Compound

Abstract

To provide a composition for forming an organic film that can exhibit high etching resistance and excellent twisting resistance, that has good film formability, and that causes reduced sublimate component to be an out gas; a patterning process using this composition; and a compound suitable for such a composition for forming an organic film.SOLUTION: The present invention provides a composition for forming an organic film, including: a compound represented by the following general formula (1); and an organic solvent. In the general formula (1), X represents a specific linking group.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] In recent years, with the increasing integration and speed of semiconductor elements, there has been a demand for finer pattern rules. In lithography, which uses optical exposure and is currently used as a general-purpose technology, various technological developments have been carried out to enable finer and more accurate pattern processing for the light source used.

[0003] As a light source for lithography used in forming resist patterns, light exposure using mercury lamp g-line (436 nm) or i-line (365 nm) light sources is widely used in areas with low integration. On the other hand, in areas with high integration and requiring finer detail, lithography using shorter wavelength KrF excimer lasers (248 nm) and ArF excimer lasers (193 nm) has also been put to practical use, and for the most advanced generation requiring even finer detail, extreme ultraviolet (EUV, 13.5 nm) lithography is approaching practical use.

[0004] As resist patterns become thinner, the ratio of pattern height to pattern linewidth (aspect ratio) increases in the single-layer resist method, a typical method for forming resist patterns, and it is well known that this causes pattern collapse during development due to the surface tension of the developer. Therefore, multilayer resist methods, in which films with different dry etching properties are stacked to form patterns, are known to be superior for forming high-aspect-ratio patterns on uneven substrates. Two-layer resist methods (e.g., Patent Document 1) have been developed, which combine a photoresist top layer made of a silicon-containing photosensitive polymer with an organic film made of an organic polymer primarily composed of carbon, hydrogen, and oxygen, such as a novolac polymer. Three-layer resist methods (e.g., Patent Document 2) have also been developed, which combine a photoresist top layer made of an organic photosensitive polymer used in the single-layer resist method with a silicon-containing resist middle layer made of a silicon-containing polymer or silicon-based CVD film and an organic film made of an organic polymer.

[0005] In this three-layer resist method, first, a pattern of a photoresist upper layer film is transferred to a silicon-containing resist middle layer using a fluorocarbon dry etching gas, and then the pattern is used as a mask to transfer the pattern to an organic film (organic lower layer film) whose main constituent elements are carbon and hydrogen using an oxygen-containing gas by dry etching, and then the pattern is formed on the workpiece by dry etching using this as a mask. However, in semiconductor device manufacturing processes for the 20 nm generation and beyond, when the pattern of this organic film is used as a hard mask to transfer the pattern to the workpiece by dry etching, the organic film pattern can become twisted or bent.

[0006] The carbon hard mask formed directly on the workpiece is typically an amorphous carbon (CVD-C) film, created by the CVD method using gases such as methane, ethane, and acetylene. This CVD-C film is known to be highly effective at preventing the above-mentioned pattern distortion and warping, as it can minimize the amount of hydrogen atoms in the film. However, if the underlying workpiece has steps, the CVD process makes it difficult to fill these steps flatly. Therefore, if a workpiece with steps is filled with CVD-C film and then patterned with photoresist, the steps on the workpiece will cause steps on the coated surface of the photoresist, resulting in uneven photoresist thickness and resulting degradation of the focus tolerance and pattern shape during lithography.

[0007] On the other hand, when an organic film is formed by spin coating as a carbon hard mask directly on a workpiece, it is known to have the advantage of being able to fill in the unevenness of the substrate. Planarizing the substrate with this organic film material suppresses film thickness variations in the silicon-containing resist intermediate film and photoresist top layer film formed on top of it, expanding the focus tolerance of lithography and enabling the formation of normal patterns.

[0008] Therefore, there is a demand for an organic film material and a method for forming an organic film that can be formed by a spin coating method, which has high etching resistance when dry etching a workpiece and allows the formation of a film with high flatness on the workpiece.

[0009] Conventionally, condensation resins, which use carbonyl compounds such as ketones or aldehydes or aromatic alcohols as condensing agents with phenolic or naphtholic compounds, have been known as organic film-forming materials for multilayer resist processes. Examples include the fluorene bisphenol novolak resin described in Patent Document 2, the bisphenol compound and its novolak resin described in Patent Document 3, the adamantane phenol compound novolak resin described in Patent Document 4, and the bisnaphthol compound and its novolak resin described in Patent Document 5. Resins used in such materials have a main skeleton formed from naphthalene, fluorene, adamantane, or the like, which has a high carbon density. However, because the structural units contain oxygen atoms derived from phenolic hydroxyl groups, deterioration of etching resistance cannot be avoided.

[0010] Furthermore, as a resin for organic film materials that does not contain heteroatoms such as oxygen to avoid deterioration of etching resistance, a resin having a fluorene structure as described in Patent Document 6 is exemplified. However, the resin itself does not contribute to thermosetting, and a cured film is formed by using a composition to which a crosslinking agent such as a methylol compound is added. Therefore, even if the carbon content of the resin is increased, a crosslinking agent with a low carbon content such as a methylol compound must be used, which poses a problem of impairing the inherent etching resistance of the highly carbonized resin.

[0011] An example of an organic film material that does not contain additives such as crosslinking agents that cause deterioration of etching resistance and does not contain heteroatoms such as oxygen to improve etching resistance is the organic film material that uses a monomolecular compound described in Patent Document 7. However, because a monomolecular compound is used, there remain issues with the heat resistance and etching resistance properties of the organic film after curing, such as problems with application to substrates with complex shapes and problems with sublimation caused by small molecules that occur during baking.

[0012] In order to maximize carbon density, various fullerene derivatives have been investigated, as described in Patent Documents 8 and 9. However, fullerene itself is not curable, and film formation is difficult due to issues with solvent solubility. Therefore, when using fullerene, it is necessary to add resins or crosslinking agents, and further to introduce various substituents to improve solvent solubility. However, the decrease in carbon density and the deterioration of heat resistance due to the introduction of substituents are major challenges for application to organic film materials. [Prior art documents] [Patent documents]

[0013] [Patent Document 1] Japanese Patent Application Publication No. 6-118651 [Patent Document 2] Japanese Patent Application Laid-Open No. 2005-128509 [Patent Document 3] Japanese Patent Application Laid-Open No. 2006-293298 [Patent Document 4] Japanese Patent Application Laid-Open No. 2006-285095 [Patent Document 5] Japanese Patent Application Laid-Open No. 2010-122656 [Patent Document 6] International Publication No. 2013 / 047106 Brochure [Patent Document 7] Japanese Patent Application Laid-Open No. 2008-164806 [Patent Document 8] International Publication No. 2008 / 126804 Brochure [Patent Document 9] International Publication No. 2016 / 143436 Brochure Summary of the Invention [Problem to be solved by the invention]

[0014] The present invention has been made to solve the above problems, and aims to provide a composition for forming an organic film that uses a compound that has a high carbon content and is thermosetting, thereby enabling high etching resistance and excellent distortion resistance to be achieved without impairing the carbon content inherent to the resin, and that also has good film-forming properties and contains few sublimates that become outgassed, a pattern formation method using the same, and a compound that is suitable for such a composition for forming an organic film. [Means for solving the problem]

[0015] In order to achieve the above object, the present invention provides: An organic film-forming composition, The present invention provides a composition for forming an organic film, characterized in that the composition for forming an organic film contains a compound represented by the following general formula (1) and an organic solvent. [ka] (In the above general formula (1), X is any one of the groups X1 to X3 represented by the following general formulas (2), (3), and (5), and two or more types of X may be used in combination.) [ka] [ka] (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).) [ka] [ka] (In the above general formula (5), R2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R3 is one of the following groups.) [ka]

[0016] Such a composition for forming an organic film has a high carbon content, and can exhibit high etching resistance and excellent twist resistance without impairing the carbon content inherent in the resin, and can also provide a composition for forming an organic film that has good film-forming properties and contains few sublimates that become outgassed.

[0017] Furthermore, the compound represented by the general formula (1) preferably has a ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn in terms of polystyrene measured by gel permeation chromatography, of 1.00≦Mw / Mn≦1.15.

[0018] Such a composition for forming an organic film can form an organic film having excellent filling properties and flatness.

[0019] The organic solvent is preferably a mixture of one or more organic solvents having a boiling point of less than 180°C and one or more organic solvents having a boiling point of 180°C or higher.

[0020] In the case of such a composition for forming an organic film, the addition of a high-boiling point organic solvent to the compound represented by the general formula (1) provides the organic film with thermal fluidity, and the composition for forming an organic film also has high filling / planarizing properties.

[0021] The organic film-forming composition preferably further contains at least one of a surfactant and a plasticizer.

[0022] Such a composition for forming an organic film has excellent coating properties and filling / flattening properties.

[0023] The present invention also provides The present invention can provide a pattern formation method including forming an organic film on a workpiece using the organic film-forming composition, 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, transferring the pattern to the silicon-containing resist intermediate film by etching using the resist upper layer film on which the pattern has been formed as a mask, transferring the pattern to the organic film by etching using the silicon-containing resist intermediate film on which the pattern has been transferred as a mask, and further forming a pattern on the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0024] By using such a pattern forming method using a three-layer resist process, it is possible to form a fine pattern on a workpiece with high precision.

[0025] The present invention also provides The present invention can provide a pattern formation method, which includes forming an organic film on a workpiece using the organic film-forming composition, forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material, forming an organic antireflective coating (BARC) on the silicon-containing resist intermediate film, forming a resist top layer film on the BARC using a photoresist composition to form a four-layer film structure, forming a circuit pattern on the resist top layer film, using the resist top layer film on which the pattern has been formed as a mask to transfer the pattern to the BARC film and the silicon-containing resist intermediate film by etching, using the silicon-containing resist intermediate film on which the pattern has been transferred as a mask to transfer the pattern to the organic film by etching, and further etching the workpiece using the organic film on which the pattern has been transferred as a mask to form a pattern on the workpiece.

[0026] By using such a pattern formation method using a four-layer resist process, it is possible to form fine patterns on a workpiece with even greater precision.

[0027] The present invention also provides The present invention can provide a pattern formation method, which includes forming an organic film on a workpiece using the organic film-forming composition, forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming a resist upper layer film on the inorganic hard mask using a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the inorganic hard mask by etching using the resist upper layer film on which the pattern has been formed as a mask, transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask, and further etching the workpiece using the organic film on which the pattern has been transferred as a mask, thereby forming a pattern on the workpiece.

[0028] By using such a pattern forming method using a three-layer resist process, it is possible to form a fine pattern on a workpiece with high precision.

[0029] Furthermore, the present invention provides a photoresist composition for forming an organic film on a workpiece; forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film; forming an organic antireflective coating (BARC) on the inorganic hard mask; forming a resist top layer film on the BARC using a photoresist composition to form a four-layer film structure; forming a circuit pattern on the resist top layer film; transferring the pattern to the BARC film and the inorganic hard mask by etching using the resist top layer film on which the pattern has been formed as a mask; transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask; and etching the workpiece using the organic film on which the pattern has been transferred as a mask to form a pattern on the workpiece.

[0030] This pattern formation method using a four-layer resist process allows fine patterns to be formed on the workpiece with higher precision.

[0031] The inorganic hard mask is preferably formed by a CVD method or an ALD method.

[0032] When the inorganic hard mask is formed by the CVD method or the ALD method, a fine pattern can be formed on the workpiece with higher precision.

[0033] The circuit pattern is preferably formed by photolithography with a wavelength of 10 nm or more and 300 nm or less, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[0034] By using such a circuit pattern forming method, it is possible to form a fine pattern on a workpiece with higher precision.

[0035] In forming the circuit pattern, it is preferable to develop the circuit pattern using an alkali developer or an organic solvent.

[0036] By using such a pattern forming method, it is possible to form a fine pattern on a workpiece with higher precision.

[0037] In forming the circuit pattern, the workpiece is preferably a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal carbide oxide film, or a metal oxynitride film.

[0038] If such a workpiece is used, a better pattern can be formed.

[0039] In addition, in forming the circuit pattern, 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.

[0040] If such a metal is used for the workpiece, a better pattern can be formed.

[0041] The present invention also provides a compound represented by the following general formula (1): [ka] (In the above general formula (1), X is any one of the groups X1 to X3 represented by the following general formulas (2), (3), and (5), and two or more types of X may be used in combination.) [ka] [ka] (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).) [ka] [ka] (In the above general formula (5), R2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R3 is one of the following groups.) [ka]

[0042] Such a compound has a high carbon content, and can exhibit high etching resistance and excellent twist resistance without impairing the carbon content inherent in the resin, and can provide a compound suitable for an organic film-forming composition that has good film-forming properties and contains few sublimates that become outgassed. [Effects of the Invention]

[0043] In general, sumanene derivatives correspond to the cap structure of fullerenes or carbon nanotubes, and the curved structure of the sumanene structure allows sumanene molecules to easily overlap with each other to form two-dimensional molecular aggregates. An organic film-forming composition containing the sumanene derivative represented by the general formula (1) can form a high-density, strong carbon film by virtue of this tendency to easily form molecular aggregates and the solubility in organic solvents and thermosetting properties imparted by the substituent represented by X. Therefore, when an organic film formed using the organic film-forming composition of the present invention is used as an organic film for a resist, it has excellent dry etching resistance and warping resistance.

[0044] The sumanene derivatives of the present invention are thermosetting and comprise a fused aromatic ring structure with a high carbon content, which corresponds to the partial structure of fullerene, and therefore serve as a component for providing an organic film-forming composition that can form an organic film having both high distortion resistance and dry etching resistance. Furthermore, these sumanene derivatives are not limited to applications as compounds for resist organic film materials, and are expected to be used in next-generation materials such as molecular semiconductors based on their tendency to easily form molecular aggregates.

[0045] As described above, the compound of the present invention is a high-density carbon compound having a sumanene structure as its main skeleton, making it a useful compound for forming organic films with excellent etching resistance and distortion resistance. Furthermore, the organic film-forming composition of the present invention containing this compound is a useful material for forming organic films that combine not only excellent etching resistance and distortion resistance but also various properties such as heat resistance and embedding / planarization characteristics. Therefore, it is extremely useful as a resist organic film material in multilayer resist processes such as a two-layer resist process, a three-layer resist process using a silicon-containing resist interlayer, or a four-layer resist process using a silicon-containing resist interlayer and an organic antireflective coating (BARC). Furthermore, the pattern formation method of the present invention enables highly accurate formation of fine patterns on a substrate to be processed in a multilayer resist process. [Brief explanation of the drawings]

[0046] [Figure 1] 1A to 1C are process diagrams illustrating an example of a pattern forming method of the present invention. [Figure 2] 1 is a cross-sectional view showing an example of an organic film formed by applying the organic film-forming composition of the present invention onto an SiO2 wafer substrate having a trench pattern. DETAILED DESCRIPTION OF THE INVENTION

[0047] As described above, there has been a demand for the development of an organic film-forming composition that has high etching resistance and excellent distortion resistance, and further has excellent substrate filling properties and planarization properties, a pattern formation method using the same, and a compound that is suitable for such an organic film-forming composition.

[0048] As a result of extensive research into the above-mentioned problems, the present inventors have found that thermosetting properties and solubility in organic solvents can be imparted to sumanene by introducing a specific partial structure. Furthermore, they have found that an organic film-forming composition containing the compound and an organic solvent can form an organic film that has excellent etching resistance and twist resistance, as well as various properties such as heat resistance, filling / planarization properties, film-forming properties, and a small amount of sublimate components, and have completed the present invention.

[0049] That is, the present invention provides: An organic film-forming composition, The composition for forming an organic film is characterized by containing a compound represented by the following general formula (1) and an organic solvent. [ka] (In the above general formula (1), X is any one of the groups X1 to X3 represented by the following general formulas (2), (3), and (5), and two or more types of X may be used in combination.) [ka] [ka] (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).) [ka] [ka] (In the above general formula (5), R2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R3 is one of the following groups.) [ka]

[0050] The present invention will be described in detail below, but the present invention is not limited thereto.

[0051] [Compound] The organic film-forming composition of the present invention contains a compound represented by the following general formula (1). [ka] (In the above general formula (1), X is any one of the groups X1 to X3 represented by the following general formulas (2), (3), and (5), and two or more types of X may be used in combination.) [ka] [ka] (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).) [ka] [ka] (In the above general formula (5), R2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R3 is one of the following groups.) [ka]

[0052] When the partial structure represented by X in the general formula (1) is X1, it is a structure represented by the following formula (2), which is preferable from the viewpoint of imparting curability, solvent solubility, and etching resistance.

[0053] [ka]

[0054] Among the partial structures represented by X in the general formula (1), X2 is represented by the general formula (3) above, and specific examples thereof include the following. The aromatic ring constituting these may have a substituent, and examples thereof include a hydroxyl group, a methyl group, a methoxy group, a nitro group, a halogen group, and a trifluoromethyl group. Among the following X2, from the viewpoint of etching resistance, those satisfying n1=1 and having an ethynyl group or an ethynylphenyl group as the substituent represented by R1 are preferred. [ka]

[0055] [ka]

[0056] Of the partial structures represented by X in general formula (1), X3 is represented by general formula (5) above, and specific examples include the following. When an aromatic ring is contained with these as components, the aromatic ring may have a substituent, and examples include a hydroxyl group, a methyl group, a methoxy group, a nitro group, a halogen group, and a trifluoromethyl group. Of the following X3, R2 is preferably a hydrogen atom from the viewpoint of thermosetting properties, and R3 is preferably naphthalene or diphenylacetylene from the viewpoints of etching resistance and thermosetting properties. [ka]

[0057] [ka]

[0058] [ka]

[0059] [ka]

[0060] Among the partial structures represented by X in the general formula (1), the compound of X3 not only exhibits thermosetting properties due to the action of the substituent R3, but also undergoes a condensation reaction accompanied by dehydration or dealcoholization between molecules due to the action of heat or acid, as shown below, and can form a dense film. [ka]

[0061] In addition, the compound represented by general formula (1) preferably has a ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn in terms of polystyrene, as measured by gel permeation chromatography, of 1.00≦Mw / Mn≦1.15. By definition, a monomolecular compound has an Mw / Mn of 1.00, but due to the separation characteristics of gel permeation chromatography, the measured value may exceed 1.00. Generally, it is extremely difficult to achieve an Mw / Mn ratio approaching 1.00 for polymers having repeating units unless a special polymerization method is used; the Mw distribution results in an Mw / Mn value exceeding 1. In the present invention, in order to distinguish between monomolecular compounds and polymers, the ratio 1.00≦Mw / Mn≦1.15 is defined as an index of monomolecularity.

[0062] By controlling the Mw / Mn of the compound for the organic film-forming composition within such a range, the organic film-forming composition can form an organic film that has excellent filling properties and planarization properties.

[0063] The compound for the organic film-forming composition represented by general formula (1) is preferably added in an amount of 1 to 20 parts by mass, more preferably 5 to 15 parts by mass, per 100 parts by mass of the organic film-forming composition.

[0064] [Method of manufacturing the compound] The compound of the present invention represented by the general formula (1) can be synthesized using sumanene or an oxide of sumanene as a raw material. The production methods are shown below for the cases where X is X1, X2, and X3.

[0065] When X is X1, for example, a substitution reaction of sumanene with a halide, tosylate or mesylate of a propargyl group using a base catalyst can be exemplified, as shown below: X4 in the following formula is a halogen, a tosyl group or a mesyl group. [ka]

[0066] Examples of the base catalyst used in the substitution reaction include inorganic base compounds such as sodium hydrogen carbonate, sodium carbonate, potassium carbonate, calcium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, and potassium phosphate, and organic amine compounds such as triethylamine, pyridine, and N-methylmorpholine, which may be used alone or in combination of two or more. The amount of these catalysts used is in the range of 0.1 to 20 moles, preferably 0.2 to 10 moles, relative to the number of moles of the raw material sumanene.

[0067] The solvent used in this reaction is not particularly limited as long as it is inert to the reaction, and examples thereof include ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; aromatic solvents such as benzene, toluene, and xylene; acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, and water, which can be used alone or in combination. These solvents can be used in an amount of 0 to 2000 parts by mass per 100 parts by mass of the reaction raw materials, and the reaction temperature is preferably from -50°C to the boiling point of the solvent, more preferably from room temperature to 150°C. The reaction time is appropriately selected from the range of 0.1 to 100 hours.

[0068] Reaction methods include charging sumanene, a halide, tosylate, or mesylate of a propargyl group, and an acid catalyst all at once; dispersing or dissolving sumanene, a halide, tosylate, or mesylate, and then adding the catalyst all at once or in portions, or diluting with a solvent and adding dropwise; dispersing or dissolving the catalyst, and then adding sumanene, a halide, tosylate, or mesylate all at once or in portions, or diluting with a solvent and adding dropwise. In this case, depending on the reactivity of the aromatic compounds, it is preferable to use 2 moles or more of a halide, tosylate, or mesylate of a propargyl group per mole of sumanene. After the reaction is complete, the catalyst used in the reaction is removed by diluting with an organic solvent, followed by separation and washing to recover the target product.

[0069] Furthermore, during the reaction, in addition to the above propargyl-type halides, tosylates, and mesylates, alkyl-type halides, tosylates, and mesylates, or allyl-type halides, tosylates, and mesylates, etc., can be used in combination. Furthermore, by controlling the reaction rate of the substitution reaction, it is possible to control the introduction rate of the propargyl group. By combining multiple substituents and controlling the introduction rate, it is possible to control the film-forming properties and adhesion to the substrate.

[0070] The organic solvent used in the separation washing is not particularly limited as long as it can dissolve the target substance and separate into two layers when mixed with water. Examples include hydrocarbons such as hexane, heptane, benzene, toluene, and xylene; esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate; ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, and methyl isobutyl ketone; ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, and ethyl cyclopentyl methyl ether; chlorinated solvents such as methylene chloride, chloroform, dichloroethane, and trichloroethylene; and mixtures thereof. The washing water used in this process is typically what is known as deionized water or ultrapure water. While one or more washings are sufficient, washing more than 10 times does not necessarily provide the desired effect, so washing is preferably performed 1 to 5 times.

[0071] In order to remove acidic components from the system during separation washing, washing may be performed with a basic aqueous solution. Specific examples of the base include alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates, ammonia, and organic ammonium.

[0072] Furthermore, in order to remove metal impurities or basic components from the system during separation washing, washing with an acidic aqueous solution may be performed. Specific examples of the acid include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropolyacids, and organic acids such as oxalic acid, fumaric acid, maleic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid.

[0073] The separation washing with the basic aqueous solution and the acidic aqueous solution may be carried out either alone or in combination. From the viewpoint of removing metal impurities, the separation washing is preferably carried out in the order of the basic aqueous solution and the acidic aqueous solution.

[0074] After the separation washing with the basic aqueous solution or acidic aqueous solution, washing with neutral water may be carried out subsequently. The number of washings may be one or more times, but is preferably about 1 to 5 times. As the neutral water, the above-mentioned deionized water or ultrapure water may be used. The number of washings may be one or more times, but if the number of washings is too few, the basic components and acidic components may not be removed. Washing 10 or more times does not necessarily provide the effect of washing alone, so it is preferably about 1 to 5 times.

[0075] Furthermore, the reaction product after the separation operation can be recovered as a powder by concentrating the solvent to dryness or crystallizing it under reduced pressure or normal pressure, but it can also be left in a solution state with a moderate concentration to improve operability when preparing an organic film-forming composition. The concentration in this case is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass. At such a concentration, the viscosity is unlikely to increase, preventing a loss of operability, and the amount of solvent is not excessive, making it economical.

[0076] The solvent used in this case is not particularly limited as long as it can dissolve the compound, and specific examples include ketones such as cyclohexanone and methyl 2-amyl ketone; 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 can be used alone or in combination of two or more.

[0077] When X is X2, the production 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 a condensation reaction between sumanene and aromatic aldehydes (reaction method 1). When W is a nitrogen atom, it can be obtained by a condensation reaction between sumanene oxide and aromatic amines (reaction method 2). n1, n2, and R1 in the following formula are the same as above.

[0078] Reaction method 1: When W is a carbon atom [ka]

[0079] Reaction Method 2: When W is a nitrogen atom [ka]

[0080] Examples of the base catalyst used in the condensation reaction of sumanene with aromatic aldehydes shown in Reaction Method 1 include inorganic base compounds such as sodium hydrogen carbonate, sodium carbonate, potassium carbonate, calcium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, and potassium phosphate, and organic amine compounds such as triethylamine, pyridine, and N-methylmorpholine, and these may be used alone or in combination of two or more. The amount of these catalysts used is in the range of 0.1 to 20 moles, preferably 0.2 to 10 moles, relative to the number of moles of sumanene as a raw material.

[0081] The solvent used in Reaction Method 1 is not particularly limited as long as it is inert to the above reaction, but examples include ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; aromatic solvents such as benzene, toluene, and xylene; acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, and water, which can be used alone or in combination. These solvents can be used in an amount of 0 to 2000 parts by mass per 100 parts by mass of the reaction raw materials, and the reaction temperature is preferably from -50°C to the boiling point of the solvent, more preferably from room temperature to 150°C. The reaction time is appropriately selected from the range of 0.1 to 100 hours.

[0082] The reaction method and recovery method of Reaction Method 1 can be the same as those described above for X1.

[0083] Aromatic aldehydes having a substituent other than R1 can be used alone or in combination to suit the required performance when preparing the compound used in the organic film material obtained by Reaction Method 1. For example, aromatic aldehydes having a substituent that contributes to improving planarization characteristics and film-forming properties, or a substituent that contributes to etching resistance and heat resistance, can be combined in any ratio.

[0084] Examples of acid catalysts that can be used in the condensation reaction of sumanene oxide with aromatic amines shown in Reaction Method 2 include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropolyacids; organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid; and Lewis acids such as aluminum trichloride, aluminum ethoxide, aluminum isopropoxide, boron trifluoride, boron trichloride, boron tribromide, tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dibutyltin dimethoxide, dibutyltin oxide, titanium tetrachloride, titanium tetrabromide, titanium(IV) methoxide, titanium(IV) ethoxide, titanium(IV) isopropoxide, and titanium(IV) oxide. The amount of catalyst used is 0.1 to 20 moles, preferably 0.2 to 10 moles, relative to the number of moles of the intermediate bis(indole-2,3-diones).

[0085] The solvent used in reaction method 2 is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; ethers such as diethyl ether, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and 1,4-dioxane; chlorinated solvents such as methylene chloride, chloroform, dichloroethane, and trichloroethylene; hydrocarbons such as hexane, heptane, benzene, toluene, xylene, and cumene; nitriles such as acetonitrile; ketones such as acetone, ethyl methyl ketone, and isobutyl methyl ketone; esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate; and aprotic polar solvents such as dimethyl sulfoxide, N,N-dimethylformamide, and hexamethylphosphoric triamide. These 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 per 100 parts by mass of the reaction raw materials, and the reaction temperature is preferably from −50° C. to the boiling point of the solvent, more preferably from room temperature to 150° C. The reaction time is appropriately selected from the range of 0.1 to 100 hours.

[0086] The reaction method and recovery method of Reaction Method 2 can be the same as those described above for X1.

[0087] Aromatic amines having a substituent other than R1 can be used alone or in combination depending on the required performance in preparing the compound used in the organic film-forming composition obtained by reaction method 2. For example, aromatic amines having a substituent that contributes to improving planarization properties and film-forming properties, and a substituent that contributes to etching resistance and heat resistance can be combined in any ratio.

[0088] When X is X3, the production method differs depending on whether R2 is a hydrogen atom or an alkyl group. When R2 is a hydrogen atom, it can be obtained by reacting sumanene oxide with an organometallic reagent represented by R3-M (Step 1). When R2 is an alkyl group, it can be obtained by condensing the sumanene derivative obtained in Step 1 as an intermediate with an alcohol represented by R2-OH, or by condensing alcohol-alcohol sumanene oxide with aromatic amines (Step 2). In the formula below, R2 and R3 are the same as above, M is Li or MgX5, and X5 is a halogen atom.

[0089] [ka]

[0090] Examples of organometallic reagents used in Step 1 include Grignard reagents, organolithium reagents, organozinc reagents, and organotitanium reagents, with Grignard reagents and organolithium reagents being particularly preferred. Grignard reagents and organolithium reagents may be prepared by direct metallation of the corresponding halide with metallic magnesium or metallic lithium, or by a metal-halogen exchange reaction with an aliphatic organometallic compound such as isopropylmagnesium halide, methyllithium, or butyllithium.

[0091] Organozinc and organotitanium reagents can be prepared from the corresponding Grignard or organolithium reagents by reaction with zinc halide, titanium(IV) halide, or alkoxytitanium(IV). A metal salt compound may be present during the preparation of the organometallic reagent or during the reaction of the organometallic reagent with sumanene oxide. The reaction proceeds in the presence of a transition metal catalyst such as palladium or nickel.

[0092] Examples of the metal salt compound include cyanides, halides, and perhalogenates. Preferred examples of the metal salt compound include 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.

[0093] The metal salt compound can be added in an amount of 0.01 to 5.0 equivalents, preferably 0.2 to 2.0 equivalents, to the organometallic reagent to increase the solubility of the organometallic reagent, making its preparation easier, and also to adjust the nucleophilicity and Lewis acidity of the reagent.

[0094] As the solvent used in the preparation of the organometallic reagent and the reaction with sumanene 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.

[0095] The reaction temperature depends on the types and reaction conditions of the sumenene oxide and organometallic reagent, but is preferably -70 to 150°C. For example, when the organometallic reagent is an organozinc reagent or a Grignard reagent, the reaction temperature can be selected from various temperatures depending on the reaction, such as room temperature to reflux at the boiling point of the solvent. The reaction time is usually preferably 30 minutes to 48 hours.

[0096] The reaction method in Step 1 and the recovery method after quenching the reaction with the organometallic reagent with water or the like can be the same as those described above for X1.

[0097] The acid catalyst and solvent used in the condensation reaction with the alcohol represented by R2-OH in Step 2 can be the same as those used in the condensation reaction of sumanene oxide with aromatic amines in (Reaction Method 2). In addition, the reaction method and recovery method can be the same as those described above for X1.

[0098] As described above, the compound of the present invention represented by the general formula (1) provides a composition for forming an organic film that can exhibit high etching resistance and excellent twist resistance.

[0099] <Composition for organic film formation> The present invention also provides a composition for forming an organic film, which contains a compound represented by the general formula (1) and an organic solvent. In the composition for forming an organic film of the present invention, the compound represented by the general formula (1) of the present invention can be used alone or in combination.

[0100] The organic film-forming composition of the present invention can also be blended with a modifier such as a blending compound or another polymer. The modifier is mixed with the organic film-forming composition of the present invention to improve the film-forming properties of spin coating and the filling properties on substrates having steps.

[0101] Such modifiers include 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, pyrogallol, 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, dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene, methyl 3-hydroxynaphthalene-2-carboxylate, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, and biphenyl Examples of suitable resins include novolak resins such as bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborn-2-ene, α-pinene, β-pinene, and limonene, polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthylene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricyclene, poly(meth)acrylate, and copolymers thereof.

[0102] Also usable are blends of naphthol dicyclopentadiene copolymers described in JP 2004-205685 A, fluorene bisphenol novolac resins described in JP 2005-128509 A, acenaphthylene copolymers described in JP 2005-250434 A, fullerenes having phenol groups described in JP 2006-227391 A, bisphenol compounds and novolac resins thereof described in JP 2006-293298 A, novolac resins of adamantanephenol compounds described in JP 2006-285095 A, bisnaphthol compounds and novolac resins thereof described in JP 2010-122656 A, and fullerene resin compounds described in JP 2008-158002 A.

[0103] The amount of the modifier to be added 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 invention.

[0104] [Organic solvents] The organic solvent that can be used in the organic film-forming composition of the present invention is not particularly limited as long as it dissolves the compound represented by the general formula (1), the acid generator, the crosslinking agent, other additives, etc. Specifically, solvents having a boiling point of less than 180°C, such as those described in paragraphs (0091) and (0092) of JP-A No. 2007-199653, can be used.

[0105] Among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether, 2-heptanone, cyclopentanone, cyclohexanone (CyHO), and mixtures of two or more of these are preferably used.

[0106] A composition containing the organic solvent as described above can be applied by spin coating, and since it contains the compound of the present invention represented by the general formula (1) as described above, it becomes a composition for forming an organic film that has good dry etching resistance, heat resistance, and high-level filling / planarization properties.

[0107] Furthermore, in the organic film-forming composition of the present invention, it is also possible to add a high-boiling organic solvent having a boiling point of 180°C or higher to an organic solvent having a boiling point of less than 180°C as the organic solvent (a mixture of an organic solvent having a boiling point of less than 180°C and an organic solvent having a boiling point of 180°C or higher).

[0108] The high-boiling organic solvent is not particularly limited as long as it can dissolve the compound represented by the general formula (1), and may be any of hydrocarbons, alcohols, ketones, esters, ethers, chlorinated solvents, etc., but specific examples include 1,6-diacetoxyhexane, 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecyl, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 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, glycerin, 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 mono-n-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-n-butyl ether, triethylene glycol butyl methyl ether, triethylene ethylene glycol diacetate, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-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-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,Examples of the diester include 6-hexanediol diacetate, triethylene glycol diacetate, γ-butyrolactone, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, and dibutyl adipate, and these may be used alone or in combination.

[0109] The boiling point of the high-boiling organic solvent may be appropriately selected according to the temperature at which the organic film-forming composition is heat-treated. The boiling point of the high-boiling organic solvent to be added is preferably 180°C to 300°C, and more preferably 200°C to 300°C. If the boiling point is 180°C or higher, there is no risk of the high-boiling point solvent volatilizing too quickly during baking (heat treatment) due to a boiling point that is too low, and sufficient thermal fluidity can be obtained. Furthermore, if the boiling point is 300°C or lower, the boiling point is not too high and the high-boiling point solvent does not remain in the organic film without volatilizing after baking, and there is no risk of adversely affecting the physical properties of the organic film, such as etching resistance.

[0110] Furthermore, when the high-boiling organic solvent is used, the blending amount of the high-boiling organic solvent is preferably 1 to 30 parts by mass per 100 parts by mass of the solvent having a boiling point of less than 180° C. If the blending amount is within this range, there is no risk that sufficient thermal fluidity cannot be imparted during baking, or that the high-boiling organic solvent will remain in the organic film, leading to deterioration of film properties such as etching resistance.

[0111] In the case of such a composition for forming an organic film, the addition of a high-boiling point organic solvent to the compound represented by the general formula (1) gives it thermal fluidity, and the composition for forming an organic film has both high filling and planarizing properties.

[0112] The total amount of the organic solvent in the organic film-forming composition is preferably 70 to 95 mass %, more preferably 80 to 90 mass %.

[0113] [Other additives] In the organic film-forming composition of the present invention, an acid generator can be added to further accelerate the curing reaction. Acid generators include those that generate acid by thermal decomposition and those that generate acid by light irradiation, and either can be added. Specifically, materials described in paragraphs (0061) to (0085) of JP-A-2007-199653 can be added, but are not limited to these.

[0114] The acid generators can be used alone or in combination of two or more. When an acid generator is added, the amount added is preferably 0.05 to 50 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the compound represented by general formula (1).

[0115] A surfactant may be added to the organic film-forming composition of the present invention to improve the coating properties in spin coating. Examples of the surfactant include those described in (0142) to (0147) of JP-A-2009-269953.

[0116] When a surfactant is added, the amount added is preferably 0.001 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, relative to 100 parts by mass of the compound represented by the general formula (1).

[0117] A crosslinking agent may also be added to the organic film-forming composition of the present invention to enhance curability and further suppress intermixing with the overlying film. The crosslinking agent is not particularly limited, and a wide variety of known crosslinking agents can be used. Examples include melamine-based crosslinking agents, glycoluril-based crosslinking agents, benzoguanamine-based crosslinking agents, urea-based crosslinking agents, β-hydroxyalkylamide-based crosslinking agents, isocyanurate-based crosslinking agents, aziridine-based crosslinking agents, oxazoline-based crosslinking agents, and epoxy-based crosslinking agents.

[0118] When a crosslinking agent is added, the amount added is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, per 100 parts by mass of the compound represented by the general formula (1).

[0119] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylated melamine, hexabutoxymethylated melamine, alkoxy- and / or hydroxy-substituted products thereof, and partial self-condensates thereof.

[0120] Specific examples of glycoluril crosslinking agents include tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, alkoxy and / or hydroxy substituted products thereof, and partial self-condensates thereof.

[0121] Specific examples of benzoguanamine-based crosslinking agents include tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, alkoxy- and / or hydroxy-substituted products thereof, and partial self-condensates thereof.

[0122] Specific examples of urea-based crosslinking agents include dimethoxymethylated dimethoxyethylene urea, its alkoxy and / or hydroxy substituted derivatives, and partial self-condensates thereof.

[0123] A specific example of the β-hydroxyalkylamide crosslinking agent is N,N,N',N'-tetra(2-hydroxyethyl)adipamide.

[0124] Specific examples of the isocyanurate crosslinking agent include triglycidyl isocyanurate and triallyl isocyanurate.

[0125] Specific examples of the aziridine crosslinking agent include 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate].

[0126] Specific examples of the oxazoline-based crosslinking agent include 2,2'-isopropylidenebis(4-benzyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), 2,2'-methylenebis4,5-diphenyl-2-oxazoline, 2,2'-methylenebis-4-phenyl-2-oxazoline, 2,2'-methylenebis-4-tertbutyl-2-oxazoline, 2,2'-bis(2-oxazoline), 1,3-phenylenebis(2-oxazoline), 1,4-phenylenebis(2-oxazoline), and 2-isopropenyloxazoline copolymer.

[0127] Specific examples of epoxy-based crosslinking agents include diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, poly(glycidyl methacrylate), trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, and pentaerythritol tetraglycidyl ether.

[0128] A plasticizer can be added to the organic film-forming composition of the present invention to further improve the planarization / filling properties. The plasticizer is not particularly limited, and various known plasticizers can be widely used. Examples include low-molecular-weight compounds such as phthalates, adipates, phosphates, trimellitates, and citrates, as well as polymers such as polyethers, polyesters, and polyacetal polymers described in JP-A-2013-253227.

[0129] When a plasticizer is added, the amount added is preferably 5 to 500 parts by mass, more preferably 10 to 200 parts by mass, per 100 parts by mass of the compound represented by the general formula (1).

[0130] Furthermore, in the organic film-forming composition of the present invention, additives for imparting filling / planarizing properties in the same manner as plasticizers are preferably used, such as liquid additives having a polyethylene glycol or polypropylene glycol structure, or thermally decomposable polymers having a weight loss rate of 40% by mass or more between 30° C. and 250° C. and a weight-average molecular weight of 300 to 200,000. These thermally decomposable polymers preferably contain repeating units having an acetal structure represented by the following general formulas (DP1) and (DP2).

[0131] [ka] (In the formula, R4 is a hydrogen atom or an optionally substituted saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms. Y is a saturated or unsaturated divalent organic group having 2 to 30 carbon atoms.) [ka] (In the formula, R5 is an alkyl group having 1 to 4 carbon atoms. Z is a saturated or unsaturated divalent hydrocarbon group having 4 to 10 carbon atoms, which may have an ether bond. n represents the average number of repeating units and is 3 to 500.)

[0132] The organic film-forming composition of the present invention can be used alone or in combination of two or more. The organic film-forming composition can be used as a resist organic film material or a planarizing material for manufacturing semiconductor devices.

[0133] Furthermore, the organic film-forming composition of the present invention is extremely useful as an organic film material for multilayer resist processes, such as a two-layer resist process, a three-layer resist process using a silicon-containing resist interlayer, a four-layer resist process using a silicon-containing resist interlayer, a silicon-containing inorganic hard mask, and an organic antireflective coating (BARC).

[0134] <Organic film formation method> In the present invention, the organic film-forming composition can be used to form an organic film that functions as an organic underlayer film for a multilayer resist film used in lithography or a planarizing film for semiconductor manufacturing.

[0135] In the present invention, the organic film-forming composition is coated onto a substrate to be processed by spin coating or the like. By using spin coating or the like, excellent embedding properties can be obtained. After spin coating, the solvent is evaporated, and baking (heat treatment) is performed to promote the crosslinking reaction and prevent mixing with the resist top layer or silicon-containing resist intermediate layer. Baking is preferably performed at 100°C or higher and 600°C or lower for 10 to 600 seconds, more preferably 200°C or higher and 500°C or lower for 10 to 300 seconds. Considering the effects on device damage and wafer deformation, the upper limit of the heating temperature in lithography wafer processing is preferably 600°C or lower, more preferably 500°C or lower.

[0136] In addition, in the present invention, an organic film can also be formed by coating the organic film-forming composition of the present invention onto a workpiece by a spin coating method or the like as described above, and then baking and curing the organic film-forming composition in an atmosphere with an oxygen concentration of 0.1% or more and 21% or less.

[0137] By baking the organic film-forming composition of the present invention in such an oxygen atmosphere, a sufficiently cured organic film can be obtained. Although air can be used as the atmosphere during baking, it is preferable to seal in an inert gas such as N2, Ar, or He to reduce oxygen and prevent oxidation of the organic film. To prevent oxidation, the oxygen concentration must be controlled, preferably to 1000 ppm or less, more preferably to 100 ppm or less. Preventing oxidation of the organic film during baking is preferable because it prevents increased absorption and reduced etching resistance.

[0138] The organic film-forming composition of the present invention has excellent filling / planarizing properties, making it possible to obtain a flat organic film regardless of the unevenness of the substrate to be processed, and is therefore extremely useful when forming a flat organic film on a workpiece having structures or steps with a height of 30 nm or more.

[0139] The thickness of the organic underlayer film or the organic film such as the planarizing film for semiconductor device production may be appropriately selected, but is preferably 30 to 20,000 nm, and more preferably 50 to 15,000 nm.

[0140] (Pattern formation method) The present invention provides a pattern formation method by a three-layer resist process using such an organic film-forming composition, which is a method for forming a pattern on a workpiece, comprising at least the steps of: forming an organic film on the workpiece using the organic film-forming composition of the present invention; 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; transferring the pattern by etching to the silicon-containing resist intermediate film using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern by etching to the organic film using the silicon-containing resist intermediate film on which the pattern has been transferred as a mask; and forming a pattern on the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0141] The silicon-containing resist intermediate film in the three-layer resist process exhibits resistance to etching by oxygen gas or hydrogen gas. 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 composed of oxygen gas or hydrogen gas.

[0142] Polysiloxane-based interlayers are also preferred as the silicon-containing resist interlayer in the three-layer resist process. By providing the silicon-containing resist interlayer with anti-reflection properties, reflection can be reduced. For 193 nm exposure, in particular, using an organic film containing many aromatic groups and exhibiting high etching selectivity with respect to the substrate increases the k value and substrate reflection. However, by providing the silicon-containing resist interlayer with an absorption that results in an appropriate k value, reflection can be reduced, reducing substrate reflection to 0.5% or less. For silicon-containing resist interlayers with anti-reflection properties, anthracene is preferred for 248 nm and 157 nm exposure, while for 193 nm exposure, polysiloxanes with pendant light-absorbing groups having phenyl groups or silicon-silicon bonds and crosslinked by acid or heat are preferred.

[0143] An organic antireflective coating (BARC) may be formed on the silicon-containing resist interlayer. In this case, a pattern can be formed on the workpiece by the following steps: forming an organic film on the workpiece using the organic film-forming composition of the present invention; forming a silicon-containing resist interlayer on the organic film using a silicon-containing resist interlayer material; forming a BARC on the silicon-containing resist interlayer; forming a resist top layer on the BARC using a photoresist composition; forming a circuit pattern on the resist top layer; using the resist top layer on which the circuit pattern has been formed as a mask to sequentially etch the BARC and the silicon-containing resist interlayer; transferring the pattern to the organic film by etching using the silicon-containing resist interlayer to which the pattern has been transferred as a mask; and etching the workpiece to form a pattern on the workpiece using the organic film to which the pattern has been transferred as a mask.

[0144] Alternatively, an inorganic hard mask may be formed as the resist intermediate film. In this case, a pattern can be formed on the workpiece by the following steps: forming an organic film on a workpiece substrate using the organic film-forming composition of the present invention; forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film; forming a resist upper layer film on the inorganic hard mask using a photoresist composition; forming a circuit pattern on the resist upper layer film; etching the inorganic hard mask using the resist upper layer film on which the circuit pattern has been formed as a mask to transfer the pattern; etching the organic film on which the pattern has been formed as a mask to transfer the pattern; and etching the workpiece using the organic film on which the pattern has been formed as a mask to form a pattern on the workpiece.

[0145] As described above, when forming an inorganic hard mask on an organic film, a silicon oxide film, a silicon nitride film, or a silicon oxynitride film (SiON film) can be formed by a CVD method, an ALD method, or the like. For example, methods for forming a silicon nitride film are described in JP 2002-334869 A and WO 2004 / 066377 A. The thickness of the inorganic hard mask is preferably 5 to 200 nm, more preferably 10 to 100 nm. Furthermore, a SiON film, which is highly effective as an anti-reflective coating, is most preferably used as the inorganic hard mask. Since the substrate temperature during SiON film formation is 300 to 500°C, the underlying organic film must be able to withstand temperatures of 300 to 500°C. The organic film-forming composition used in the present invention has high heat resistance and can withstand high temperatures of 300 to 500°C, making it possible to combine an inorganic hard mask formed by a CVD method or an ALD method with an organic film formed by a spin-coating method.

[0146] The present invention is also suitable as a four-layer resist process using an organic antireflective coating (BARC). In this case, a pattern can be formed on a workpiece by the following steps: forming an organic film on the workpiece using the organic film-forming composition of the present invention; forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film; forming a BARC on the inorganic hard mask; forming a resist upper layer film on the BARC using a photoresist composition; forming a circuit pattern on the resist upper layer film; sequentially etching the BARC and the inorganic hard mask using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern to the BARC and the inorganic hard mask by etching using the inorganic hard mask on which the pattern has been transferred as a mask; and etching the workpiece using the organic film on which the pattern has been transferred as a mask to form a pattern on the workpiece.

[0147] As mentioned above, a photoresist film can be formed on an inorganic hard mask as a resist top layer, or a BARC can be formed on the inorganic hard mask by spin coating and then a photoresist film can be formed on top of that. In particular, when a SiON film is used as the inorganic hard mask, the two-layer anti-reflection coating of the SiON film and the BARC can suppress reflection even in immersion lithography with a high NA exceeding 1.0. Another advantage of forming a BARC is that it reduces the footing of the photoresist pattern directly above the SiON film.

[0148] The resist top layer film in the three-layer resist process may be either positive or negative, and the same photoresist compositions as those commonly used can be used. After spin-coating the photoresist composition, pre-baking is performed, preferably at 60 to 180°C for 10 to 300 seconds. Thereafter, exposure is performed according to a conventional method, followed by post-exposure baking (PEB) and development to obtain a resist pattern. The thickness of the resist top layer film is not particularly limited, but is preferably 30 to 500 nm, more preferably 50 to 400 nm.

[0149] Examples of exposure light include high energy rays with a wavelength of 300 nm or less, specifically excimer lasers with wavelengths of 248 nm, 193 nm, and 157 nm, soft X-rays with wavelengths of 3 to 20 nm, electron beams, and X-rays.

[0150] In the pattern forming method of the present invention, the circuit pattern is preferably formed on the resist upper layer film by photolithography with a wavelength of 10 nm or more and 300 nm or less, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[0151] In the pattern forming method of the present invention, it is preferable to use alkaline development or development with an organic solvent as the development method.

[0152] Next, etching is performed using the obtained resist pattern as a mask. In the three-layer resist process, etching of the silicon-containing resist intermediate film and the inorganic hard mask is performed using a fluorocarbon gas as a mask for the upper resist pattern. This results in the formation of a silicon-containing resist intermediate film pattern and an inorganic hard mask pattern.

[0153] Next, the organic film is etched using the resulting silicon-containing resist intermediate film pattern or inorganic hard mask pattern as a mask.

[0154] Etching of the workpiece, such as the substrate to be processed, can also be performed using standard methods. For example, if the workpiece is made of SiO2, SiN, or a silica-based low-k dielectric insulating film, etching is performed primarily with fluorocarbon-based gases, while etching of p-Si, Al, or W is performed primarily with chlorine- or bromine-based gases. When etching the substrate with fluorocarbon-based gases, the silicon-containing resist intermediate film pattern in the three-layer resist process is stripped at the same time as the substrate is processed. When etching the substrate with chlorine- or bromine-based gases, the silicon-containing resist intermediate film pattern must be stripped separately by dry etching using fluorocarbon-based gases after substrate processing.

[0155] The organic film obtained from the organic film-forming composition of the present invention is characterized by excellent etching resistance when etching the workpiece.

[0156] In the pattern formation method of the present invention, the workpiece is preferably 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.

[0157] Furthermore, it is preferable to use silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof as the metal.

[0158] The workpiece is not particularly limited, and examples thereof include substrates of Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, etc., and substrates with a workpiece layer formed thereon. Examples of workpiece layers include low-k films and their stopper films, such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, and Al-Si, and can be formed to a thickness of preferably 50 to 10,000 nm, more preferably 100 to 5,000 nm. When forming a workpiece layer, the substrate and workpiece layer are made of different materials.

[0159] It is also preferable to use an object to be processed that has a structure or step with a height of 30 nm or more.

[0160] An example of a three-layer resist process is specifically shown below with reference to FIG.

[0161] In the case of a three-layer resist process, as shown in FIG. 1(A), an organic film 3 is formed on a workpiece 2 stacked on a substrate 1 using the organic film-forming composition of the present invention, followed by forming a silicon-containing resist intermediate film 4 and then forming a resist upper layer film 5 thereon.

[0162] Next, as shown in FIG. 1(B), a desired portion 6 of the resist top layer is exposed, followed by PEB and development to form a resist pattern 5a (FIG. 1(C)). Using the resulting resist pattern 5a as a mask, the silicon-containing resist intermediate film 4 is etched using a CF-based gas to form a silicon-containing resist intermediate film pattern 4a (FIG. 1(D)). After removing the resist pattern 5a, the organic film 3 is oxygen-plasma etched using the resulting silicon-containing resist intermediate film pattern 4a as a mask to form an organic film pattern 3a (FIG. 1(E)). After further removing the silicon-containing resist intermediate film pattern 4a, the workpiece 2 is etched using the organic film pattern 3a as a mask to form a pattern 2a (FIG. 1(F)).

[0163] When an inorganic hard mask is used, the silicon-containing resist intermediate film 4 is the inorganic hard mask, and when a BARC is laid down, a BARC layer is provided between the silicon-containing resist intermediate film 4 or the inorganic hard mask and the resist top layer film 5. Etching of the BARC may be performed prior to and consecutively with etching of the silicon-containing resist intermediate film 4, or etching of the silicon-containing resist intermediate film 4 may be performed after etching of the BARC alone, by changing the etching equipment, or the like.

[0164] As described above, the pattern forming method of the present invention makes it possible to form a fine pattern on a substrate to be processed with high precision in a multi-layer resist process. [Example]

[0165] The present invention will be explained in more detail below with reference to Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples, but is not limited thereto. The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) were determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent, and the polydispersity (Mw / Mn) was calculated.

[0166] The compounds (A1) to (A8) contained in the organic film-forming composition were synthesized using the following sumanenes (B1) to (B2), aromatic aldehydes (C1) to (C3), propargyl bromide (C4), aromatic Grignard reagents (C5) to (C6), and aromatic amine (C7). The aromatic Grignard reagent (C6) and sumanene oxide (B2) were synthesized by the methods described in Synthesis Example 1 and Synthesis Example 2, respectively.

[0167] Sumanenes: [ka]

[0168] Aromatic aldehydes (C1)-(C3), propargyl bromide (C4), aromatic Grignard reagents (C5)-(C6), aromatic amines (C7) [ka]

[0169] (Synthesis Example 1) Synthesis of aromatic Grignard reagent (C6) [ka] 1.2 g of magnesium was placed in a flask and heated with a heat gun under reduced pressure to degas and dehydrate. 20 g of dehydrated THF and 2.0 g of iodine were added under a nitrogen atmosphere and stirred. A solution of 5.0 g of 2-bromonaphthalene dissolved in 10 g of THF was added and stirred at 40°C for 3 hours to obtain a THF solution of (C6).

[0170] (Synthesis Example 2) Synthesis of Sumanene (B2) [ka]

[0171] 10.0 g of Sumanene (B1) was added to 200 ml of dichloromethane, 30.0 g of pyridine, 17.0 g of ruthenium (III) chloride hydrate, and 100 g of 70% aqueous tert-butyl hydroperoxide, and the mixture was stirred at 40°C for 100 hours. A small amount of silica gel was then added, and the mixture was dried under reduced pressure using an evaporator. Impurities were then removed using silica gel column chromatography. The product was dissolved in methyl isobutyl ketone (MIBK), crystallized with hexane, and then recovered and dried in vacuo at 70°C, yielding 8.1 g (70%) of (B2). The instrumental analysis data for this compound is shown below.

[0172] (Synthesis Example 3) Synthesis of Compound (A1) [ka]

[0173] Under a nitrogen atmosphere, 1.0 g of sumanene (B1), 5.5 g of n-tetrabutylammonium bromide, 100 ml of 30 wt% aqueous sodium hydroxide solution (previously degassed by nitrogen bubbling), and 50 ml of THF were added. Then, 3.5 g of 4-ethynylbenzaldehyde (C1) was added and stirred at room temperature for 15 hours. 150 ml of MIBK was added and the mixture was washed with deionized water until neutral. The resulting organic layer was concentrated, dissolved in MIBK, and crystallized with methanol. The crystals were filtered, washed, and then collected. Vacuum-dried at 70°C to yield 1.7 g (74%) of (A1). The instrumental analysis data for this compound are shown below.

[0174] IR (ATR method): 3443, 3289, 3036, 2957, 2870, 2106, 1698, 1661, 1505, 1403, 1367, 1308, 1224, 1163, 1110, 1016, 887, 827, 653, 544cm ―1 1 H-NMR (600MHz in CDCl3): 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 13C-NMR(150MHz in CDCl3): 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, 56.092ppm GPC: Mw / Mn = 1.08 MS(Calcd fоr C 48 H 24 +H + ):601.195 MS(LC-MS):601.194

[0175] (Synthesis Example 4) Synthesis of Compound (A2) [ka]

[0176] Compound (A2) 2.2 g (69%) was obtained in the same manner as compound (A1), except that 4-ethynylphenylbenzaldehyde (C2) was used instead of 4-ethynylbenzaldehyde (C1). The instrumental analysis data for this compound are shown below.

[0177] IR (ATR method): 3290, 3054, 2960, 2873, 2738, 2213, 2121, 1693, 1598, 1507, 1487, 1 442, 1394, 1311, 1223, 1180, 1159, 1107, 1069, 1018, 910, 887, 824, 754, 689cm -1 1H-NMR (600MHz in CDCl3): 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 13 C―NMR(150MHz in CDCl3):162.513, 147.535, 147.453, 147.403, 146.084, 145.787, 145.733, 145.495, 143.406, 143.159, 141.578, 141.12 5, 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, 1 25.776, 123.898, 123.765, 123.717, 123.512, 123.273, 121.209, 121.135, 121.010, 120.924, 115.325, 91.22, 89.57ppm. GPC: Mw / Mn = 1.02 MS(Calcd fоr C 66 H 36 +H + ):829.289 MS(LC-MS):829.288

[0178] (Synthesis Example 5) Synthesis of Compound (A3) [ka]

[0179] Compound (A3) 2.0 g (75%) was obtained in the same manner as compound (A1), except that 4-(propargyloxy)benzaldehyde (C3) was used instead of 4-ethynylbenzaldehyde (C1). The instrumental analysis data for this compound are shown below. IR (ATR method): 3287, 3041, 2923, 2120, 1686, 1600, 1507, 1445, 1394, 1370, 1304, 1224, 1173, 1113, 1020, 978, 826, 681, 630cm -1 1 H-NMR (600MHz in CDCl3): 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 13 C-NMR(150MHz in CDCl3):158.139, 147.871, 147.547, 146.013, 145.667, 145.517, 145.237, 145.074, 143.373, 14 3.321, 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, 29.844ppm GPC: Mw / Mn = 1.06 MS (Calcd for C 51 H 30 O3+H + ):691.227 MS (LC-MS): 691.226

[0180] (Synthesis Example 6) Synthesis of Compound (A4)

change

[0181] Under a nitrogen atmosphere, 1.0 g of sumanene (B1), 5.5 g of n-tetrabutylammonium bromide, 100 ml of 30 wt% aqueous sodium hydroxide solution (previously degassed by nitrogen bubbling), and 50 ml of THF were added. Then, 10.0 g of an 80 wt% toluene solution of propargyl bromide (C4) was added and stirred at room temperature for 100 hours. 150 ml of MIBK was added and the mixture was washed with deionized water until neutral. The resulting organic layer was concentrated, dissolved in MIBK, and crystallized with hexane. The mixture was filtered, washed, and vacuum dried at 70°C to obtain 1.5 g (80%) of (A4). The instrumental analysis data for this compound are shown below.

[0182] IR (ATR method): 3433, 3296, 2929, 2118, 1723, 1426, 1366, 1257, 1086, 825, 643cm -1 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) 13 C-NMR (150MHz in CDCl3): 154.911, 146.056, 122.961, 81.228, 71.604, 59.549, 24.629ppm GPC: Mw / Mn = 1.07 MS(Calcd fоr C 39 H 24 +H + ):493.195 MS(LC-MS):493.195

[0183] (Synthesis Example 7) Synthesis of Compound (A5) [ka]

[0184] Under a nitrogen atmosphere, 1.0 g of trioxosumanene (B2) and 30 ml of THF were added. While stirring at room temperature, 30 ml of a 1 M THF solution of phenylmagnesium bromide (C5) was added and stirred overnight. 50 g of aqueous ammonium chloride solution was added to stop the reaction, and extraction was performed 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 using silica gel column chromatography. The mixture 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 instrumental analysis data for this compound is shown below.

[0185] IR (ATR method): 3533, 3381, 3051, 3001, 1611, 1510, 1476, 1451, 1359cm -1 1 H-NMR (600MHz in CDCl3): 7.28(15H, m), 7.02(6H, s), 5.72(3H, s)ppm 13 C-NMR (150MHz in CDCl3): 160.321, 158.2, 146.223, 130.211, 122.415, 122.511, 116.283, 83.728ppm GPC: Mw / Mn = 1.03

[0186] (Synthesis Example 8) Synthesis of Compound (A6) [ka]

[0187] Compound (A6) 2.4 g (71%) was obtained in the same manner as compound (A5), except that 2-naphthylmagnesium bromide (C6) prepared in Synthesis Example 1 was used instead of phenylmagnesium bromide (C5). The yield and instrumental analysis data of this compound are shown below.

[0188] IR (ATR method): 3531, 3394, 3053, 3019, 1601, 1505, 1474, 1448, 1357cm -1 1 H-NMR (600MHz in CDCl3): 8.03~7.09 (21H, m), 7.04 (6H, s), 5.78 (3H, s) ppm 13 C―NMR(150MHz in CDCl3):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, 83.712ppm GPC: Mw / Mn = 1.05

[0189] (Synthesis Example 9) Synthesis of Compound (A7) [ka]

[0190] Under a nitrogen atmosphere, 1.0 g of compound (A6) synthesized in Synthesis Example 8 and 20.0 g of methanol were added. 2.0 g of methanesulfonic acid was added dropwise, and the mixture was stirred under reflux for 3 hours. 150 ml of toluene was added, and the mixture was washed with deionized water until neutral. The resulting organic layer was concentrated, dissolved in MIBK, and crystallized by adding hexane. After filtration and washing, 0.93 g (88%) of (A7) was obtained. The instrumental analysis data for this compound are shown below.

[0191] IR (ATR method): 3051, 2927, 2826, 1603, 1446, 1160, 1082cm -1 1 H-NMR (600MHz in CDCl3): 8.03~7.09 (21H, m), 7.04 (6H, s), 3.06 (9H, s) 13 C-NMR(150MHz 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, 51.445ppm GPC: Mw / Mn = 1.04

[0192] (Synthesis Example 10) Synthesis of Compound (A8) [ka]

[0193] Under a nitrogen atmosphere, 1.5 g of trioxosumanene (B2), 5.3 g of 4-ethynylaniline (C7), 5.0 g of activated molecular sieves (MS4A), and 20 ml of dehydrated toluene were added and reacted at 120°C for 6 hours. An additional 5.3 g of 4-ethynylaniline (C7) and 5.0 g of activated molecular sieves (MS4A) were added, and the reaction was continued for another 24 hours. The reaction solution was dried under reduced pressure using an evaporator, and impurities were removed using silica gel column chromatography. The product was dissolved in MIBK, crystallized with hexane, filtered, washed, and vacuum dried at 70°C to obtain 1.3 g (39%) of (A8). The instrumental analysis data for this compound are shown below.

[0194] IR (ATR method): 3339, 3021, 2911, 2850, 1888, 1717, 1651, 1611, 1553, 1499, 1388cm ―1 1 H-NMR (600MHz in CDCl3): 6.08 (2H, d), 6.50 (2H, d), 6.92~7.30 (12H, m) 7.61 (2H, d) ppm 13C-NMR(150MHz in CDCl3): 163.186, 162.893, 148.965, 148.800, 148.466, 148.399, 148.365, 148.300, 148.28 6, 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, 12 4.900, 124.813, 124.644, 124.625, 120.961, 120.922, 120.744, 76.496, 56.092ppm. GPC: Mw / Mn = 1.08

[0195] (Comparative synthesis example) (Comparative Synthesis Example 1) Synthesis of Compound (R1) [ka]

[0196] Under a nitrogen atmosphere, 120 g of 2-acetylfluorene and 120 g of m-xylene were added and heated to 110°C to form a homogeneous solution. 21.0 g of dodecylbenzenesulfonic acid was added, and the temperature was raised to 140°C and the reaction was carried out for 16 hours. The reaction solution was added to methanol to cause crystallization, which was then filtered, washed, and vacuum dried at 70°C to obtain (R1). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC to be Mw = 620 and Mw / Mn = 1.03.

[0197] (Comparative Synthesis Example 2) Synthesis of Compound (R2) [ka]

[0198] Under a nitrogen atmosphere, 10.0 g of compound (R1) synthesized in Comparative Synthesis Example 1, 25.0 g of n-tetrabutylammonium bromide, 300 ml of 30 wt % aqueous sodium hydroxide solution (previously degassed by nitrogen bubbling), and 100 ml of THF were added. Then, 14.0 g of 4-ethynylbenzaldehyde (C1) was added and stirred at room temperature for 15 hours. 150 ml of MIBK was added and the mixture was washed with deionized water until neutral. The resulting organic layer was concentrated, dissolved in MIBK, and crystallized with methanol. The crystals were filtered, washed, and dried under vacuum at 70°C to obtain (R2). The weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC to be Mw = 960 and Mw / Mn = 1.04.

[0199] (Comparative Synthesis Example 3) Synthesis of Compound (R3) [ka]

[0200] Compound (R3) was obtained in the same manner as compound (R2), except that 4-(propargyloxy)benzaldehyde (C3) was used instead of 4-ethynylbenzaldehyde (C1). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC to be Mw = 960 and Mw / Mn = 1.04.

[0201] (Comparative Synthesis Example 4) Synthesis of Compound (R4) [ka]

[0202] Under a nitrogen atmosphere, 10.0 g of compound (R1) synthesized in Comparative Synthesis Example 1, 25.0 g of n-tetrabutylammonium bromide, 300 ml of 30 wt% aqueous sodium hydroxide solution that had been degassed by nitrogen bubbling, and 100 ml of THF were added. Then, 100 g of an 80 wt% toluene solution of propargyl bromide (C4) was added, and the mixture was stirred at 90°C for 48 hours. 150 ml of MIBK was added, and the mixture was washed with deionized water until neutral. The resulting organic layer was concentrated, dissolved in MIBK, and crystallized with hexane. The crystals were filtered, washed, and dried under vacuum at 70°C to obtain (R4). The weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC to be Mw = 820 and Mw / Mn = 1.05.

[0203] (Comparative Synthesis Example 5) Synthesis of Compound (R5) [ka]

[0204] Under a nitrogen atmosphere, 1.0 g of Sumanene (B1), 5.5 g of n-tetrabutylammonium bromide, 100 ml of 30 wt% aqueous sodium hydroxide solution (previously degassed by nitrogen bubbling), 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 resulting organic layer was concentrated, dissolved in MIBK, and crystallized with hexane. The crystal was filtered, washed, and dried in vacuum at 70°C to obtain (R5). The weight-average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC to be Mw = 520 and Mw / Mn = 1.05.

[0205] ( Preparation of organic film-forming compositions (UDL-1 to 15, comparative UDL-1 to 5) The compounds (A1) to (A8) and comparative compounds (R1) to (R5) were dissolved in propylene glycol monomethyl ether acetate (PGMEA) containing 0.1% by mass of FC-4430 (manufactured by Sumitomo 3M Limited) and cyclohexanone (CyHO) in the proportions shown in Table 1 using high-boiling organic solvents (S1) 1,6-diacetoxyhexane (boiling point 260°C) and (S2) tripropylene glycol monomethyl ether (boiling point 242°C). The organic film-forming compositions (UDL-1 to 15, comparative UDL-1 to 5) were prepared by filtering through a 0.1 μm fluororesin filter. UDL-6, 8, and 10 contained a thermal acid generator (TAG) represented by the following formula:

[0206] [Table 1]

[0207] [ka]

[0208] Examples 1-1 to 1-15, Comparative Examples 1-1 to 1-5 (Solvent Resistance Measurement) The UDL-1 to 15 and comparative UDL-1 to 5 were coated onto silicon substrates and baked in air at 350°C for 60 seconds. The film thickness was then measured. PGMEA solvent was dispensed onto the coated substrate, left for 30 seconds, spin-dried, and baked at 100°C for 60 seconds to evaporate the PGMEA. The film thicknesses before and after the PGMEA treatment were measured. The film thickness after the deposition and the film thickness after the PGMEA treatment were used to calculate the residual film ratio. The results are shown in Table 2.

[0209] [Table 2]

[0210] As shown in Table 2, organic films using the compounds of the present invention (Examples 1-1 to 1-15) had a film retention rate of 99% or more after PGMEA treatment, indicating that crosslinking reactions occurred upon heat treatment, resulting in sufficient solvent resistance. These results demonstrate that compounds having specific partial structures of the present invention have thermosetting properties. Comparing Examples 1-5, 1-7, and 1-9 with Examples 1-6, 1-8, and 1-10, the addition of a thermal acid generator increased the film retention rate by 0.4 to 0.7% compared to the compound alone, demonstrating that a denser film was formed due to the action of the acid catalyst. It was also confirmed that organic films using compounds with similar partial structures (Comparative Examples 1-2 to 1-4) and an organic film using a compound with a sumanene skeleton (Comparative Example 1-5) also exhibited solvent resistance.

[0211] Examples 2-1 to 2-15, Comparative Examples 2-1 to 2-5 (Hardness Measurement) The UDL-1 to 15 and comparative UDL-1 to 5 were coated onto silicon substrates and baked in air at 350°C for 60 seconds to form organic films with a thickness of 200 nm. These organic films were subjected to nanoindentation testing using a Toyo Corporation Nanoindenter SA2 model device to measure the hardness of the organic films. The results are shown in Table 3.

[0212] [Table 3]

[0213] As shown in Table 3, a comparison of Examples 2-1 to 2-15 and Comparative Examples 2-1 to 2-4 reveals that compounds having a sumanene structure have excellent film hardness. Furthermore, a comparison of Examples 2-5, 2-7, and 2-9 with Examples 2-6, 2-8, and 2-10 in Examples 2-5 to 2-10 reveals that Examples 2-6, 2-8, and 2-10 have higher hardness. This demonstrates that, as in Example 1, the addition of a thermal acid generator improves hardness and results in the formation of dense films. A comparison of 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, reveals that the compounds incorporating the sumanene-containing structure of the present invention have higher hardness. This is due to the densification of the film resulting from the sumanene structure, which is presumably due to the fact that sumanene itself has the property of easily forming aggregates. Furthermore, when comparing Example 2-4 having a sumanene structure with Comparative Example 2-5, it was confirmed that the compound having a propargyl group introduced therein has higher hardness than the compound having an allyl group, and can form a denser film. This is in line with the results of the solvent resistance test in Example 1, and it can be inferred that a denser film can be formed as well, since the propargyl group substitution had better solvent resistance.

[0214] Examples 3-1 to 3-15, Comparative Examples 3-1 to 3-5 (etching test) [Etching test using CF4 / CHF3 gas] The UDL-1 to 15 and comparative UDL-1 to 5 were coated onto silicon substrates and baked in air at 350°C for 60 seconds to form organic films with a thickness of 200 nm. An etching test was then performed using a CF4 / CHF3 gas under the following conditions, and the difference in thickness of the organic films before and after etching was determined. The results are shown in Table 4. A dry etching system TE-8500 manufactured by Tokyo Electron Limited was used for etching.

[0215] The etching conditions are as follows: Chamber pressure 40.0Pa RF power 1,000W CHF3 gas flow rate 10ml / min CF4 gas flow rate 100ml / min He gas flow rate: 200 ml / min Time 20sec

[0216] [Table 4]

[0217] In Table 4, the film thickness reduction of each of the Examples and Comparative Examples is expressed as a ratio, with the film thickness reduction of Comparative UDL-1 due to etching with CF / CHF gas being set at 100%. The smaller the ratio, the better the etching resistance.

[0218] [Etching test using O2-based gas] The UDL-1 to 15 and comparative UDL-1 to 5 were coated onto silicon substrates and baked in air at 350°C for 60 seconds to form organic films with a thickness of 200 nm. An etching test was then conducted using an O2-based gas under the following conditions, and the difference in thickness of the organic film before and after etching was determined. The results are also shown in Table 4. The etching was performed using a dry etching system TE-8500 manufactured by Tokyo Electron Limited.

[0219] The etching conditions are as follows: Chamber pressure 40.0Pa RF power 100W O2 gas flow rate 30ml / min N2 gas flow rate 70ml / min Time 60sec

[0220] As with the CF / CHF etching test, the film thickness reduction for the Examples and Comparative Examples is shown as a percentage of the film thickness reduction for Comparative UDL-1 after etching with O gas in Table 4. The smaller the ratio, the better the etching resistance.

[0221] As shown in Table 4, comparing Examples 3-1 to 3-15 with Comparative Examples 3-1 to 3-4, in both the CF / CHF-based and O-based gas etching tests, the post-etch loss of the films in the Examples was comparable to or less than that of the Comparative Examples, demonstrating the formation of organic films with excellent etching resistance. In particular, Examples 3-1, 3-2, and 3-4, which do not contain heteroatom structures, and Examples 3-5 to 3-10, which eliminate heteroatoms upon curing, showed excellent etching resistance. Furthermore, comparing Example 3-1 with Comparative Example 3-2, Example 3-3 with Comparative Example 3-3, and Example 3-4 with Comparative Example 3-4, each of which has the same substituent structure as in Example 2, reveals that when comparing etching resistance between compounds with the same substituent structure, organic films with superior etching resistance are formed using compounds with a sumanene structure. Similarly, comparing Example 3-4 with Comparative Example 3-5, which has a sumanene skeleton, Example 3-4 exhibited better etching resistance, confirming that the propargyl group provides superior etching resistance over the allyl group. As shown in Examples 1 and 2, these are thought to have excellent solvent resistance and hardness, resulting in the formation of a denser film.

[0222] Examples 4-1 to 4-15, Comparative Examples 4-1 to 4-5 (Pattern Etching Test) The UDL1-1 to 1-15 and Comparative UDL1-1 to 1-5 were applied to a 300 mm diameter Si wafer substrate with a 200 nm thick SiO2 film formed thereon, and baked in air at 350°C for 60 seconds to form an organic film with a thickness of 200 nm. A silicon-containing resist intermediate film material (SOG-1) was applied on top of the organic film and baked at 220°C for 60 seconds to form a 35 nm thick resist intermediate film. A resist top layer material (ArF SL resist) was applied and baked at 105°C for 60 seconds to form a 100 nm thick resist top layer. An immersion protective film (TC-1) was applied to the resist top layer and baked at 90°C for 60 seconds to form a 50 nm thick protective film.

[0223] A resist top layer 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 a basic compound (Amine1) represented by the following formula in 2500 parts by mass of PGMEA containing 0.1% by mass of FC-430 (manufactured by Sumitomo 3M Limited), and filtering the solution through a 0.1 μm fluororesin filter.

[0224] [ka]

[0225] The immersion protective film material (TC-1) was prepared by dissolving 100 parts by mass of a protective film polymer (PP1) represented by the following formula in an organic solvent consisting of 2,700 parts by mass of diisoamyl ether and 270 parts by mass of 2-methyl-1-butanol, and filtering the solution through a 0.1 μm fluororesin filter.

[0226] [ka]

[0227] The silicon-containing resist interlayer material (SOG-1) was prepared by dissolving 100 parts by mass of an ArF silicon-containing interlayer polymer (SiP1) represented by the following formula and 1 part by mass of a crosslinking catalyst (CAT1) represented by the following formula in 4,000 parts by mass of PGMEA containing 0.1% by mass of FC-4430 (manufactured by Sumitomo 3M Limited), and filtering the solution through a fluororesin filter with a pore size of 0.1 μm.

[0228] [ka]

[0229] Next, the resist was exposed to light using an ArF immersion exposure system (Nikon Corporation; NSR-S610C, NA 1.30, σ 0.98 / 0.65, 35-degree dipole s-polarized illumination, 6% halftone phase-shift mask) while varying the exposure dose, baked at 100°C for 60 seconds (PEB), and developed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds, yielding a positive line-and-space pattern with a pitch of 100 nm and resist line widths ranging from 50 nm to 30 nm.

[0230] After that, using the Tokyo Electron etching device Telius, we sequentially processed the silicon-containing resist intermediate film using the resist pattern as a mask by dry etching, processed the organic film using the silicon-containing resist intermediate film as a mask, and processed the SiO2 film (workpiece) using the organic film as a mask.

[0231] The etching conditions are as follows: Transfer conditions for resist pattern onto SOG film (silicon-containing resist interlayer): Chamber pressure 10.0Pa RF power 1,500W CF4 gas flow rate 15sccm O2 gas flow rate 75sccm Time 15sec

[0232] Conditions for transferring SOG film (silicon-containing resist interlayer) to organic film: Chamber pressure 2.0Pa RF power 500W Ar gas flow rate 75sccm O2 gas flow rate: 45sccm Time 120sec

[0233] Transfer conditions to SiO2 film (workpiece): Chamber pressure 2.0Pa RF power 2,200W C5F 12 Gas flow rate: 20sccm C2F6 gas flow rate 10sccm Ar gas flow rate: 300sccm O2 60sccm Time 90sec

[0234] The cross sections of the pattern after development, the shape after transfer etching of the silicon-containing resist intermediate film, the shape after transfer etching of the organic film, and the shape after transfer etching of the workpiece were observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd., and the twist-free critical dimensions (nm) of the patterns after transfer etching of the workpiece were measured and summarized in Table 5.

[0235] [Table 5]

[0236] The results of Examples 4-1 to 4-15 show that when UDL-1 to 15 are used as organic films in three-layer resists for immersion lithography, the resist shape after development is good in the pattern shape evaluation, and they have a useful effect as anti-reflection films. Similar results were also obtained in the comparative examples.

[0237] In the post-etching pattern shape, the resist shape after development, the shape of the organic film after oxygen etching, and the shape of the organic film after substrate processing etching were all good in all Examples and Comparative Examples. Meanwhile, the critical dimension of the pattern without distortion after the workpiece transfer etching changed according to the resist line width created by exposure. In Comparative Example 4-1, pattern distortion occurred at a line width of about 33 nm, but Examples 4-1 to 4-15 using the compound of the present invention showed no distortion down to pattern dimensions of 30 nm or less, demonstrating high distortion resistance. Comparing compounds having the same substituent structure as the present invention, 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, it was found that the organic film using the compound of the present invention having a sumanene structure had better distortion resistance.

[0238] Examples 5-1 to 5-15 and Comparative Examples 5-1 to 5-5 (Embedding characteristics) An organic film was formed on a SiO2 substrate with a dense hole pattern of 500 nm thick and 160 nm in diameter by coating UDL-1 to 15 on a flat substrate at 350°C for 60 seconds to form an 80 nm thick film. The substrate with the organic film was then cut and observed with a scanning electron microscope (SEM) to determine whether the organic film had filled the holes to the bottom. The results are shown in Table 6.

[0239] [Table 6]

[0240] As shown in Table 6, in Examples 5-1 to 5-15, in which organic films were formed using UDL-1 to UDL-15 of the present invention, all of the holes were well filled to the bottom, and sufficient filling properties can be expected even when there are steps in the workpiece, demonstrating that these materials have useful properties as organic film materials for multilayer processes. Similar results were also obtained in the comparative examples.

[0241] Examples 6-1 to 6-6 (flattening characteristics) Each of the organic film-forming compositions (UDL-1, 4, 12-15) was applied to a SiO2 wafer substrate with a large isolated trench pattern (trench width: 10 μm, trench depth: 0.10 μm) and baked in air at 350°C for 60 seconds. The step difference (delta in Figure 2) between the trench and non-trench areas of the organic film was then observed using a Park Systems NX10 atomic force microscope (AFM). The results are shown in Table 7. In this evaluation, the smaller the step difference, the better the planarization characteristics. Note that in this evaluation, a 0.10 μm-deep trench pattern was planarized using an organic film-forming composition with a typical film thickness of approximately 0.2 μm, which provides strict evaluation conditions for evaluating the superiority or inferiority of planarization characteristics.

[0242] [Table 7]

[0243] 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 no high-boiling organic solvent was added, the steps in Examples 6-3 to 6-6 were comparable or smaller, indicating that the addition of a high-boiling organic solvent improved the flatness. It was confirmed that the flatness could also be improved by adjusting the organic solvent composition of the compound of the present invention.

[0244] Examples 7-1 to 7-15 and Comparative Examples 7-1 to 7-5 (Heat Resistance Test) Each of the organic film-forming compositions (UDL-1 to 15, Comparative UDL-1 to 5) was applied to a Si substrate, baked in nitrogen at 350°C for 60 seconds, and the film thickness was measured. The film was then baked at 450°C for another 60 seconds, and the film thickness was measured again. The film thickness reduction rate (%) was then calculated using the following formula, and this film thickness reduction rate was used as a measure of heat resistance. ML = { ( m 1 - m 2 ) / m 1} × 1 0 0 In the above formula, ML is the film thickness reduction rate (%), m1 is the film thickness (nm) after baking at 350°C, and m2 is the film thickness (nm) after baking at 450°C. The smaller the film thickness reduction rate, the less sublimate and decomposition products were generated when the organic film was heated, and the better the heat resistance. In other words, the smaller the film thickness reduction rate, the higher the heat resistance. The measurement results are shown in Table 8.

[0245] [Table 8]

[0246] As shown in Table 8, Examples 7-1 to 7-15, in which organic films were formed using UDL-1 to UDL-15 of the present invention, had film thickness reduction rates of 3% or less, demonstrating excellent heat resistance. Furthermore, when Example 7-1 and Comparative Example 7-2, Example 7-3 and Comparative Example 7-3, and Example 7-4 and Comparative Example 7-4, which have the same substituent structure, are compared, it is found that when etching resistance is compared between compounds with the same substituent structure, compounds having a sumanene structure have superior heat resistance. Furthermore, when comparing Example 7-4 and Comparative Example 7-5, which is a comparison between sumanene compounds, it is shown that Example 7-4 has superior heat resistance, confirming the effectiveness of the propargyl group introduced in the present invention.

[0247] Examples 8-1 to 8-15, Comparative Examples 8-1 to 8-5 (Coatability Test) The organic film-forming compositions (UDL-1 to 15, Comparative UDL-1 to 5) were applied to bare Si substrates, hexamethyldisilazane (HMDS)-treated substrates, and SiON-treated substrates shown in Table 9, and baked in air at 350°C for 60 seconds to form organic films with a thickness of 200 nm. After formation, the organic films were observed using an optical microscope (Nikon ECLIPSE L200) to check for coating defects. The results are shown in Table 9.

[0248] [Table 9]

[0249] As shown in Table 9, in Examples 8-1 to 8-15 in which organic films were formed using UDL-1 to UDL-15 of the present invention, uniform organic films without substrate dependency and coating defects were formed. In addition, in Comparative Examples 8-1 to 8-4, pinhole defects were not observed on substrates other than bare-Si substrates. In Comparative Example 8-5, a film could be formed without dependency on the substrate, and the effect of improving film formability due to the introduction of the sumanene structure was confirmed.

[0250] As described above, the resist organic film material of the present invention has high etching resistance and excellent resistance to distortion during etching, and is therefore extremely useful as an organic film for a multilayer resist process, particularly a three-layer resist process, for ultrafine and high-precision pattern processing.

[0251] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention. [Explanation of symbols]

[0252] 1...substrate, 2...workpiece, 2a...pattern formed on substrate, 3...organic film, 3a...organic film pattern, 4...silicon-containing resist intermediate film, 4a...silicon-containing resist intermediate film pattern, 5...resist upper layer film, 5a...resist pattern, 6...required part.

Claims

[Claim 1] A compound represented by the following general formula (1): 【Chemical 1】 (In the above general formula (1), X is any one of the groups X1 to X3 represented by the following general formulas (2), (3), and (5), and two or more types of X may be used in combination.) 【Chemistry 2】 【Chemistry 3】 (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 R １ are independently any group represented by the following general formula (4): 【Chemistry 4】 【Chemistry 5】 (In the above general formula (5), R ２ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ３ is one of the following groups: 【Chemistry 6】

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