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 is a demand for finer pattern rules. In the lithography using light exposure, which is currently used as a general-purpose technology, various technological developments are being made to fabricate finer and more accurate patterns for the light source used.

[0003] As a light source for lithography used in forming resist patterns, light exposure using mercury lamps' 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 wavelengths such as 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 the resist pattern becomes thinner, it is well known that the ratio of the pattern height to the pattern line width (aspect ratio) increases in the single-layer resist method used as a typical resist pattern forming method, and the pattern collapses due to the surface tension of the developer during development. Therefore, it is known that a multi-layer resist method in which films with different dry etching characteristics are laminated to form a pattern with a high aspect ratio on a stepped substrate is excellent, and a two-layer resist method (Patent Document 1, etc.) that combines a photoresist upper layer film made of a silicon-containing photosensitive polymer with an organic polymer containing carbon, hydrogen, and oxygen as main constituent elements, such as an organic film made of a novolac polymer, and a three-layer resist method (Patent Document 2, etc.) that combines a photoresist upper layer film made of an organic photosensitive polymer used in the single-layer resist method with a silicon-containing resist intermediate film made of a silicon-containing polymer or a silicon-containing CVD film with an organic film made of an organic polymer have been developed.

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

[0006] The carbon hard mask formed directly on the workpiece is generally an amorphous carbon (hereafter referred to as CVD-C) film created by the CVD method using methane gas, ethane gas, acetylene gas, etc. as raw materials. This CVD-C film is known to be extremely effective in preventing the above-mentioned pattern distortion and bending, as it can reduce the amount of hydrogen atoms in the film. However, it is also known that if the underlying workpiece has steps, it is difficult to fill such steps flatly due to the characteristics of the CVD process. Therefore, if a workpiece with steps is filled with a CVD-C film and then patterned with photoresist, steps will occur on the coated surface of the photoresist due to the effects of the steps on the workpiece, which will result in unevenness in the film thickness of the photoresist, resulting in deterioration 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 formed directly on a workpiece, it is known to have the advantage that the steps of the stepped substrate can be filled flatly. When the substrate is planarized with this organic film material, the film thickness fluctuation of the silicon-containing resist intermediate film and the photoresist upper layer film formed on the substrate is suppressed, the focus tolerance of lithography can be expanded, and a normal pattern can be formed.

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

[0009] Conventionally, such organic film materials include condensation resins using carbonyl compounds such as ketones and aldehydes or aromatic alcohols as condensation agents for phenolic or naphtholic compounds as organic film forming materials for multilayer resist methods. For example, fluorene bisphenol novolac resin described in Patent Document 2, bisphenol compounds and their novolac resins described in Patent Document 3, adamantane phenol compound novolac resins described in Patent Document 4, and bisnaphthol compounds and their novolac resins described in Patent Document 5 can be exemplified. The resins used in such materials have a main skeleton made of naphthalene, fluorene, adamantane, etc., which have high carbon density, but since they have oxygen atoms derived from phenolic hydroxyl groups in their structural units, deterioration of etching resistance could not be avoided.

[0010] Furthermore, as an example of a resin for organic film materials that does not contain a heteroatom such as oxygen in order to avoid deterioration of etching resistance, a resin having a fluorene structure as described in Patent Document 6 is given. 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 causes a problem that the inherent etching resistance of the highly carbonized resin is impaired.

[0011] An example of an organic film material that does not contain additives such as crosslinking agents that deteriorate etching resistance and does not contain heteroatoms such as oxygen to improve etching resistance is an organic film material that uses a monomolecular compound described in Patent Document 7. However, since 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 onto substrates with complex shapes and problems with sublimates caused by low molecular weight compounds that occur during baking.

[0012] In order to maximize the carbon density, various fullerene derivatives have been investigated, such as those described in Patent Documents 8 and 9. However, fullerene itself is not curable, and film formation is difficult due to the problem of solvent solubility. Therefore, when applying fullerene, it is necessary to add resins or crosslinking agents, and further to introduce various substituents to improve solvent solubility, but the decrease in carbon density and the deterioration of heat resistance due to the introduction of substituents are major issues 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] JP 2005-128509 A [Patent Document 3] JP 2006-293298 A [Patent Document 4] JP 2006-285095 A [Patent Document 5] JP 2010-122656 A [Patent Document 6] International Publication No. 2013 / 047106 Brochure [Patent Document 7] JP 2008-164806 A [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 has an object to provide a composition for forming an organic film, which has a high carbon content and is thermosetting, thereby enabling high etching resistance and excellent warping resistance to be exhibited without impairing the inherent carbon content of the resin, and which also has good film-forming properties and contains few sublimates that become outgassing, a pattern formation method using the same, and a compound 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 A composition for forming an organic film, The composition for forming an organic film is characterized in that it 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 R 1 are independently any group represented by the following general formula (4): [ka] [ka] (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: [ka]

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

[0017] In addition, the compound represented by the general formula (1) preferably has a ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn in terms of polystyrene measured by gel permeation chromatography, which is 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 such a composition for forming an organic film, the thermal fluidity of the organic film is imparted by adding a high-boiling point organic solvent to the compound represented by the general formula (1), so that 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 a method for producing a method for manufacturing a semiconductor device comprising the steps of: It is possible to provide a pattern forming 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 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 formation 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 a method for producing a method for manufacturing a semiconductor device comprising the steps of: A pattern forming method can be provided in which an organic film is formed on a workpiece using the organic film-forming composition, a silicon-containing resist intermediate film is formed on the organic film using a silicon-containing resist intermediate film material, an organic antireflective coating (BARC) is formed on the silicon-containing resist intermediate film, a resist top layer film is formed on the BARC using a photoresist composition to form a four-layer film structure, a circuit pattern is formed on the resist top layer film, the pattern is transferred to the BARC film and the silicon-containing resist intermediate film by etching using the resist top layer film on which the pattern has been formed as a mask, the pattern is transferred 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 the workpiece is etched 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, fine patterns can be formed on a workpiece with even greater precision.

[0027] The present invention also provides a method for producing a method for manufacturing a semiconductor device comprising the steps of: It is possible to provide a pattern forming method, which includes forming an organic film on a workpiece using the above-mentioned 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 to form a pattern on the workpiece.

[0028] By using such a pattern formation 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 relates to a method for producing a The present invention provides a pattern formation method, comprising the steps of: forming an organic film on a workpiece using the composition for forming an organic film; 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] By using such a pattern formation method using a four-layer resist process, fine patterns can be formed on a workpiece with high 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 a CVD method or an ALD method, a fine pattern can be formed on a workpiece with higher accuracy.

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

[0034] By using such a circuit pattern forming method, a fine pattern can be formed 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, a fine pattern can be formed 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 oxide carbide film, or a metal oxide nitride film.

[0038] By using such a workpiece, a better pattern can be formed.

[0039] 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 R 1 are independently any group represented by the following general formula (4): [ka] [ka] (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: [ka]

[0042] Such a compound has a high carbon content, and can exhibit high etching resistance and excellent warping resistance without impairing the inherent carbon content of the resin, and further has film-forming properties and a low content of sublimates that become outgassed, making it possible to provide a compound suitable for use in an organic film-forming composition. Effect of the Invention

[0043] Generally, a sumanene derivative corresponds to the cap structure of fullerenes or carbon nanotubes, and has a characteristic that the curved structure of the sumanene structure allows the sumanene molecules to easily overlap with each other to form a two-dimensional molecular aggregate. The organic film-forming composition containing the sumanene derivative represented by the general formula (1) can form a high-density and strong carbon film by imparting this characteristic of easily forming a molecular aggregate and solubility in organic solvents and thermosetting properties due to the substituent represented by X. Therefore, when an organic film formed by 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 twist resistance.

[0044] The Sumanene derivatives of the present invention are thermosetting and composed of a condensed aromatic ring structure with a high carbon content, which corresponds to the partial structure of fullerene, and therefore are components that provide compositions for forming organic films capable of forming organic films having both high twist resistance and dry etching resistance. Furthermore, these Sumanene derivatives are not limited to use only 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 form molecular aggregates.

[0045] As described above, the compound of the present invention is a high-density carbon compound having a main skeleton of a Sumanene structure, and is therefore a useful compound for forming an organic film having excellent etching resistance and twist resistance. In addition, the organic film-forming composition of the present invention containing this compound is a useful material for forming an organic film having not only excellent etching resistance and twist resistance, but also various properties such as heat resistance and embedding / flattening properties. Therefore, it is extremely useful as a resist organic film material in a multilayer resist process such as a two-layer resist process, a three-layer resist process using a silicon-containing resist intermediate film, or a four-layer resist process using a silicon-containing resist intermediate film and an organic antireflective film (BARC). In addition, the pattern formation method of the present invention allows a fine pattern to be formed on a substrate to be processed with high precision in a multilayer resist process. [Brief description of the drawings]

[0046] [Figure 1] 1 is a process diagram showing an example of a pattern forming method of the present invention. [Diagram 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 a SiO2 wafer substrate having a trench pattern. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

[0048] As a result of intensive research into the above-mentioned problems, the present inventors have found that the introduction of a specific partial structure into Sumanene can impart thermosetting properties and solubility in organic solvents. Furthermore, they have found that a composition for forming an organic film containing the compound and an organic solvent forms an organic film having excellent etching resistance and twist resistance, as well as various properties such as heat resistance, filling / flattening properties, film-forming properties, and a small amount of sublimate components, and have completed the present invention.

[0049] That is, the present invention provides: A composition for forming an organic film, 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 R 1 are independently any group represented by the following general formula (4): [ka] [ka] (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: [ka]

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

[0051] [Compound] The composition for forming an organic film 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 R 1 are independently any group represented by the following general formula (4): [ka] [ka] (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: [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 viewpoints 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. These may have a substituent on the aromatic ring constituting them, 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, n1=1 is satisfied and R 1 Preferably, the substituent represented by the following formula (I) has an ethynyl group or an ethynylphenyl group. [ka]

[0055] [ka]

[0056] Among the partial structures represented by X in the general formula (1), X3 is represented by the general formula (5) above, and specific examples thereof include the following. When an aromatic ring is contained as a component of these, the aromatic ring 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 X3, R2 is preferably a hydrogen atom, and from the viewpoint of etching resistance and thermosetting properties, R 3 is preferably naphthalene or diphenylacetylene. [ka]

[0057] [ka]

[0058] [ka]

[0059] [ka]

[0060] Among the partial structures represented by X in the general formula (1), the compound X3 is a substituent R 3 In addition to the thermosetting effect of the above, as shown below, the action of heat or acid causes a condensation reaction involving dehydration or dealcoholization between molecules, forming a dense film. [ka]

[0061] In addition, the compound represented by the general formula (1) preferably has a ratio Mw / Mn of the weight average molecular weight Mw and 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, if it is a monomolecular compound, Mw / Mn is 1.00, but due to the separation property of the gel permeation chromatography method, the measured value may exceed 1.00. In general, it is extremely difficult for a polymer having a repeating unit to approach Mw / Mn=1.00 unless a special polymerization method is used, and the Mw / Mn value exceeds 1 due to the Mw distribution. In the present invention, in order to distinguish between a monomolecular compound and a polymer, 1.00≦Mw / Mn≦1.15 is defined as an index indicating 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 having excellent filling properties and planarization properties.

[0063] The compound for an organic film-forming composition represented by the general formula (1) is preferably added in an amount of 1 to 20 parts by mass, and 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 represented by the general formula (1) of the present invention can be synthesized by using Sumanene or an oxide of Sumanene as a raw material. The manufacturing method is shown below for each of the cases where X is X1, X2, and X3.

[0065] When X is X1, for example, the following substitution reaction of sumanene with a halide of a propargyl group, tosylate or mesylate, and a base catalyst can be used. 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 mole number of the raw material Sumanene.

[0067] The solvent used in this case is not particularly limited as long as it is a solvent inert to the above reaction, but for example, ether solvents such as diethyl ether, tetrahydrofuran, dioxane, etc., aromatic solvents such as benzene, toluene, xylene, etc., acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, water, etc., can be used alone or in combination. 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 0.1 to 100 hours.

[0068] The reaction method includes a method of charging the halide, tosylate or mesylate of the propargyl group and the acid catalyst all at once, a method of dispersing or dissolving the sumanene, the halide or tosylate, or the mesylate, and then adding the catalyst all at once or in portions, or a method of diluting with a solvent and then dropping, a method of dispersing or dissolving the catalyst, and then adding the sumanene, the halide or tosylate, or the mesylate, all at once or in portions, or a method of diluting with a solvent and then dropping. In this case, depending on the reactivity of the aromatic compounds, it is preferable to use 2 moles or more of the halide, tosylate or mesylate of the propargyl group when the sumanene is taken as 1 mole. After the reaction is completed, the target product can be recovered by diluting with an organic solvent to remove the catalyst used in the reaction, and then performing separation and washing.

[0069] Furthermore, in addition to the above propargyl-type halides, tosylates, and mesylates, alkyl-type halides, tosylates, mesylates, or allyl-type halides, tosylates, and mesylates can be used in combination during the reaction. 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 or 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 liquid separation washing is not particularly limited as long as it can dissolve the target substance and separate into two layers even when mixed with water, but examples thereof 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 ethylcyclopentyl methyl ether, chlorine-based solvents such as methylene chloride, chloroform, dichloroethane, and trichloroethylene, and mixtures thereof. The washing water used in this case is usually what is called deionized water or ultrapure water. The number of washings may be one or more times, but since washing 10 or more times does not necessarily provide the effect of washing alone, it is preferably about 1 to 5 times.

[0071] In order to remove acidic components in 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 base components in 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 above-mentioned separation washing with a basic aqueous solution and an acidic aqueous solution may be performed either alone or in combination. From the viewpoint of removing metal impurities, the separation washing is preferably performed in the order of a basic aqueous solution and an acidic aqueous solution.

[0074] After the above-mentioned separation washing with the basic aqueous solution or acidic aqueous solution, washing with neutral water may be performed successively. 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. Even if washing is performed 10 times or more, the effect of washing alone may not be obtained, so it is preferably about 1 to 5 times.

[0075] Furthermore, the reaction product after the liquid 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 of a moderate concentration in order to improve operability when preparing an organic film-forming composition. The concentration at this time is preferably 0.1 to 50 mass%, more preferably 0.5 to 30 mass%. If the concentration is such, the viscosity is unlikely to increase, so that the operability is prevented from being impaired, and the amount of the solvent is not excessive, so that it is 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 manufacturing method differs depending on whether W is a carbon atom or a nitrogen atom. When W is a carbon atom, it can be obtained by 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 R in the following formula are 1 is 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 and aromatic aldehydes shown in the 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 mole number of Sumanene as the raw material.

[0081] The solvent used in reaction method 1 is not particularly limited as long as it is a solvent inert to the above 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, water, and the like, which can be used alone or in combination. 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 0.1 to 100 hours.

[0082] The reaction method and recovery method of Reaction Method 1 can be the methods described above as methods that can be used in the case of X1.

[0083] The compound used in the preparation of the organic film material obtained by reaction method 1 has a substituent R 1 Aromatic aldehydes having a substituent other than the above may be used alone or in combination according to the required performance. For example, aromatic aldehydes having a substituent that contributes to the improvement of flattening properties and film-forming properties, and a substituent that contributes to etching resistance and heat resistance may be combined in any ratio.

[0084] As the acid catalyst used in the condensation reaction of the sumenene oxide and aromatic amines shown in the reaction method 2, inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, heteropolyacids, etc., organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc., 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, titanium (IV) oxide, etc. can be used. The amount of the catalyst 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 intermediate bis(indole-2,3-diones).

[0085] The solvent used in the 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; chlorine-based 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 0.1 to 100 hours.

[0086] The reaction method and recovery method of Reaction Method 2 can be the methods described above as methods that can be used in the case of X1.

[0087] In the preparation of the compound used in the organic film-forming composition obtained by the reaction method 2, the substituent R 1 Aromatic amines having substituents other than those mentioned above can be used alone or in combination according to the required performance. For example, aromatic amines having substituents that contribute to the improvement of flattening properties and film-forming properties, and those that contribute to etching resistance and heat resistance can be combined in any ratio.

[0088] When X is X3, R 2 The manufacturing method differs depending on whether R is a hydrogen atom or an alkyl group.2 When R is a hydrogen atom, it is called sumane oxide and R 3 It can be obtained by reacting with an organometallic reagent represented by R 2 When R is an alkyl group, the sumanene derivative obtained in Step 1 is used as an intermediate. 2 The alcohol can be obtained by a condensation reaction between alcohol-represented by -OH and alcohol-represented by condensation reaction between alcohol-represented by -OH and aromatic amines (Step 2). 2 , R 3 is the same as above, M is Li or MgX 5 , X 5 is a halogen atom.

[0089] [ka]

[0090] Examples of the organometallic reagent used in Step 1 include Grignard reagents, organolithium reagents, organozinc reagents, organotitanium reagents, etc., 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] In addition, organozinc reagents and organotitanium reagents can be prepared from the corresponding Grignard reagents or organolithium reagents by reaction with zinc halide, titanium(IV) halide, alkoxytitanium(IV), etc. Metal salt compounds may be present during the preparation of the organometallic reagents or during the reaction of the organometallic reagents with sumanene oxide. In this case, 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 above 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 and facilitate its preparation, and can also adjust the nucleophilicity and Lewis acidity of the reagent.

[0094] As the solvent used in the preparation of the above-mentioned organometallic reagent and the reaction with the sumanene oxide, ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, cyclopentyl methyl ether, etc., hydrocarbons such as benzene, toluene, xylene, mesitylene, hexane, heptane, octane, isooctane, etc., and aprotic polar solvents such as N,N,N',N'-tetramethylethylenediamine, hexamethylphosphoric triamide, N,N-dimethylformamide, etc. can be used alone or in combination.

[0095] The reaction temperature depends on the type 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 methods described above as methods that can be used in the case of X1.

[0097] Step 2 R 2The acid catalyst and solvent used in the condensation reaction with the alcohol represented by -OH can be the same as those used in the condensation reaction of the sumenene oxide and aromatic amines in (Reaction Method 2). In addition, the reaction method and recovery method can be the same as those described above as methods that can be used in the case of 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 capable of exhibiting 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 composition for forming an organic film of the present invention may further be blended with a modifier such as a blending compound, another polymer, etc. The modifier is mixed with the composition for forming an organic film of the present invention and plays a role in improving the film forming properties of spin coating and the filling properties on a substrate having a step.

[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, 3-hydroxynaphthalene-2-methyl carboxylate, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, and biphenyl. , bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborn-2-ene, α-pinene, β-pinene, limonene and other novolac resins, 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-A-2004-205685, fluorene bisphenol novolac resins described in JP-A-2005-128509, acenaphthylene copolymers described in JP-A-2005-250434, fullerenes having phenol groups described in JP-A-2006-227391, bisphenol compounds and novolac resins thereof described in JP-A-2006-293298, novolac resins of adamantanephenol compounds described in JP-A-2006-285095, bisnaphthol compounds and novolac resins thereof described in JP-A-2010-122656, and fullerene resin compounds described in JP-A-2008-158002.

[0103] The amount of the modifier to be added is preferably 0 to 1,000 parts by mass, and more preferably 0 to 500 parts by mass, based on 100 parts by mass of the compound represented by the general formula (1) of the present invention.

[0104] [Organic solvents] The organic solvent usable 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) to (0092) of JP-A-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 above-mentioned organic solvent can be applied by spin coating, and since it contains the compound represented by the general formula (1) of the present invention 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, as the organic solvent, an organic solvent having a boiling point of 180°C or higher to an organic solvent having a boiling point of less than 180°C (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, and chlorine-based solvents. Specific examples include 1,6-diacetoxyhexane, 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecal, 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 glycol 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 monomer 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, and 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 the boiling point being too low, and sufficient thermal fluidity can be obtained. In addition, 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 even after baking, so there is no risk of adversely affecting the organic film properties 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 remains in the organic film, leading to deterioration of the film properties such as etching resistance.

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

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

[0113] [Other additives] In the organic film-forming composition of the present invention, an acid generator can be added to further promote the curing reaction. The acid generator may be one that generates an acid by thermal decomposition or one that generates an acid by light irradiation, and any of these may be added. Specifically, the materials described in paragraphs (0061) to (0085) of JP-A-2007-199653 may be added, but are not limited thereto.

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

[0115] A surfactant can be added to the organic film-forming composition of the present invention in order to improve the coating property in spin coating. As the surfactant, for example, those described in (0142) to (0147) of JP-A-2009-269953 can be used.

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

[0117] In addition, a crosslinking agent may be added to the organic film-forming composition of the present invention in order to enhance the curability and further suppress intermixing with the upper layer film. The crosslinking agent is not particularly limited, and various known crosslinking agents may be widely 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, and more preferably 10 to 40 parts by mass, based on 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 the urea-based crosslinking agent include dimethoxymethylated dimethoxyethyleneurea, its alkoxy and / or hydroxyl 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 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 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] In addition, a plasticizer can be added to the organic film-forming composition of the present invention in order to further improve the flattening / 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, adipic esters, phosphates, trimellitates, and citrates, 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, and more preferably 10 to 200 parts by mass, based on 100 parts by mass of the compound represented by the general formula (1).

[0130] In addition, in the organic film-forming composition of the present invention, as an additive for imparting filling / flattening properties in the same manner as a plasticizer, for example, a liquid additive having a polyethylene glycol or polypropylene glycol structure, or a thermally decomposable polymer 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 is preferably used. This thermally decomposable polymer preferably contains a repeating unit having an acetal structure represented by the following general formula (DP1) or (DP2).

[0131] [ka] (In the formula, R 4 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, R 5 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 a semiconductor device.

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

[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 of a multi-layer resist film used in lithography or a planarizing film for semiconductor manufacturing.

[0135] In the present invention, the organic film-forming composition is coated on a substrate to be processed by spin coating or the like. By using spin coating or the like, good embedding properties can be obtained. After spin coating, the solvent is evaporated, and baking (heat treatment) is performed to promote a crosslinking reaction in order to prevent mixing with the resist upper layer film or the silicon-containing resist intermediate film. Baking is preferably performed at 100°C or higher and 600°C or lower for 10 to 600 seconds, more preferably at 200°C or higher and 500°C or lower for 10 to 300 seconds. Considering the influence on device damage and wafer deformation, the upper limit of the heating temperature in the lithography wafer process 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 on a workpiece by a spin coating method or the like as described above, and baking and hardening the organic film-forming composition in an atmosphere having 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. The atmosphere during baking may be air, but N 2 It is preferable to seal an inert gas such as Ar or He in order to prevent oxidation of the organic film. In order to prevent oxidation, it is necessary to control the oxygen concentration, which is preferably 1000 ppm or less, and more preferably 100 ppm or less. Preventing oxidation of the organic film during baking is preferable because it prevents the absorption from increasing and the etching resistance from decreasing.

[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 being processed. Therefore, it is extremely useful when forming a flat organic film on a workpiece having a structure or step having a height of 30 nm or more.

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

[0140] (Pattern formation method) In the present invention, as a pattern formation method by a three-layer resist process using such an organic film-forming composition, a pattern formation method can be provided which is a method for forming a pattern on a workpiece, the pattern formation method including at least a step of forming an organic film on the workpiece using the organic film-forming composition of the present invention, a step of forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material, a step of forming a resist upper layer film on the silicon-containing resist intermediate film using a photoresist composition, a step of forming a circuit pattern on the resist upper layer film, a step of transferring a pattern to the silicon-containing resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, a step of transferring a pattern to the organic film by etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask, and a step of forming a pattern on the workpiece by etching using the organic film to 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, so in the three-layer resist process, it is preferable that the dry etching of the organic film performed using the silicon-containing resist intermediate film as a mask is performed using an etching gas mainly composed of oxygen gas or hydrogen gas.

[0142] As the silicon-containing resist intermediate film in the above three-layer resist process, a polysiloxane-based intermediate film is also preferably used. By imparting an anti-reflection effect to the silicon-containing resist intermediate film, reflection can be suppressed. In particular, for 193 nm exposure, if a material containing many aromatic groups and having high etching selectivity with the substrate is used as the organic film, the k value becomes high and the substrate reflection becomes high, but by imparting absorption to the silicon-containing resist intermediate film to obtain an appropriate k value, it becomes possible to suppress reflection, and the substrate reflection can be reduced to 0.5% or less. As the silicon-containing resist intermediate film having an anti-reflection effect, anthracene is preferably used for 248 nm and 157 nm exposure, and polysiloxane with a pendant light-absorbing group having a phenyl group or a silicon-silicon bond and crosslinked by acid or heat is preferably used for 193 nm exposure.

[0143] An organic antireflective coating (BARC) may be formed on the silicon-containing resist intermediate film. In this case, a pattern can be formed on the workpiece by 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 BARC on the silicon-containing resist intermediate film, 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 silicon-containing resist intermediate film using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring a pattern to the BARC and the silicon-containing resist intermediate film by etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask, and etching the workpiece to which the pattern has been transferred to form a pattern on the workpiece.

[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 steps of: 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; transferring a pattern to the inorganic hard mask by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring a pattern to the organic film by etching using the inorganic hard mask on which the pattern has been formed as a mask; 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 an inorganic hard mask is formed on an organic film, a silicon oxide film, a silicon nitride film, and a silicon oxide nitride film (SiON film) can be formed by a CVD method, an ALD method, or the like. For example, a method for forming a silicon nitride film is described in JP-A-2002-334869 and WO-A-2004 / 066377. The thickness of the inorganic hard mask is preferably 5 to 200 nm, more preferably 10 to 100 nm. In addition, as the inorganic hard mask, a SiON film, which has a high effect as an anti-reflection film, is most preferably used. Since the substrate temperature when forming the SiON film is 300 to 500°C, the organic film in the lower layer needs to withstand a temperature 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, so that it is 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 the workpiece by the steps of: 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; transferring a pattern to the BARC and the inorganic hard mask by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring a 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.

[0147] As described above, a photoresist film may be formed on the inorganic hard mask as a resist top layer, but a BARC may be formed on the inorganic hard mask by spin coating, and a photoresist film may be formed on top of that. In particular, when a SiON film is used as the inorganic hard mask, the two-layer anti-reflection film of the SiON film and the BARC makes it possible to suppress reflection even in immersion exposure with a high NA exceeding 1.0. Another advantage of forming a BARC is that it has the effect of reducing the tailing of the photoresist pattern directly above the SiON film.

[0148] The resist upper layer film in the three-layer resist process may be either positive or negative, and may be the same as a commonly used photoresist composition. 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 upper layer film is not particularly limited, but is preferably 30 to 500 nm, more preferably 50 to 400 nm.

[0149] Examples of the 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 method for forming a circuit pattern on the resist upper layer film preferably uses 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 an alkali development or an organic solvent development as a 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 forms 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] The next etching of the workpiece, such as the workpiece substrate, can also be performed by a conventional method. For example, if the workpiece is SiO 2 For SiN or silica-based low dielectric constant insulating films, etching is primarily performed with fluorocarbon gases, while for p-Si, Al, or W, etching is primarily performed with chlorine- or bromine-based gases. When etching the substrate with fluorocarbon 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 with fluorocarbon 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, as the metal, silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof.

[0158] The workpiece is not particularly limited, and may be Si, α-Si, p-Si, SiO 2 The substrate may be made of a material such as SiN, SiON, W, TiN, or Al, or a substrate having a layer to be processed formed thereon. 2 Various low-k films and stopper films thereof such as SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, and Al-Si can be used, and can be formed to a thickness of preferably 50 to 10,000 nm, more preferably 100 to 5,000 nm. When forming a layer to be processed, the substrate and the layer to be processed are made of different materials.

[0159] In addition, it is preferable to use a workpiece having a structure or step having 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 laminated on a substrate 1 using the organic film-forming composition of the present invention, and then a silicon-containing resist intermediate film 4 is formed thereon, and a resist upper layer film 5 is formed thereon.

[0162] Next, as shown in FIG. 1(B), a desired portion 6 of the resist upper layer film is exposed, and PEB and development are performed to form a resist pattern 5a (FIG. 1(C)). Using the obtained 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 obtained silicon-containing resist intermediate film pattern 4a as a mask to form an organic film pattern 3a (FIG. 1(E)). Furthermore, after 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 consecutively prior to etching of the silicon-containing resist intermediate film 4, or etching of only the BARC may be performed before etching of the silicon-containing resist intermediate film 4 by changing the etching device, for example.

[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. EXAMPLES

[0165] The present invention will be described in more detail below with reference to Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples, but the present invention 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] 1.2g of magnesium was placed in a flask, and the flask was heated with a heat gun under reduced pressure to degas and dehydrate. 20g of dehydrated THF and 2.0g of iodine were added under a nitrogen atmosphere and stirred. A solution of 5.0g of 2-bromonaphthalene dissolved in 10g of THF was added and stirred at 40℃ for 3 hours to obtain a THF solution of (C6).

[0170] (Synthesis Example 2) Synthesis of Sumanenes (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 solution, and the mixture was stirred at 40°C for 100 hours. A small amount of silica gel was then added, the mixture was dried under reduced pressure using an evaporator, and impurities were removed using silica gel column chromatography. The mixture was dissolved in methyl isobutyl ketone (MIBK), crystallized with hexane, and then collected and dried in vacuum at 70°C to obtain 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 that had been 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 washed with deionized water until it became neutral. The resulting organic layer was concentrated, dissolved in MIBK, and crystallized by adding methanol, filtered and washed, and then collected, and dried in vacuum at 70°C to obtain 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 CDCl 3 ):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 CDCl 3 ): 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 for 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 of 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 1 H-NMR (600MHz in CDCl 3):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 CDCl 3 ):162.513, 147.535, 147.453, 147.403, 146.084, 145.787, 145.733, 145.495, 143.406, 143.159, 141.578, 141.125, 141.008, 136.370, 136.288, 136.218, 136.132, 132.213, 132.134, 132.047, 132.014, 131.914, 131.827, 131.751, 130.75 5, 130.207, 129.989, 129.837, 129.775, 128.573, 128.531, 128.334, 128.058, 127.815, 127.757, 127.516, 126.978, 12 5.776, 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 for 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 of 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 CDCl 3 ):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 CDCl 3 ):158.139, 147.871, 147.547, 146.013, 145.667, 145.517, 145.237, 145.074, 143.373, 143.321, 139.383, 139.296, 132.048, 132.045, 131.347, 131.324, 131.298, 131.275, 130.171, 129.8 87, 129.847, 129.728, 128.270, 128.119, 127.902, 127.822, 127.608, 123.491, 123.343, 120.8 01, 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 O 3 +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 that had been degassed by nitrogen bubbling, and 50 ml of THF were added. Then, 10.0 g of 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 washed with deionized water until it became neutral. The resulting organic layer was concentrated, dissolved in MIBK, crystallized by adding hexane, filtered, washed, and dried in vacuum 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 CDCl 3 ):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 CDCl 3 ):154.911, 146.056, 122.961, 81.228, 71.604, 59.549, 24.629ppm GPC: Mw / Mn = 1.07 MS(Calcd for 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 1M THF solution of phenylmagnesium bromide (C5) was added and stirred overnight. 50 g of an aqueous solution of ammonium chloride 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 it became neutral. The mixture was dried under reduced pressure using an evaporator, and impurities were removed by silica gel column chromatography. The mixture was dissolved in MIBK, crystallized with hexane, filtered, washed, and vacuum dried at 70°C to obtain 1.4 g (80%) of (A5). The instrumental analysis data for this compound are shown below.

[0185] IR (ATR method): 3533, 3381, 3051, 3001, 1611, 1510, 1476, 1451, 1359cm -1 1 H-NMR (600MHz in CDCl 3 ): 7.28(15H, m), 7.02(6H, s), 5.72(3H, s)ppm 13 C-NMR (150MHz in CDCl 3 ): 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] Except for using 2-naphthylmagnesium bromide (C6) prepared in Synthesis Example 1 instead of phenylmagnesium bromide (C5), the same procedure as for compound (A5) was followed to obtain 2.4 g (71%) of (A6). 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 CDCl 3 ):8.03~7.09 (21H, m), 7.04 (6H, s), 5.78 (3H, s)ppm 13 C-NMR (150MHz in CDCl 3 ):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 stirred under reflux for 3 hours. 150 ml of toluene was added and washed with deionized water until it became neutral. The resulting organic layer was concentrated, dissolved in MIBK, and crystallized by adding hexane, followed by filtration and washing to obtain 0.93 g (88%) of (A7). 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 CDCl 3 ): 8.03~7.09 (21H, m), 7.04 (6H, s), 3.06 (9H, s) 13 C-NMR (150MHz in CDCl 3): 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] In 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. 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 by 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 CDCl 3 ): 6.08(2H, d), 6.50(2H, d), 6.92~7.30(12H, m)7.61(2H, d)ppm 13 C-NMR (150MHz in CDCl 3): 163.186, 162.893, 148.965, 148.800, 148.466, 148.399, 148.365, 148.300, 148.286, 148.211, 148.191, 148.139, 147.941, 147.851, 136.213, 136.279, 136.173, 136. 122, 130.235, 130.220, 130.099, 130.077, 126.801, 126.635, 126.603, 126.516, 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 obtain a homogeneous solution. 21.0 g of dodecylbenzenesulfonic acid was added, heated to 140°C, and reacted for 16 hours. The reaction solution was added to methanol for crystallization, 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 the 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, 14.0 g of 4-ethynylbenzaldehyde (C1) was added and stirred at room temperature for 15 hours. 150 ml of MIBK was added and washed with deionized water until it became neutral. The obtained organic layer was concentrated, dissolved in MIBK, crystallized by adding methanol, filtered, washed, and dried in 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 the 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 it became neutral. The organic layer obtained was concentrated, dissolved in MIBK, and crystallized by adding hexane, filtered, washed, and dried in vacuum at 70°C to obtain (R4). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and were found 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 Sumanen (B1), 5.5 g of n-tetrabutylammonium bromide, 100 ml of 30 wt% aqueous sodium hydroxide solution that had been degassed by nitrogen bubbling, and 50 ml of THF were added. Then, 10.0 g of allyl bromide was added and stirred at room temperature for 45 hours. 150 ml of MIBK was added and washed with deionized water until it became neutral. The obtained organic layer was concentrated, dissolved in MIBK, crystallized by adding hexane, 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 the compounds (R1) to (R5) for comparison were dissolved in the ratios shown in Table 1 using 1,6-diacetoxyhexane (boiling point 260°C) (S1) and tripropylene glycol monomethyl ether (boiling point 242°C) (S2) as high boiling point organic solvents, propylene glycol monomethyl ether acetate (PGMEA) containing 0.1 mass% of FC-4430 (manufactured by Sumitomo 3M Limited) and cyclohexanone (CyHO), and filtered through a 0.1 μm fluorine resin filter to prepare compositions for forming organic films (UDL-1 to 15, comparative UDL-1 to 5). Note that for UDL-6, 8, and 10, a thermal acid generator (TAG) represented by the following formula was used.

[0206] [Table 1]

[0207] [ka]

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

[0209] [Table 2]

[0210] As shown in Table 2, the organic films using the compounds of the present invention (Examples 1-1 to 1-15) have a residual film rate of 99% or more after PGMEA treatment, and it is understood that a crosslinking reaction occurs by heat treatment, and sufficient solvent resistance is exhibited. From these results, it is understood that the compounds having a specific partial structure of the present invention have thermosetting properties. Comparing Examples 1-5, 1-7, and 1-9 with 1-6, 1-8, and 1-10, it is understood that the residual film rate increases by about 0.4 to 0.7% by adding a thermal acid generator compared to the compound alone, and a denser film is formed by the action of the acid catalyst. It was confirmed that the organic films using compounds having the same partial structure (Comparative Examples 1-2 to 1-4) and the organic film using a compound having a sumanene skeleton (Comparative Example 1-5) also exhibit solvent resistance.

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

[0212] [Table 3]

[0213] As shown in Table 3, when Examples 2-1 to 2-15 and Comparative Examples 2-1 to 2-4 are compared, it is found that the compound having a Sumanene structure has excellent film hardness. In addition, when Examples 2-5, 2-7, and 2-9 are compared with Examples 2-6, 2-8, and 2-10 in Examples 2-5 to 2-10, it is found that the hardness of Examples 2-6, 2-8, and 2-10 is higher, and thus it is found that the addition of a thermal acid generator improves the hardness and forms a dense film, as in Example 1. When Examples 2-1 and Comparative Example 2-2, Examples 2-3 and Comparative Example 2-3, and Examples 2-4 and Comparative Example 2-4, which have the same substituent structure, it is found that the compound having the Sumanene-containing structure of the present invention has higher hardness. This is due to the densification of the film caused by the Sumanene structure, and it can be presumed that this is due to the fact that Sumanene itself has a 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 allyl group, and can form a denser film. This is in accordance with the results of the solvent resistance test in Example 1, and it can be inferred that a denser film can be formed because the propargyl group substitution had better solvent resistance.

[0214] Examples 3-1 to 3-15 and Comparative Examples 3-1 to 3-5 (etching test) [CF 4 / CHF 3 Etching test using fluorine-based gas] The UDL-1 to 15 and Comparative UDL-1 to 5 were applied onto a silicon substrate and baked in air at 350° C. for 60 seconds to form an organic film with a thickness of 200 nm. Then, CF 4 / CHF 3 An etching test was performed using the above-mentioned gas, and the difference in the thickness of the organic film before and after etching was determined. The results are shown in Table 4. The etching was performed using a dry etching device TE-8500 manufactured by Tokyo Electron Limited.

[0215] The etching conditions are as follows. Chamber pressure 40.0Pa RF power 1,000W CHF 3Gas flow rate: 10ml / min CF 4 Gas flow rate: 100ml / min He gas flow rate: 200ml / min Time 20sec

[0216] [Table 4]

[0217] In Table 4, the CF of comparative UDL-1 4 / CHF 3 The film thickness reduction due to etching with the system gas is taken as 100%, and the film thickness reduction in each of the examples and comparative examples is expressed as a ratio. The smaller the ratio, the more excellent the etching resistance.

[0218] [O 2 Etching test using fluorine-based gas] The UDL-1 to 15 and Comparative UDL-1 to 5 were applied onto a silicon substrate and baked in air at 350° C. for 60 seconds to form an organic film with a thickness of 200 nm. 2 An etching test was performed using the above-mentioned gas, and the difference in the 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 device TE-8500 manufactured by Tokyo Electron Limited.

[0219] The etching conditions are as follows. Chamber pressure 40.0Pa RF power 100W O 2 Gas flow rate: 30ml / min N 2 Gas flow rate: 70ml / min Time 60sec

[0220] CF 4 / CHF 3 As in the etching test with the O system gas, in Table 4, 2The film thickness reduction due to etching with the system gas is taken as 100%, and the film thickness reduction in each of the examples and comparative examples is expressed as a ratio. The smaller the ratio, the more excellent the etching resistance.

[0221] As shown in Table 4, when Examples 3-1 to 3-15 are compared with Comparative Examples 3-1 to 3-4, CF 4 / CHF 3 Gases, O 2 In any of the etching tests using the system gas, the amount of reduction after etching of the film of the embodiment is equal to or smaller than that of the comparative example, and it can be seen that an organic film with excellent etching resistance is formed. In particular, the etching resistance of the Examples 3-1, 3-2, and 3-4, which do not contain a heteroatom structure, and the Examples 3-5 to 3-10, which have no heteroatom structure due to curing, was good. In addition, when comparing the etching resistance of the compounds having the same substituent structure as in Example 2, Example 3-1 and Comparative Example 3-2, Example 3-3 and Comparative Example 3-3, and Example 3-4 and Comparative Example 3-4, it can be seen that an organic film with excellent etching resistance is formed when using a compound having a sumanene structure when comparing the etching resistance of the compounds having the same substituent structure. Similarly, when comparing Example 3-4 and Comparative Example 3-5, which have a sumanene skeleton, Example 3-4 has better etching resistance, and it was confirmed that the propargyl group has a superior effect on etching resistance than the allyl group. As shown in Examples 1 and 2, it is considered that these have excellent solvent resistance and hardness, and therefore a denser film is formed.

[0222] Examples 4-1 to 4-15 and Comparative Examples 4-1 to 4-5 (Pattern Etching Test) The UDL1-1 to 1-15 and the comparative UDL1-1 to 1-5 were each formed of a SiO 2The organic film was formed on a 300 mm diameter Si wafer substrate and baked in air at 350°C for 60 seconds to 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 resist intermediate film with a thickness of 35 nm, and a resist top layer film material (ArF SL resist) was applied and baked at 105°C for 60 seconds to form a resist top layer film with a thickness of 100 nm. An immersion protective film (TC-1) was applied to the resist top layer film and baked at 90°C for 60 seconds to form a protective film with a thickness of 50 nm.

[0223] A resist upper 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 2,500 parts by mass of PGMEA containing 0.1% by mass of FC-430 (manufactured by Sumitomo 3M Limited), and filtering the resultant 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 intermediate film material (SOG-1) was prepared by dissolving 100 parts by mass of an ArF silicon-containing intermediate film 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 resultant mixture through a fluororesin filter having a pore size of 0.1 μm.

[0228] [ka]

[0229] Next, the resist was exposed to light using an ArF immersion exposure apparatus (Nikon Corporation; NSR-S610C, NA 1.30, σ 0.98 / 0.65, 35 degree dipole s-polarized illumination, 6% halftone phase shift mask) while changing the exposure dose, baked at 100°C for 60 seconds (PEB), and developed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds to obtain 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 equipment Telius, we processed the silicon-containing resist intermediate film by dry etching using the resist pattern as a mask, processed the organic film using the silicon-containing resist intermediate film as a mask, and processed the SiO 2 The film (workpiece) was processed in sequence.

[0231] The etching conditions are as follows. Transfer conditions for resist pattern onto SOG film (silicon-containing resist intermediate film): Chamber pressure 10.0Pa RF power 1,500W CF 4 Gas flow rate: 15sccm O 2 Gas flow rate: 75sccm Time 15sec

[0232] Conditions for transferring SOG film (silicon-containing resist intermediate film) to organic film: Chamber pressure 2.0Pa RF power 500W Ar gas flow rate: 75sccm O 2 Gas flow rate: 45sccm Time 120sec

[0233] SiO 2 Transfer conditions for film (workpiece): Chamber pressure 2.0Pa RF power: 2,200W C 5 F 12 Gas flow rate: 20sccm C 2 F 6 Gas flow rate: 10sccm Ar gas flow rate: 300sccm O 2 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] From the results of Examples 4-1 to 4-15, when UDL-1 to 15 are used as an organic film of a three-layer resist for immersion lithography, the resist shape after development is good in the pattern shape evaluation, and it is found to have a useful effect as an anti-reflection film. Similar results were also obtained in the comparative examples.

[0237] In the pattern shape after etching, the resist shape after development, the shape of the organic film after oxygen etching, and the shape after substrate processing etching were all good in all of the examples and comparative examples. On the other hand, the limit dimension without twist of the pattern after the transfer etching of the processed body changes according to the resist line width created by exposure, and the pattern twist occurred at a line width of about 33 nm in comparative example 4-1, but it can be seen that examples 4-1 to 4-15 using the compound of the present invention have no twist up to a pattern dimension of 30 nm or less, and have high twist resistance. When comparing the 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 can be seen that the organic film using the compound of the present invention having a sumanene structure has better twist resistance.

[0238] Examples 5-1 to 5-15 and Comparative Examples 5-1 to 5-5 (Embedding Characteristics) SiO 2 A dense hole pattern with a thickness of 500 nm and a diameter of 160 nm is formed on a SiO 2 UDL-1 to 15 were applied to the uneven substrate under the condition that the film thickness would be 80 nm on the flat substrate by baking at 350°C for 60 seconds to form an organic film. The substrate on which the organic film was formed was cut, and it was observed with a scanning electron microscope (SEM) whether the organic film was embedded to the bottom of the hole. 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 them were able to be filled well to the bottom of the hole, and sufficient filling characteristics can be expected even when there is a step in the workpiece, and it is found that they have useful characteristics 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 compositions for forming organic films (UDL-1, 4, 12 to 15) was applied to a SiO 2 After coating on a wafer substrate and baking in air at 350°C for 60 seconds, the step (delta in Figure 2) between the trench and non-trench parts of the organic film was observed using an atomic force microscope (AFM) NX10 manufactured by Park Systems. The results are shown in Table 7. In this evaluation, the smaller the step, the better the planarization characteristics. In this evaluation, a trench pattern with a depth of 0.10 μm was planarized using an organic film-forming composition with a normal film thickness of about 0.2 μm, which is a strict evaluation condition for evaluating the superiority or inferiority of the 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 a high-boiling organic solvent was not added, the steps in Examples 6-3 to 6-6 were the same 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) The organic film-forming compositions (UDL-1 to 15, Comparative UDL-1 to 5) were each applied onto a Si substrate, baked in nitrogen at 350°C for 60 seconds, and the film thickness was measured. After that, the film was further baked at 450°C for 60 seconds, and the film thickness was measured again. The film thickness reduction rate (%) was then measured 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 of the organic film 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, in Examples 7-1 to 7-15 in which organic films were formed using UDL-1 to 15 of the present invention, the film thickness reduction rate was suppressed to 3% or less, and it was found that the heat resistance was excellent. In addition, when comparing 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, it was found that the compound having the Sumanene structure has better heat resistance when comparing etching resistance between compounds having the same substituent structure. Furthermore, when comparing Example 7-4 and Comparative Example 7-5 as a comparison between Sumanene compounds, it was shown that Example 7-4 has better heat resistance, and the effectiveness of the propargyl group introduced in the present invention was also confirmed.

[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 the bare-Si substrates, hexamethyldisilazane (HMDS)-treated substrates, and SiON-treated substrates shown in Table 9, and baked at 350°C for 60 seconds in air to form organic films with a thickness of 200 nm. The organic films after formation were observed using an optical microscope (Nikon ECLIPSE L200) to check for coating abnormalities. 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 were formed without substrate dependency and without coating defects. In addition, in Comparative Examples 8-1 to 8-4, pinhole defects were not observed on substrates other than the bare-Si substrate. In Comparative Example 8-5, a film could be formed without dependency on the substrate, and the effect of improving the film formability by introducing 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 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 embodiment. The above-described embodiment is merely an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included in 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 portion.

Claims

[Claim 1] A compound represented by the following general formula (1): 【Chemistry 1】 (In the above general formula (1), X is any one of 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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