°C to obtain (A8) 1.3 g (39%). The following shows the instrumental analysis data of this compound.

[0357] IR (ATR method): 3339, 3021, 2911, 2850, 1888, 1717, 1651, 1611, 1553, 1499, 1388 cm ―1

[0358] 1 H―NMR (600 MHz in CDC13): 6.08 (2H, d), 6.50 (2H, d), 6.92-7.30 (12H, m) 7.61 (2H, d) ppm

[0359] 13 C―NMR (150 MHz in CDC13): 163.186, 162.893, 148.965, 148.800, 148.466, 148.399, 148.365, 148.300, 148.286, 148.211, 148.191, 148.139, 147.941, 147.851, 136.213, 136.279, 136.173, 136.122, 130.235, 130.220, 130.099, 130.077, 126.801, 126.635, 126.603, 126.516, 124.900, 124.813, 124.644, 124.625, 120.961, 120.922, 120.744, 76.496, 56.092 ppm.

[0360] GPC: Mw / Mn = 1.08

[0361] (Comparative Synthesis Example)

[0362] (Synthesis of Compound (R1) (Comparative Synthesis Example 1)

[0363] [Chemical Formula 51]

[0364]

[0365] Under nitrogen atmosphere, 2-acetylfluorene 120 g, m-xylene 120 g were added and warmed to 110°C to make a homogeneous solution. Dodecylbenzenesulfonic acid 21.0 g was added and warmed to 140°C to carry out the reaction for 16 hours. The reaction solution was added to methanol and crystallized, filtered, washed, and vacuum dried at 70°C to obtain (R1). Using GPC, the weight average molecular weight (Mw) and the dispersity (Mw / Mn) were calculated, and the results were Mw = 620, Mw / Mn = 1.03.

[0366] (Synthesis of Compound (R2) (Comparative Synthesis Example 2)

[0367] [Chemical Formula 52]

[0368]

[0369] Under a nitrogen atmosphere, compound (Rl) 10.0 g, n-butyl bromide 25.0 g, 30 wt% sodium hydroxide aqueous solution 300 ml degassed by bubbling nitrogen, THF 100 ml were added. After that, 4-ethynylbenzaldehyde (Cl) 14.0 g was added, and stirred at room temperature for 15 hours. MIBK 150 ml was added, and washed with deionized water until neutral. The obtained organic layer was concentrated, dissolved in MIBK, methanol was added and crystallized, filtered, washed, and dried at 70°C under vacuum to obtain (R2). The weight average molecular weight (Mw), and the dispersity (Mw / Mn) were determined by GPC, and the results were Mw = 960, Mw / Mn = 1.04.

[0370] (Synthetic Example 3) Synthesis of compound (R3)

[0371] [Chemical Formula 53]

[0372]

[0373] 4-ethynylbenzaldehyde (Cl) was changed to 4-(propargyloxy)benzaldehyde (C3), and the same as compound (R2) was performed except for this to obtain compound (R3). The weight average molecular weight (Mw), and the dispersity (Mw / Mn) were determined by GPC, and the results were Mw = 960, Mw / Mn = 1.04.

[0374] (Synthetic Example 4) Synthesis of compound (R4)

[0375] [Chemical Formula 54]

[0376]

[0377] Under a nitrogen atmosphere, compound (Rl) 10.0 g, n-butyl bromide 25.0 g, 30 wt% sodium hydroxide aqueous solution 300 ml degassed by bubbling nitrogen, THF 100 ml were added. After that, 4-ethynylbenzaldehyde (Cl) 14.0 g was added, and stirred at room temperature for 15 hours. MIBK 150 ml was added, and washed with deionized water until neutral. The obtained organic layer was concentrated, dissolved in MIBK, methanol was added and crystallized, filtered, washed, and dried at 70°C under vacuum to obtain (R2). The weight average molecular weight (Mw), and the dispersity (Mw / Mn) were determined by GPC, and the results were Mw = 960, Mw / Mn = 1.04.

[0378] (Synthetic Example 5) Synthesis of compound (R5)

[0379] [Chemical Formula 55]

[0380]

[0381] Under nitrogen atmosphere, 1.0 g of thremanne (B1), 5.5 g of tetrabutylammonium bromide, 100 ml of 30 wt% sodium hydroxide aqueous solution degassed by bubbling with nitrogen, and 50 ml of THF were added. Then, 10.0 g of allyl bromide was added, and the mixture was stirred at room temperature for 45 hours. 150 ml of MIBK was added, and the mixture was washed with deionized water until neutral. The obtained organic layer was concentrated, dissolved in MIBK, and crystallized with hexane. After filtration and washing, the mixture was dried under vacuum at 70 °C to obtain (R5). The weight-average molecular weight (Mw) and dispersity (Mw / Mn) were calculated using GPC, yielding Mw = 520 and Mw / Mn = 1.05.

[0382] Preparation of organic film forming compositions (UDL-1 to 15, comparative UDL-1 to 5)

[0383] Using the aforementioned compounds (A1) to (A8) and the comparative examples (R1) to (R5), as high-boiling organic solvents, (S1) 1,6-diacetoxyhexane (boiling point 260°C) and (S2) tripropylene glycol monomethyl ether (boiling point 242°C), and propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (CyHO) containing 0.1% by mass of FC-4430 (manufactured by Sumitomo 3M), the compounds were dissolved in the proportions shown in Table 1 and filtered through a 0.1 μm fluoropolymer filter to prepare organic film-forming compositions (UDL-1 to 15, comparative UDL-1 to 5). Furthermore, UDL-6, 8, and 10 used a thermal acid generator (TAG) represented by the following formula.

[0384] [Table 1]

[0385]

[0386] [Chemistry 56]

[0387]

[0388] Examples 1-1 to 1-15, Comparative Examples 1-1 to 1-5 (Solvent Resistance Test)

[0389] The aforementioned UDL-1 to 15 and comparative UDL-1 to 5 were coated onto a silicon substrate. After baking at 350°C for 60 seconds in atmospheric conditions, the film thickness was measured. PGMEA solvent was then applied to the substrate, left to stand for 30 seconds, and then spun dry. The substrate was then baked at 100°C for 60 seconds to evaporate the PGMEA. The film thickness before and after PGMEA treatment was measured. The residual film yield was calculated using both the post-coating film thickness and the PGMEA-treated film thickness. The results are shown in Table 2.

[0390] [Table 2]

[0391]

[0392] As shown in Table 2, the organic films (Examples 1-1 to 1-15) using the compounds of the present application had a residual film rate of 99% or more after PGMEA treatment, and it was found that the cross-linking reaction due to heat treatment was exhibited, and sufficient solvent resistance was exhibited. From these results, it was found that the compound having the specific partial structure of the present application had a thermal curing property. When comparing Examples 1-5, 1-7, 1-9 and 1-6, 1-8, 1-10, it was found that the residual film rate was increased by about 0.4 to 0.7% by adding a thermal acid generator compared to the compound alone, and a denser film was formed due to the action of the acid catalyst. It was confirmed that the organic films using the compounds having the same partial structure (Comparative Examples 1-2 to 1-4) and the organic films using the compounds having a suisen skeleton (Comparative Example 1-5) also exhibited solvent resistance.

[0393] Examples 2-1 to 2-15, Comparative Examples 2-1 to 2-5 (hardness measurement)

[0394] The aforementioned UDL-1 to 15 and Comparative UDL-1 to 5 were coated on a silicon substrate, and baked at 350°C for 60 seconds in the air to form an organic film having a film thickness of 200 nm. Nanoindentation test was performed on these organic films using a nanoindenter SA2 manufactured by TOYO TECHNICA Corporation, and the hardness of the aforementioned organic films was measured. The results are shown in Table 3.

[0395] [Table 3]

[0396] Composition for organic film formation Hardness (GPa) Example 2-1 UDL-1 0.80 Example 2-2 UDL-2 0.78 Example 2-3 UDL-3 0.75 Example 2-4 UDL-4 0.73 Example 2-5 UDL-5 0.71 Example 2-6 UDL-6 0.75 Example 2-7 UDL-7 0.72 Example 2-8 UDL-8 0.76 Example 2-9 UDL-9 0.70 Example 2-10 UDL-10 0.77 Example 2-11 UDL-11 0.75 Example 2-12 UDL-12 0.79 Example 2-13 UDL-13 0.72 Example 2-14 UDL-14 0.80 Example 2-15 UDL-15 0.72 Comparative Example 2-1 Comparative UDL-1 0.63 Comparative Example 2-2 Comparative UDL-2 0.66 Comparative Example 2-3 Comparative UDL-3 0.64 Comparative Example 2-4 Comparative UDL-4 0.65 Comparative Example 2-5 Comparative UDL-5 0.69

[0397] As shown in Table 3, when comparing Examples 2-1 to 2-15 and Comparative Examples 2-1 to 2-4, it was found that the compound having a suisen structure had a superior film hardness. Also, when comparing Examples 2-5 to 2-10, Examples 2-5, 2-7, 2-9 and Examples 2-6, 2-8, 2-10, it was found that the hardness of Examples 2-6, 2-8, 2-10 was higher, and thus, as in Example 1, the hardness was increased by adding a thermal acid generator, and a denser film was formed. When comparing Examples 2-1 and Comparative Example 2-2, Examples 2-3 and Comparative Example 2-3, and Examples 2-4 and Comparative Example 2-4, which have the same substituent structure, it was found that the compound having the suisen-containing structure of the present application had a higher hardness. It is presumed that this is due to the densification of the film due to the suisen structure, and the property of suisen itself to easily form aggregates. Furthermore, when comparing Example 2-4 having a suisen structure and Comparative Example 2-5, it was confirmed that the hardness of the compound having a propargyl group was higher than that of the compound having an allyl group, and a denser film could be formed, and as in the results of the solvent resistance test of Example 1, the propargyl group had superior solvent resistance, and it was similarly presumed that a denser film could be formed.

[0398] Examples 3-1 to 3-15, Comparative Examples 3-1 to 3-5 (etching test)

[0399] [Etching test with CF4 / CHF3-based gas]

[0400] The aforementioned UDL-1 to 15 and Comparative UDL-1 to 5 were applied to a silicon substrate, baked at 350°C for 60 seconds in the atmosphere to form an organic film with a film thickness of 200 nm, and then an etching test with a CF4 / CHF3-based gas was performed under the following conditions to obtain the film thickness difference of the organic film before and after etching. The results are shown in Table 4. Also, the etching was performed using a dry etching device TE-8500 manufactured by Tokyo Electron Limited.

[0401] The etching conditions are shown below.

[0402]

[0403] [Table 4]

[0404]

[0405] Table 4 shows the film reduction ratio of each of the examples and comparative examples when the film thickness reduced by etching with a CF4 / CHF3-based gas of Comparative UDL-1 is set to 100%. The smaller this ratio, the more excellent the etching resistance.

[0406] [Etching test with O2-based gas]

[0407] The aforementioned UDL-1 to 15 and Comparative UDL-1 to 5 were applied to a silicon substrate, baked at 350°C for 60 seconds in the atmosphere to form an organic film with a film thickness of 200 nm, and then an etching test with an O2-based gas was performed under the following conditions to obtain the film thickness difference of the organic film before and after etching. The results are shown in Table 4. Also, the etching was performed using a dry etching device TE-8500 manufactured by Tokyo Electron Limited.

[0408] The etching conditions are shown below.

[0409]

[0410] As with the etching test with a CF4 / CHF3-based gas, Table 4 shows the film reduction ratio of each of the examples and comparative examples when the film thickness reduced by etching with an O2-based gas of Comparative UDL-1 is set to 100%. The smaller this ratio, the more excellent the etching resistance.

[0411] As shown in Table 4, if Examples 3-1 to 3-15 are compared with Comparative Examples 3-1 to 3-4, the amount of reduction in the film after etching in CF4 / CHF3-based gas and O2-based gas is the same or less in the examples than in the comparative examples, and it is understood that an organic film having excellent etching resistance is formed. In particular, the etching resistance of Examples 3-1, 3-2, 3-4, and Examples 3-5 to 3-10, which do not contain a heteroatom structure or become free of a heteroatom due to hardening, is a good result. Also, if Examples 3-1, 3-3, and 3-4, which have the same substituent structure as in Example 2, are compared with Comparative Examples 3-2, 3-3, and 3-4, respectively, it is understood that the same substituent structure is used, and if the etching resistance is compared, the use of a compound having a suisenene structure forms an organic film having more excellent etching resistance. Also, if Example 3-4, which has a suisenene skeleton, is compared with Comparative Example 3-5, the etching resistance of Example 3-4 is better, and it is confirmed that a propargyl group is more effective than an allyl group in terms of etching resistance. It is believed that, as shown in Examples 1 and 2, because of excellent solvent resistance and hardness, a denser film is formed.

[0412] Examples 4-1 to 4-15, Comparative Examples 4-1 to 4-5 (pattern etching test)

[0413] The aforementioned UDL-1 to 15 and Comparative UDL-1 to 5 were applied to a Si wafer substrate of 300 mm in diameter on which a SiO2 film of 200 nm in thickness had been formed, and an organic film was formed at 350°C in the atmosphere so that the film thickness after baking for 60 seconds was 200 nm. A silicon-containing resist intermediate film material (SOG-1) was applied thereto, and baking was performed at 220°C for 60 seconds to form a resist intermediate film of 35 nm in thickness, and a resist upper film material (SL resist for ArF) was applied, and baking was performed at 105°C for 60 seconds to form a resist upper film of 100 nm in thickness. A penetration protection film (TC-1) was applied to the resist upper film, and baking was performed at 90°C for 60 seconds to form a protection film of 50 nm in thickness.

[0414] The resist upper film material (SL resist for ArF) was prepared by dissolving 100 parts by mass of a polymer (RP1) represented by the following formula, 6.6 parts by mass of an acid generator (PAG1) represented by the following formula, and 0.8 parts by mass of an alkaline compound (Amine1) represented by the following formula in PGMEA 2500 parts by mass containing 0.1% by mass of FC-430 (Sumitomo 3M Co., Ltd.) and filtering with a filter made of a fluorine resin of 0.1 μm.

[0415] [Chem. 57]

[0416]

[0417] The underlayer protective film material (TC-1) was prepared by dissolving 100 parts by mass of the protective film polymer (PP1) represented by the following formula in an organic solvent composed of diisopentyl ether 2700 parts by mass and 2-methyl-l-butanol 270 parts by mass, and filtering with a filter made of a fluororesin having a pore size of 0.1 μm.

[0418] [Chemical 58]

[0419]

[0420] The silicon-containing resist intermediate film material (SOG-1) was prepared by dissolving 100 parts by mass of the ArF silicon-containing intermediate film polymer (SiP1) represented by the following formula and 1 part by mass of the crosslinking catalyst (CAT1) represented by the following formula in PGMEA 4000 parts by mass containing 0.1 mass% of FC-4430 (manufactured by Sumitomo 3M Company), and filtering with a filter made of a fluororesin having a pore size of 0.1 μm.

[0421] [Chemical 59]

[0422]

[0423] Then, exposure was performed with an ArF immersion exposure device (manufactured by Nikon Corporation; NSR-S610C, NA 1.30, σ 0.98 / 0.65, 35-degree dipole s-polarized light illumination, 6% half-step phase shift mask) while changing the exposure amount, baking (PEB) was performed at 100°C for 60 seconds, development was performed with 2.38 mass% aqueous tetramethylammonium hydroxide (TMAH) solution for 30 seconds, and a positive-type line-and-space pattern having a line width of 50 nm to 30 nm at a pitch of 100 nm was obtained.

[0424] Subsequently, using an etching device Telius manufactured by Tokyo Electron Limited, processing of the silicon-containing resist intermediate film with the resist pattern as a mask, processing of the organic film with the silicon-containing resist intermediate film as a mask, and processing of the SiO2 film (processed object) with the organic film as a mask were sequentially performed by dry etching.

[0425] The etching conditions are shown below.

[0426] Transfer conditions of the resist pattern to the SOG film (silicon-containing resist intermediate film):

[0427]

[0428] Transfer conditions of the SOG film (silicon-containing resist intermediate film) to the organic film:

[0429]

[0430] Transfer conditions to the SiO2 film (processed object):

[0431]

[0432]

[0433] Each pattern cross-section of the developed pattern shape, the shape of the silicon-containing resist intermediate film after transfer etching, the shape of the organic film after transfer etching, and the shape of the processed body after transfer etching was observed with a Hitachi Ltd. (stock) electron microscope (S-4700), and the twist-free limit size (nm) of the pattern after transfer etching of the processed body was measured, respectively, and the results are shown in Table 5.

[0434] [Table 5]

[0435]

[0436] From the results of Examples 4-1 to 4-15, it was found that when UDL-1 to 15 were used as the organic film of the 3-layer resist for immersion lithography, the resist shape after development was good in the pattern shape evaluation, and the compounds of the present application had a useful effect as an antireflection film. Also, the comparative examples gave the same results.

[0437] With respect to the pattern shape after etching, the resist shape after development, the shape of the organic film after oxygen etching, and the shape of the substrate after processing etching were good in both the examples and the comparative examples. However, the twist-free limit size of the pattern after transfer etching of the processed body varied depending on the line width of the resist produced by exposure, and pattern twisting occurred at a line width of about 33 nm in Comparative Example 4-1, but the examples 4-1 to 4-15 using the compounds of the present application did not twist even at a pattern size of 30 nm or less, and it was found that they had high twist resistance. When the compounds having the same substituent structure as the present application, Example 4-1 and Comparative Example 4-2, Example 4-3 and Comparative Example 4-3, and Example 4-4 and Comparative Example 4-4 were compared, it was found that the organic film using the compound of the present application having a smalleyne structure had superior twist resistance.

[0438] Examples 5-1 to 5-15 and Comparative Examples 5-1 to 5-5 (filling properties)

[0439] UDL-1 to 15 were applied to a SiO2step substrate on which a dense hole pattern of 160 nm in diameter had been formed on a SiO2substrate with a thickness of 500 nm under the conditions that the baking at 350°C for 60 seconds was used to form a film thickness of 80 nm on a flat substrate. The substrate on which the organic film had been formed was cut, and a scanning electron microscope (SEM) was used to observe whether the organic film had filled the hole bottom. The results are shown in Table 6.

[0440] [Table 6]

[0441] Composition for organic film formation Landfill property Example 5-1 UDL-1 Until the hole is well filled Example 5-2 UDL-2 Until the hole is well filled Example 5-3 UDL-3 Until the hole is well filled Example 5-4 UDL-4 Until the hole is well filled Example 5-5 UDL-5 Until the hole is well filled Example 5-6 UDL-6 Until the hole is well filled Example 5-7 UDL-7 Until the hole is well filled Example 5-8 UDL-8 Until the hole is well filled Example 5-9 UDL-9 Until the hole is well filled Example 5-10 UDL-10 Until the hole is well filled Example 5-11 UDL-11 Until the hole is well filled Example 5-12 UDL-12 Until the hole is well filled Example 5-13 UDL-13 Until the hole is well filled Example 5-14 UDL-14 Until the hole is well filled Example 5-15 UDL-15 Until the hole is well filled Comparative Example 5-1 Comparative UDL-1 Until the hole is well filled Comparative Example 5-2 Comparative UDL-2 Until the hole is well filled Comparative Example 5-3 Comparative UDL-3 Until the hole is well filled Comparative Example 5-4 Comparative UDL-4 Until the hole is well filled Comparative Example 5-5 Comparative UDL-5 Until the hole is well filled

[0442] As shown in Table 6, Examples 5-1 to 5-15 in which the UDL-1 to UDL-15 of the present application were used to form organic films, all filled up to the bottom of the holes, and it was expected that even if the processed body had unevenness, sufficient filling properties would be obtained, and it was found that the organic film material was useful as a material for multilayer processing. Also, the comparative examples also gave the same results.

[0443] Examples 6-1 to 6-6 (planarization property)

[0444] Each of the organic film-forming compositions (UDL-1, 4, 12 to 15) was applied to a SiO2 wafer substrate having a large isolated trench pattern (trench width 10 μm, trench depth 0.10 μm), and after calcination at 350°C for 60 seconds in air, the difference in height (delta) of the organic film in the trench portion and the non-trench portion was observed using an NX10 atomic force microscope (AFM) manufactured by Park Systems. The results are shown in Table 7. In this evaluation, the smaller the difference in height, the better the planarization properties. Also, in this evaluation, the trench pattern having a depth of 0.10 μm was generally planarized using an organic film-forming composition having a film thickness of about 0.2 μm, and became a strict evaluation condition for evaluating the merits and demerits of the planarization properties. Figure 2

[0445] [Table 7]

[0446] Composition for organic film formation Height difference (nm) Example 6-1 UDL-1 80 Example 6-2 UDL-4 85 Example 6-3 UDL-12 75 Example 6-4 UDL-13 80 Example 6-5 UDL-14 75 Example 6-6 UDL-15 75

[0447] As shown in Table 7, when Examples 6-3 to 6-6 in which a high-boiling organic solvent was added were compared with Examples 6-1 to 6-2 in which a high-boiling organic solvent was not added, the difference in height of Examples 6-3 to 6-6 was the same or decreased, and it was found that the planarity was improved by the addition of the high-boiling organic solvent. It was also confirmed that by adjusting the organic solvent composition of the compound of the present application, the planarity could also be improved.

[0448] Examples 7-1 to 7-15, Comparative Examples 7-1 to 7-5 (heat resistance test)

[0449] Each of the organic film-forming compositions (UDL-1 to 15, comparative UDL-1 to 5) was applied to a Si substrate, and baked at 350°C for 60 seconds in nitrogen, and the film thickness was measured. After baking at 450°C for 60 seconds, the film thickness was again measured. Furthermore, the film thickness reduction rate (%) was measured according to the following formula, and this film thickness reduction rate was defined as a measure of heat resistance.

[0450] ML = {(ml - m2) / ml} x 100

[0451] ​In the formula, ML is the film thickness reduction rate (%), ml is the film thickness after baking at 350°C (nm), and m2 is the film thickness after baking at 450°C (nm).

[0452] The heat resistance is better as the film thickness reduction rate is smaller. That is, the smaller the film thickness reduction rate, the higher the heat resistance. The results are shown in Table 8.

[0453] [Table 8]

[0454]

[0455] As shown in Table 8, the film thickness reduction rate of the organic films formed using the UDL-1 to 15 of the present application in Examples 7-1 to 7-15 was suppressed to 3% or less, and it was found that the heat resistance was excellent. Also, when comparing Example 7-1 with Comparative Example 7-2, Example 7-3 with Comparative Example 7-3, and Example 7-4 with Comparative Example 7-4, which have the same substituent structure, it was found that the heat resistance of the compound having the suisenene structure was more excellent when comparing the etching resistance. Furthermore, when comparing the suisenene compounds with each other, the heat resistance of Example 7-4 was more excellent than that of Comparative Example 7-5, and the effectiveness of the propargyl group introduced in the present application was also confirmed.

[0456] Examples 8-1 to 8-15, Comparative Examples 8-1 to 8-5 (coating property test)

[0457] The composition for forming an organic film (UDL-1 to 15, Comparative UDL-1 to 5) was coated on the Bare-Si substrate, the substrate treated with hexamethyldisilazane (HMDS), and the substrate treated with SiON shown in Table 9, respectively, and baked at 350°C for 60 seconds in the atmosphere to form an organic film having a film thickness of 200 nm. Whether or not the formed organic film had a coating abnormality was observed using an optical microscope (ECLIPSE L200 manufactured by Nikon Corporation). The results are shown in Table 9.

[0458] [Table 9]

[0459]

[0460] As shown in Table 9, the organic films of Examples 8-1 to 8-15 formed using the UDL-1 to UDL-15 of the present application were free from substrate dependency, and a uniform organic film free from a coating abnormality could be formed. Also, pinhole defects occurred in Comparative Examples 8-1 to 8-4 except for the Bare-Si substrate. Comparative Example 8-5 was able to form a film free from substrate dependency, and the improvement effect on the film formation property resulting from the introduction of the suisenene structure was confirmed.

[0461] As described above, the resist organic film material of the present application has high etching resistance and excellent twist resistance during etching, and is extremely useful as an organic film for a multi-layer resist process, particularly a 3-layer resist process, for ultra-fine and high-precision pattern processing.

[0462] Further, the present application is not limited to the above-described embodiments. The above-described embodiments are illustrative, and those having substantially the same configuration and exerting the same effects as the technical ideas recited in the claims of the present application are included in the scope of the technical ideas of the present application.

[0463] Explanation of reference signs

[0464] 1: substrate

[0465] 2: workpiece

[0466] 2a: pattern formed on substrate

[0467] 3: organic film

[0468] 3a: organic film pattern

[0469] 4: silicon-containing resist intermediate film

[0470] 4a: silicon-containing resist intermediate film pattern

[0471] 5: resist upper film

[0472] 5a: resist pattern

[0473] 6: specific portion

Claims

1. A composition for forming an organic film with a photoresist, characterized in that: The resist organic film forming composition contains a compound represented by the following general formula (1) and an organic solvent, In the general formula (1), X is any one of X1 to X3 represented by the following general formulae (2), (3), and (5), and two or more kinds of X can be used in combination. In the general formula (3), W represents a carbon atom or a nitrogen atom, n1 represents 0 or 1, n2 represents an integer of 1 to 3, and R1 is independently any group represented by the following general formula (4). In the general formula (5), R2 is a hydrogen atom or an alkyl group having a carbon number of 1 to 4, and R3 is any group.

2. The composition for resist organic film formation according to claim 1, wherein The compound represented by the general formula (1) has a ratio Mw / Mn of a weight average molecular weight Mw to a number average molecular weight Mn, which is obtained by gel permeation chromatography, of 1.00 ≤ Mw / Mn ≤ 1.

15.

3. The composition for resist organic film formation according to claim 1 or 2, wherein, The organic solvent is a mixture of one or more kinds of organic solvents having a boiling point of less than 180 degrees and one or more kinds of organic solvents having a boiling point of 180 degrees or more.

4. The composition for forming a resist organic film according to claim 1 or 2, wherein The resist organic film forming composition further contains one or more kinds of a surfactant and a plasticizer.

5. A pattern forming method characterized by: forming a resist organic film on a processed object using the resist organic film forming composition according to any one of claims 1 to 4, forming a silicon-containing resist intermediate film on the resist organic film using a silicon-containing resist intermediate film material, forming a resist upper layer film on the silicon-containing resist intermediate film using a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern on the silicon-containing resist intermediate film by etching using the patterned resist upper layer film as a mask, transferring the pattern on the resist organic film by etching using the patterned silicon-containing resist intermediate film as a mask, and forming a pattern on the processed object by etching using the patterned resist organic film as a mask.

6. A pattern forming method characterized by: forming a resist organic film on a processed object using the resist organic film forming composition according to any one of claims 1 to 4, forming a silicon-containing resist intermediate film on the resist organic film using a silicon-containing resist intermediate film material, forming an organic bottom anti-reflective coating (BARC) on the silicon-containing resist intermediate film, forming a resist upper layer film on the BARC using a photoresist composition and becoming a four-layer film structure, forming a circuit pattern on the resist upper layer film, transferring the pattern on the BARC film and the silicon-containing resist intermediate film by etching using the patterned resist upper layer film as a mask, transferring the pattern on the resist organic film by etching using the patterned silicon-containing resist intermediate film as a mask, and forming a pattern on the processed object by etching the processed object using the patterned resist organic film as a mask.

7. A pattern forming method characterized by: A photoresist organic film is formed on a workpiece using a photoresist organic film forming composition according to any one of claims 1 to 4. An inorganic hard mask selected from silicon oxide film, silicon nitride film, and silicon oxynitride film is formed on the photoresist organic film. A photoresist upper layer film is formed on the inorganic hard mask using a photoresist composition. A circuit pattern is formed on the photoresist upper layer film. The patterned photoresist upper layer film is used as a mask to transfer the pattern to the inorganic hard mask by etching. The patterned inorganic hard mask is used as a mask to transfer the pattern to the photoresist organic film by etching. The workpiece is then etched and a pattern is formed on the workpiece using the patterned photoresist organic film as a mask.

8. A method for forming a pattern, characterized by: A photoresist organic film is formed on a workpiece using a photoresist organic film forming composition according to any one of claims 1 to 4. An inorganic hard mask selected from silicon oxide film, silicon nitride film, and silicon oxynitride film is formed on the photoresist organic film. An organic antireflective film (BARC) is formed on the inorganic hard mask. A photoresist upper layer film is formed on the BARC using a photoresist composition, forming a four-layer film structure. A circuit pattern is formed on the photoresist upper layer film. The patterned photoresist upper layer film is used as a mask to transfer the pattern to the BARC film and the inorganic hard mask by etching. The patterned inorganic hard mask is used as a mask to transfer the pattern to the photoresist organic film by etching. The workpiece is then etched and a pattern is formed on the workpiece using the patterned photoresist organic film as a mask.

9. The pattern forming process as claimed in claim 7 or 8, wherein, The inorganic hard mask is formed by CVD or ALD.

10. The pattern forming process according to any one of claims 5 to 8, wherein The circuit pattern is formed using optical lithography with wavelengths above 10 nm and below 300 nm, direct drawing by electron beam, nanomolding, or a combination thereof.

11. The pattern forming process according to any one of claims 5 to 8, wherein The circuit pattern is formed by developing it with alkaline developer or organic solvent.

12. The pattern forming process according to any one of claims 5 to 8, wherein The workpiece is a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, or a metal oxide nitride film.

13. The pattern forming process according to claim 12, wherein The metal is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or alloys thereof.

14. A compound represented by the following general formula (1), In this general formula (1), X is any one of the X2 to X3 represented by the following general formulas (3) and (5), and two or more types of X can also be combined. In this general formula (3), W represents a carbon atom or a nitrogen atom, n1 represents 0 or 1, n2 represents an integer from 1 to 3, and R1 is any group represented by the following general formula (4). In this general formula (5), R2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R3 is any of the following groups:

Images