Composition for forming organic film, method for forming organic film, patterning process, and compound

Abstract

To provide an organic film-forming composition which is excellent in film-forming properties (in-plane uniformity) on a substrate (wafer) and in filling properties, suppresses humping during an EBR step, and is excellent in process tolerance when used as an organic underlayer film for a multilayer resist.SOLUTION: The composition for forming an organic film contains a resin or a compound (A) for forming an organic film, a compound (B) represented by general formula (1), and a solvent (C). Wherein R1 is a terminal group represented by the general formula (2), X is an n1-valent organic group having 2 to 50 carbon atoms, and n1 is an integer of 2 to 8. ) SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] As LSIs become more highly integrated and faster, pattern rules are becoming increasingly miniaturized. This is due to the increasing popularity of 5G high-speed communications and artificial intelligence (AI), which require high-performance devices to process these. The most advanced miniaturization technology is extreme ultraviolet (EUV) lithography with a wavelength of 13.5 nm, which is currently used to mass-produce 5 nm node devices. Furthermore, the use of EUV lithography is being considered for next-generation 3 nm node devices and the next-generation 2 nm node devices.

[0003] As resist patterns become thinner in this way, it becomes difficult to form patterns using the single-layer resist method, which is a typical method for forming resist patterns.As a method for processing fine patterns, it is known that a multi-layer resist method, in which patterns are formed by stacking films with different dry etching properties in order to form high aspect ratio patterns on uneven substrates, is superior.A three-layer resist method (Patent Documents 1 and 2) has been developed and put into practical use, which combines a photoresist layer made of an organic photosensitive polymer used in the single-layer resist method, an intermediate layer made of a silicon-based polymer or a silicon-based CVD film, and a lower layer made of an organic polymer.

[0004] In this three-layer resist method, for example, an organic film such as novolak is uniformly formed on a substrate to be processed as a resist underlayer, a silicon-containing film is formed on top of that as a resist middle layer, and a conventional organic photoresist film is formed on top of that as a resist upper layer. For dry etching using fluorine-based gas plasma, the organic resist upper layer has a good etching selectivity relative to the silicon-containing resist middle layer, so the resist pattern is transferred to the silicon-containing resist middle layer by dry etching using fluorine-based gas plasma. This method allows for pattern transfer to the silicon-containing film even when using a resist composition that is difficult to form a pattern with a sufficient thickness for directly processing the substrate to be processed, or a resist composition that does not have sufficient dry etching resistance for processing the substrate. Subsequent pattern transfer using dry etching using oxygen-based gas plasma allows for the formation of a novolak film pattern with sufficient dry etching resistance for processing.

[0005] Although many technologies for the organic underlayer film described above are already known (for example, Patent Document 3), with the recent advances in miniaturization, there is an increasing need for excellent filling properties in addition to dry etching properties. There is a need for organic underlayer film materials that can be uniformly formed on the underlying substrate to be processed, even on substrates or materials with complex shapes, and that have filling properties that enable the necessary patterns to be filled without voids.

[0006] The organic underlayer film described above is formed using a coater / developer capable of spin coating, EBR, baking, and other processes when manufacturing semiconductor substrates, etc. The EBR (Edge Bead Removal) process is a process in which, after a coating is formed on a substrate (wafer) by spin coating, the coating on the edge of the substrate is removed with a remover to prevent contamination of the coater / developer's substrate transfer arm. The remover used in the EBR process is a mixture of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether (30% by mass:70% by mass), which is widely used in the EBR process of resist films and resist underlayer films (silicon-containing intermediate films, organic underlayer films).

[0007] The remover used in the EBR process can cause a thick film thickness (hump) on the outer periphery of the organic underlayer film. Because humps can cause defects in the dry etching process used in substrate processing, there is a demand for organic underlayer films that suppress hump formation.

[0008] Resist materials used in photolithography using organic photosensitive polymers, as well as organic underlayer films, are applied in solution by spin coating or other methods, and then baked to evaporate the solvent, forming a film. As with organic underlayer films, the film thickness after baking must be uniform and flat, and the requirements for uniformity and flatness are becoming stricter every year.

[0009] In recent years, thicker resist films are required for 3D-NAND memory applications, and even greater flatness is required. As the film thickness increases, it becomes more difficult to achieve flatness within the film. Meanwhile, as miniaturization progresses, thinner films are being made, which increases the risk of pinhole defects and other defects.

[0010] The above describes examples of film materials using organic substances that are used in semiconductor processing materials, but even in film-forming materials that do not use organic substances, it would be a great industrial advantage to obtain a material that can form a film with uniform in-plane film thickness and without pinholes.

[0011] In recent years, the health effects of perfluoroalkyl substances (PFAS) have been pointed out, and there are moves to impose restrictions on the manufacture and sale of PFAS compounds under the European REACH. Perfluoroalkyl compounds have a wide range of uses, and due to their structural properties such as repelling water and oil, being resistant to heat and chemicals, and not absorbing light, they are used in a wide range of applications such as water repellents, surface treatment agents, emulsifiers, fire extinguishing agents, and coating agents, so there is an urgent need to develop alternative materials that do not contain the PFAS structure.

[0012] As an example of the above-mentioned material using a perfluoroalkyl compound, a surfactant having a fluoroalkyl group or a silicone chain is highly effective in reducing surface tension, and fluoroalkyl group surfactants are widely used, as they have a low risk of generating silicon-derived particles after dry ashing of the resist film (Patent Documents 3 and 4). Fluorine-based surfactants are also used not only in resist materials, but also in top coats formed on top of resists and in anti-reflective coatings formed on bottom layers of resists (Patent Document 5).

[0013] In view of future tightening of regulations, it is necessary to use materials that do not fall under PFAS regulations. For example, surfactants having trifluoromethoxy groups or pentafluorosulfanyl groups and their use have been proposed as surfactants mentioned above (Patent Document 6). In addition, in the field of resist materials, resist materials using photoacid generators have also been proposed (Patent Document 7). [Prior art documents] [Patent documents]

[0014] [Patent Document 1] Patent No. 4355943 etc. [Patent Document 2] Japanese Patent Application Laid-Open No. 2004-205685 [Patent Document 3] Japanese Patent Application Publication No. 6-186735 [Patent Document 4] Japanese Patent Application Publication No. 6-214380 [Patent Document 5] Japanese Patent Application Laid-Open No. 2010-139822 [Patent Document 6] Special Publication No. 2008-526792 [Patent Document 7] International Publication No. WO2023-223624 Summary of the Invention [Problem to be solved by the invention]

[0015] The present invention has been made in view of the above circumstances, and aims to provide a composition for forming an organic film that has excellent film-forming properties (in-plane uniformity) and filling properties on a substrate (wafer), suppresses humps during an EBR process, and has excellent process tolerance when used as an organic underlayer film for a multilayer resist, as well as a method for forming an organic film and a method for forming a pattern using the composition. [Means for solving the problem]

[0016] In order to solve the above problems, the present invention provides: The present invention provides a composition for forming an organic film, which comprises an organic film-forming resin or compound (A), a compound (B) represented by the following general formula (1), and a solvent (C): [ka] (In the formula, R1 is a terminal group represented by the following general formula (2), X is an n1-valent organic group having 2 to 50 carbon atoms, and n1 is an integer of 2 to 8.) [ka] (In the formula, R2 is a monovalent organic group, and the monovalent organic group contains a structure having at least a fluorine atom represented by any of the following general formulas (3). m1 is 1 or 2, and when m1 is 1, Z represents a single bond or a divalent organic group which may contain a heteroatom, and when m1 is 2, Z represents a trivalent organic group which may contain a heteroatom. * represents a bond.) [ka] (In the formula, * represents a bond.)

[0017] Such an organic film-forming composition makes it possible to form an organic film that has excellent in-plane uniformity and filling properties and that suppresses the formation of humps due to the effects of the remover in the EBR process. Furthermore, by introducing a structure having a fluorine atom as a partial structure into the terminal group of the compound (B), when the fluorine-containing compound (B) is used as an organic underlayer film, the fluorine-containing compound (B) is volatilized from the organic film surface and removed from the film by baking during cured film formation due to the action of the introduced terminal group via S, resulting in an organic film-forming composition that can form an organic film with excellent coatability for the silicon-containing intermediate film and excellent process tolerance.

[0018] Furthermore, the terminal group represented by the general formula (2) of the compound (B) is preferably one or more of the following general formulae (4) to (8). [ka] (wherein R2 is the same as above, and n2 represents an integer of 2 to 6.)

[0019] In the case of a composition for forming an organic film containing a compound having such a structure, the interaction of the fluorine structure can be adjusted by appropriately selecting the introduction form of the substituent R2 in the repeating unit, and therefore it is possible to adjust the function of the surfactant to match the compound, resin, or solvent type used in the composition for forming an organic film.

[0020] Furthermore, R2 of the compound (B) is preferably any one of the following general formula (9). [ka]

[0021] As mentioned above, chemical substance management related to PFAS regulations has been strengthened, and the fluorine atom, pentasulfanyl group, and aromatic groups substituted with pentasulfanyl groups shown above are not classified as PFAS under REACH. Furthermore, difluoromethoxy groups and aromatic groups substituted with fluorine atoms are not classified as PFAS under OECD. Therefore, organic film-forming compositions using the compounds of the present invention as surfactants not only provide excellent film-forming properties, but are also expected to be environmentally friendly materials.

[0022] The weight average molecular weight of the compound (B) is preferably 300 to 4,000.

[0023] Within this weight-average molecular weight range, it is possible to form an organic film with excellent film-forming and filling properties, and it is also possible to control the contact angle of the film surface after film formation within an appropriate range, thereby forming an organic underlayer film suitable for use in a multilayer resist process.

[0024] The ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn of the compound (B) in terms of polystyrene, as determined by gel permeation chromatography, is preferably 1.00≦Mw / Mn≦1.20.

[0025] Within this Mw / Mn (molecular weight distribution) range, the contact angle of the film surface after film formation can be controlled within an appropriate range, making it possible to form an organic underlayer film suitable for use in a multilayer resist process.

[0026] Furthermore, when the organic film-forming resin or compound (A) is taken as 100 parts by mass, the content of the compound (B) is preferably 0.01 to 5 parts by mass.

[0027] A composition for forming an organic film containing the compound (B) in such an amount is preferred because the organic film formed will have better in-plane uniformity.

[0028] The present invention also provides a method for forming an organic film used in the manufacturing process of a semiconductor device, which comprises spin-coating the above-mentioned organic film-forming composition on a substrate to be processed, and heat-treating the substrate coated with the organic film-forming composition at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds, thereby forming a cured film.

[0029] The organic film-forming composition of the present invention is particularly useful when it is used to fill complex patterns on a substrate to be processed by spin coating, to form an organic film with excellent in-plane uniformity, and to remove the organic film from the edges while suppressing humps in the EBR process.

[0030] The present invention also provides a pattern formation method, which includes forming an organic film on a workpiece using the above-mentioned organic film-forming composition, forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms, forming a resist upper layer film on the resist intermediate film using a resist upper layer film material consisting of a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the resist intermediate film on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0031] The present invention also provides a pattern formation method, which includes forming an organic film on a workpiece using the above-mentioned organic film-forming composition, forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms, forming an organic antireflective film or an adhesive film on the resist intermediate film, forming a resist upper layer film on the organic antireflective film or adhesive film using a resist upper layer film material comprising a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern by etching onto the organic antireflective film or adhesive film and the resist intermediate film using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern by etching onto the organic film using the resist intermediate film on which the pattern has been transferred as a mask, and further transferring the pattern onto the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0032] The present invention also provides a pattern formation 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 resist upper layer film material comprising 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 circuit 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 transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0033] The present invention also provides a pattern formation 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 an organic antireflective film or an adhesive film on the inorganic hard mask, forming a resist upper layer film on the organic antireflective film or adhesive film using a resist upper layer film material comprising a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern by etching onto the organic antireflective film or adhesive film and the inorganic hard mask using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern by etching onto the organic film using the inorganic hard mask on which the pattern has been transferred as a mask, and further transferring the pattern onto the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0034] As described above, the organic film-forming composition of the present invention can be suitably used in various pattern formation methods, such as a three-layer resist process using a silicon-containing resist intermediate film or an inorganic hard mask, and a four-layer resist process using an organic antireflective film or an adhesive film in addition to these. Such a pattern formation method of the present invention makes it possible to transfer and form the circuit pattern of the resist upper layer film onto the workpiece with high precision.

[0035] The inorganic hard mask is preferably formed by a CVD method or an ALD method.

[0036] In the pattern formation method of the present invention, for example, an inorganic hard mask can be formed by such a method.

[0037] In forming the circuit pattern, it is preferable to form the circuit pattern by lithography using light having a wavelength of 10 nm or more and 300 nm or less, direct drawing with an electron beam, nanoimprinting, or a combination thereof.

[0038] In forming the circuit pattern, it is preferable to develop the circuit pattern using an alkali developer or an organic solvent.

[0039] In the pattern forming method of the present invention, such circuit pattern forming means and developing means can be suitably used.

[0040] It is also preferable that the workpiece is a semiconductor device substrate, or a semiconductor device substrate on which any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film is formed.

[0041] In this case, the metal constituting the workpiece 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.

[0042] The pattern forming method of the present invention makes it possible to form a pattern by processing the above-mentioned workpiece.

[0043] The present invention also provides a compound represented by the following general formula (1): [ka] (In the formula, R1 is a terminal group represented by the following general formula (2), X is an n1-valent organic group having 2 to 50 carbon atoms, and n1 is an integer of 2 to 8.) [ka] (In the formula, R2 is a monovalent organic group, and the monovalent organic group contains a structure having at least a fluorine atom represented by any of the following general formulas (3). m1 is 1 or 2, and when m1 is 1, Z represents a single bond or a divalent organic group which may contain a heteroatom, and when m1 is 2, Z represents a trivalent organic group which may contain a heteroatom. * represents a bond.) [ka] (In the formula, * represents a bond.)

[0044] Such a compound makes it possible to form an organic film that has excellent in-plane uniformity and filling properties and that suppresses the formation of humps due to the influence of the remover in the EBR process. Furthermore, by introducing a structure having a fluorine atom as a partial structure into the terminal group of the compound, when such a fluorine-containing compound is used as an organic underlayer film, the compound is volatilized from the organic film surface and removed from the film by baking during cured film formation due to the action of the introduced terminal group via S, and therefore can form an organic film with excellent coatability for the silicon-containing intermediate film, and is a compound that can be used in an organic film-forming composition with excellent process tolerance.

[0045] Furthermore, the terminal group represented by the general formula (2) is preferably one or more of the following general formulae (4) to (8). [ka] (wherein R2 is the same as above, and n2 represents an integer of 2 to 6.)

[0046] A compound having such a structure can enhance the interaction between fluorine atoms due to the action of the fluorine atom-containing substituent R2 introduced into the terminal group, and when the compound of the present invention is used as a surfactant, it can impart good film-forming properties.

[0047] Furthermore, it is preferable that R2 is any one of the following general formula (9). [ka]

[0048] As mentioned above, compounds with the above-mentioned fluorine structure are expected to be environmentally friendly materials, particularly those that can comply with recent PFAS regulations. [Effects of the Invention]

[0049] As described above, the present invention can provide an organic film-forming composition that exhibits excellent film-forming properties (in-plane uniformity) and filling characteristics on a substrate (wafer), excellent film-forming properties on an organic film when used as an organic underlayer film, and suppresses hump formation during the EBR process. Furthermore, by combining specific terminal groups, the composition can be applied to a variety of organic film-forming materials. In particular, the organic film-forming composition of the present invention exhibits excellent film-forming properties, filling characteristics, and suppression of hump formation during the EBR process. Therefore, it is extremely useful as an organic film material used in multilayer resist processes, such as a two-layer resist process, a three-layer resist process using a silicon-containing resist interlayer or an inorganic hard mask, or a four-layer resist process using a silicon-containing resist interlayer or an inorganic hard mask and an organic antireflective film or adhesive film, or as a film-forming material for semiconductor device manufacturing, such as a photoresist material or a silicon-containing resist interlayer material. Therefore, the organic film-forming method of the present invention can form an organic film with suppressed hump formation, thereby enabling the efficient production of semiconductor devices, etc. Furthermore, the selection of a specific substituent structure can be expected to reduce environmental impact. [Brief explanation of the drawings]

[0050] [Figure 1] 1 is an example of a graph showing the height of humps measured using a contact profiler in a composition for forming an organic film in which humps are suppressed. [Figure 2] 1 is an example of a graph showing the height of humps measured using a contact profiler in an organic film-forming composition in which humps are not suppressed. [Figure 3] 1A to 1C are explanatory diagrams illustrating an example of a pattern formation method using a three-layer resist process according to the present invention. [Figure 4] FIG. 1 is an explanatory diagram of a method for evaluating filling characteristics in an example. DETAILED DESCRIPTION OF THE INVENTION

[0051] As mentioned above, there has been a demand for a material that not only provides film-forming properties as an organic film material but also has a surfactant effect with a low environmental impact. There has also been a demand for the development of an organic film-forming composition that, when used as an organic underlayer film material, has excellent film-forming properties (in-plane uniformity) and filling properties on a substrate (wafer), and that suppresses humps during the EBR process.

[0052] Typically, when forming an organic film, a resin for forming the organic film and additives are dissolved in an organic solvent to form a composition, which is then applied using a coater / developer onto a substrate on which structures, wiring, etc. have been formed. The composition is spread as the substrate rotates, and the composition at the edges is removed in an EBR process, followed by baking to form the organic film.

[0053] If the surfactant effect of the above composition is insufficient, uneven distribution of the surfactant in the film occurs, resulting in the formation of voids when filling holes or trenches with very high aspect ratios. In addition, if the resin or additives used to form the organic film have poor solubility in the remover used in the EBR process, humps may form on the periphery of the organic film.

[0054] The present inventors further conducted extensive research and found that by incorporating a compound having a specific terminal structure into a composition for forming an organic film, a composition for forming an organic film having excellent film-forming properties, high-level embedding properties, and hump suppression during the EBR process can be obtained, thereby completing the present invention. Furthermore, by selecting a specific substituent structure, it is expected that the environmental load will be reduced, and the composition for forming an organic film will be industrially useful.

[0055] That is, the present invention is a composition for forming an organic film, which comprises an organic film-forming resin or compound (A), a compound (B) represented by the above general formula (1), and a solvent (C).

[0056] The present invention will be described in detail below, but the present invention is not limited thereto.

[0057] [Compound] The compound of the present invention is a compound represented by the following general formula (1), which is compound (B) used in the organic film-forming composition of the present invention described below (hereinafter referred to as compound (B)). [ka] (In the formula, R1 is a terminal group represented by the following general formula (2), X is an n1-valent organic group having 2 to 50 carbon atoms, and n1 is an integer of 2 to 8.) [ka] (In the formula, R2 is a monovalent organic group, and the monovalent organic group contains a structure having at least a fluorine atom represented by any of the following general formulas (3). m1 is 1 or 2, and when m1 is 1, Z represents a single bond or a divalent organic group which may contain a heteroatom, and when m1 is 2, Z represents a trivalent organic group which may contain a heteroatom. * represents a bond.) [ka] (In the formula, * represents a bond.)

[0058] Examples of X in the general formula (1) of the compound (B) include the following. Among these, those in which n1 is an integer of 3 or greater are preferred, and compounds in which n1 = 4 or n1 = 6 are even more preferred. When n1 = 3 or greater, an excellent surfactant effect can be exhibited due to the interaction of the fluorine structure represented by R2 in the terminal group structure.

[0059] [ka]

[0060] [ka]

[0061] In general formula (2) representing R1, the number of carbon atoms in the organic group represented by Z, which may contain a divalent or trivalent heteroatom, is not particularly limited, but may be, for example, 1 to 20. Furthermore, in general formula (2), the monovalent organic group represented by R2 is also not particularly limited as long as it contains a structure having a fluorine atom represented by any of the above general formulas (3), but may be, for example, a monovalent organic group having 1 to 30 carbon atoms which may contain a heteroatom.

[0062] The fluorine-containing substituent R2 contained in the terminal group of the compound (B) is preferably an aromatic group substituted with a fluorine atom, an aromatic group substituted with a trifluoromethoxy group, an aromatic group substituted with a pentasulfanyl group, or an aromatic group substituted with a pentasulfanyloxy group, as shown in the following general formula (9):

[0063] [ka]

[0064] The above structure is expected to be used as a compound for forming organic films with a fluorine structure that does not fall under PFAS regulations.

[0065] The terminal group of the compound (B) represented by the general formula (2) is preferably one or more of the following general formulae (4) to (8).

[0066] [ka] (wherein R2 is the same as above, and n2 represents an integer of 2 to 6.)

[0067] [Compound: Terminal structure represented by general formula (4)] Examples of the terminal structure represented by general formula (4) include the following: Among these, those having the terminal structure represented by (9) are preferred.

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] [Compound: Method for producing a terminal structure represented by general formula (4)] The compound having the terminal structure represented by general formula (4) can be produced by an addition reaction of a halide, mesylate, or tosylate having R2 as a substituent with a thiol compound in the presence of a base catalyst, as shown below.

[0073] [ka] (In the formula, X1 represents a halide, mesylate, or tosylate, and X, R2, and n1 are the same as above.)

[0074] Examples of the base catalyst used in this case 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 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 thiol groups in the raw material.

[0075] The solvent used in this reaction is not particularly limited as long as it is inert to the reaction, but examples include ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; aromatic solvents such as benzene, toluene, and xylene; acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, and water, which can be used alone or in combination. These solvents can be used in an amount of 0 to 2000 parts by mass per 100 parts by mass of the reaction raw materials, and the reaction temperature is preferably from -50°C to the boiling point of the solvent, more preferably from room temperature to 150°C. The reaction time is appropriately selected from the range of 0.1 to 100 hours.

[0076] Reaction methods include charging the thiol compound, the halide, mesylate, or tosylate having R2 as a substituent, and the catalyst all at once, dispersing or dissolving the thiol compound and the halide, mesylate, or tosylate having R2 as a substituent, and then adding the catalyst all at once or diluting it with a solvent and adding it dropwise, or dispersing or dissolving the catalyst, and then adding the thiol compound and the halide, mesylate, or tosylate having R2 as a substituent all at once or diluting it with a solvent and adding it dropwise. After the reaction is complete, the product may be used as is as an organic film material, or it may be recovered by diluting it with an organic solvent and then separating and washing to remove unreacted raw materials, catalyst, etc. present in the system.

[0077] The organic solvent used here is not particularly limited as long as it can dissolve the compound and separate into two layers when mixed with water. Examples include hydrocarbons such as hexane, heptane, benzene, toluene, and xylene; esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate; ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, and methyl isobutyl ketone; ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, and ethyl cyclopentyl methyl ether; chlorinated solvents such as methylene chloride, chloroform, dichloroethane, and trichloroethylene; and mixtures thereof. The washing water used here is typically what is known as deionized water or ultrapure water. The number of washes may be one or more times, but washing 10 or more times does not necessarily provide the desired effect, so washing is preferably performed 1 to 5 times.

[0078] In order to remove unreacted raw materials or acidic components from the system during separation and 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.

[0079] Furthermore, in order to remove unreacted raw materials, metal impurities, or basic components from the system during separation and 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, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid.

[0080] The separation washing with the basic aqueous solution and the acidic aqueous solution may be carried out either alone or in combination. From the viewpoint of removing metal impurities, the separation washing is preferably carried out in the order of the basic aqueous solution and the acidic aqueous solution.

[0081] After the separation washing with the basic aqueous solution or acidic aqueous solution, washing with neutral water may be carried out subsequently. The number of washings may be one or more times, but is preferably about 1 to 5 times. As the neutral water, the above-mentioned deionized water or ultrapure water may be used. The number of washings may be one or more times, but if the number of washings is too few, the basic components and acidic components may not be removed. Washing 10 or more times does not necessarily provide the effect of washing alone, so it is preferably about 1 to 5 times.

[0082] Furthermore, the reaction product after the separation operation can be recovered as a powder by concentrating the solvent to dryness or crystallizing it under reduced or normal pressure, but it can also be left in a solution state with a moderate concentration to improve operability when preparing an organic film material. The concentration in this case is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by weight. At such a concentration, the viscosity is unlikely to increase, preventing a loss of operability, and the amount of solvent is not excessive, making it economical.

[0083] 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.

[0084] Furthermore, in the production of compounds obtained by this method, it is possible to use multiple types of halides, mesylates, or tosylates each having R2 as a substituent, or to use a combination of halides, tosylates, and mesylates different from R2, and various combinations can be selected according to the required performance.

[0085] [Compound: Terminal structure represented by general formula (5)] Examples of the terminal structure R2 in general formula (5) include the following: Among these, those having the terminal structure shown in (9) are preferred.

[0086] [ka]

[0087] [ka]

[0088] [ka]

[0089] [ka]

[0090] [Compound: Method for producing a terminal structure represented by general formula (5)] The compound having the terminal structure represented by general formula (5) can be produced by an addition reaction between an allyl ether compound and a thiol compound using the radical initiator shown below.

[0091] [ka] (X, R2, and n1 in the formula are the same as above)

[0092] Examples of the radical initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2-azobis(2-methylpropionate), 1,1'-azobis(1-acetoxy-1-phenylethane), benzoyl peroxide, lauroyl peroxide, etc. The amount of these initiators added is preferably 0.01 to 25 mol % based on the total amount of monomers to be polymerized.

[0093] Examples of organic solvents used in the addition reaction include toluene, benzene, THF, diethyl ether, dioxane, cyclohexane, cyclopentane, methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), and γ-butyrolactone (GBL). The reaction temperature is preferably 50 to 150°C, more preferably 60 to 100°C. These solvents can be used in an amount of 0 to 2000 parts by mass per 100 parts by mass of the reaction raw materials. The reaction temperature is preferably from -50°C to the boiling point of the solvent, more preferably room temperature to 150°C. The reaction time is appropriately selected from the range of 0.1 to 100 hours. The reaction time is preferably 2 to 24 hours, taking into account the half-life of the radical initiator, and more preferably 2 to 18 hours from the viewpoint of production efficiency.

[0094] The radical initiator may be added to a previously prepared thiol compound solution and then supplied to the reaction vessel, or an initiator solution may be prepared separately from the thiol compound solution, and each may be supplied independently to the reaction vessel.

[0095] A plurality of allyl ether compounds may be used depending on the required performance, and the number of allyl ether compounds may be appropriately selected depending on the required performance, as in the case of the reaction with the halide.

[0096] The reaction solution obtained by the above-described production method may be used as is for an organic film-forming composition, or the reaction solution may be added to a poor solvent, and the resulting powder may be treated as a final product through a purification process such as reprecipitation to obtain a powder. It is preferable to dissolve the powder obtained by the purification process in a solvent to remove the radical initiator and unreacted raw materials, and treat the resulting compound solution as a final product. The resulting powder may also be recovered by subjecting it to separation and water washing, as described in the method for producing the terminal structure represented by general formula (4).

[0097] [Compound: Terminal structure represented by general formula (6)] Examples of the terminal structure represented by general formula (6) include the following: Among these, those having a terminal structure represented by general formula (9) are preferred.

[0098] [ka]

[0099] [ka]

[0100] [ka]

[0101] [Compound: Method for producing a terminal structure represented by general formula (6)] The compound having the terminal structure represented by general formula (6) can be produced by an addition reaction between an allyl ether compound and a thiol compound using the radical initiator shown below.

[0102] [ka] (X, R2, and n1 in the formula are the same as above)

[0103] The reaction can be carried out by simply using an allyl ether compound corresponding to the terminal structure of general formula (6) as a raw material, and the product can be produced by the method described for producing the terminal structure represented by general formula (5). Multiple types of allyl ether compounds can be used in these reactions, and they can be appropriately selected according to the required performance, for example, by combining an allyl ether corresponding to the terminal structure of general formula (5) with an allyl ether compound corresponding to the terminal structure of general formula (6).

[0104] [Compound: Terminal structure represented by general formula (7)] Examples of the terminal structure represented by general formula (7) include the following: Among these, those having a terminal structure represented by general formula (9) are preferred.

[0105] [ka]

[0106] [ka]

[0107] [ka]

[0108] [ka]

[0109] [ka]

[0110] [ka]

[0111] [ka]

[0112] [ka]

[0113] [ka]

[0114] [ka]

[0115] [ka]

[0116] [ka]

[0117] [ka]

[0118] [ka]

[0119] [Compound: Method for producing a terminal structure represented by general formula (7)] The compound having the terminal structure represented by the general formula (7) can be produced by an addition reaction with an acrylate using a base catalyst as shown below.

[0120] [ka] (X, R2, and n1 in the formula are the same as above)

[0121] The reaction can be carried out by the method described for producing the terminal structure represented by general formula (4), simply by replacing the raw material with an acrylate compound corresponding to the terminal structure of general formula (7) with an allyl ether compound. Multiple types of acrylate compounds can be used simultaneously in these reactions, and they can be selected appropriately according to the required performance, for example, by combining an acrylate corresponding to the terminal structure of general formula (7) with an acrylate compound corresponding to the terminal structure of general formula (8).

[0122] [Compound: Terminal structure represented by general formula (8)] Examples of the terminal structure represented by general formula (8) include the following: Among these, those having a terminal structure represented by general formula (9) are preferred.

[0123] [ka]

[0124] [ka]

[0125] [ka]

[0126] [ka]

[0127] [ka]

[0128] [ka] (wherein n2 is the same as above)

[0129] [Compound: Method for producing a terminal structure represented by general formula (8)] The compound having the terminal structure represented by the general formula (8) can be produced by an addition reaction with an acrylate using a base catalyst as shown below.

[0130] [ka] (X, R2, n1, and n2 in the formula are the same as above)

[0131] The reaction can be carried out by the method described for producing the terminal structure represented by general formula (4), simply by replacing the raw material with an acrylate compound corresponding to the terminal structure of general formula (8) with an allyl ether compound. Multiple types of acrylate compounds can be used simultaneously in these reactions, and they can be selected appropriately according to the required performance, for example, by combining an acrylate corresponding to the terminal structure of general formula (7) with an acrylate compound corresponding to the terminal structure of general formula (8).

[0132] [Alternative method for producing compounds having terminal structures represented by general formulas (6) and (8)] As another method for producing the compounds having the terminal structure represented by the general formulas (6) and (8), there can be mentioned a method in which a compound (Step 1) having an acetylacetone structure (a structure in which R2 corresponds to a hydrogen atom) is synthesized in the same manner as in the method for producing the compounds represented by the general formulas (6) and (8) described above, and then the compound is obtained by an addition reaction (Step 2) with a halide, mesylate, tosylate, or the like having R2 as a substituent in the presence of a base catalyst.

[0133] [1] Another method for producing a compound having a terminal structure represented by general formula (6) (Step 1) Addition reaction with allyl ether compounds [ka] (Step 2) Addition reaction with halides, etc.

[0134] [ka]

[0135] [2] Another method for producing a compound having a terminal structure represented by general formula (8) (Step 1) Addition reaction with acrylate compounds [ka] (Step 2) Addition reaction with halides, etc.

[0136] [ka] (In the following formula, X1 represents a halide, mesylate, or tosylate, and X, R2, n1, and n2 are the same as above.)

[0137] When using the above production method, if the reaction in Step 2 is carried out using a halide or other compound with a single R2 structure, it is possible to produce a compound in which only R2 has been introduced as a substituent, as with the reacted allyl ether compounds and acrylic compounds described in the previous section. However, if multiple R2s are used, a mixture of compounds with multiple terminal structures will be produced, as shown below. Conversely, in the reaction product with an allyl ether compound or acrylic compound in which multiple R2s have been introduced, as described in the previous section, only the terminal structure will change, and multiple types of structures will not be introduced to the same substituent on the acetylacetone, resulting in compounds that differ only in the terminal structure. In this case, the reaction rate for the entire reaction site can be controlled by adjusting the overall feed ratio, and substituents corresponding to multiple or single R2s can be combined to suit the required performance.

[0138] (1) Alternative method: Products synthesized using halides with multiple R2 as substituents [ka] [ka]

[0139] (2) The method described in the preceding paragraph: A product obtained by synthesis using an allyl ether compound or an acrylic compound having multiple R2 groups as substituents. [ka] [ka] (X, X1, R2, and n2 are the same as above. R2' is a substituent other than R2 such that R2' ≠ R2. The above describes the compounds produced when two types of halides (R2-X1, R2'-X1) are used (for ease of understanding, the case where n1 = 1 is shown). When n1 ≥ 2, the number of substituent combinations increases and the situation becomes even more complicated.)

[0140] The compound can be obtained by the method described in the method for producing the terminal structure represented by general formula (4), simply by changing the addition reaction with an allyl ether and the addition reaction with an acrylic compound in Step 1 to correspond to the compound obtained in Step 1. The compound obtained in Step 1 can be used in the addition reaction in Step 2.

[0141] Step 2 can be produced by the same method as in the method for producing the terminal structure represented by general formula (4), except that the substrate is changed to a compound represented by R2-X1.

[0142] The weight-average molecular weight of the compound (B) is preferably 300 to 4000. If the weight-average molecular weight is 300 or more, a decrease in the compounding effect due to volatilization or the like can be suppressed, and a sufficient compounding effect can be obtained. Furthermore, if the weight-average molecular weight is 4000 or less, residue in the film can be suppressed, and an organic film with even better process tolerance can be formed. Furthermore, the weight-average molecular weight is preferably 3500 or less. If the weight-average molecular weight is 3500 or less, the risk of the surfactant remaining in the film can be further reduced. Furthermore, the weight-average molecular weight is preferably 500 or more. If the weight-average molecular weight is 500 or more, the compound can remain in the film system without volatilizing during film formation, and a sufficient surfactant effect can be exerted.

[0143] The ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn of the compound (B) in terms of polystyrene, as determined by gel permeation chromatography, is preferably 1.00≦Mw / Mn≦1.20.

[0144] Normally, for a single compound, the ratio Mw / Mn is theoretically 1.00, but for example, in compound (B) contained in the organic film-forming composition of the present invention, it is possible to combine multiple types of terminal structure R1 structures and multiple types of terminal structure substituents R2, and as described in the alternative production method, combining multiple types results in a complex mixture. Also, in gel permeation chromatography, the separation performance of compounds is affected by errors in compound properties such as compound polarity and measurement conditions such as column temperature and pressure. Considering this, it is difficult to achieve a Mw / Mn of 1.00 strictly even for a single compound. Therefore, in order to distinguish from compounds having a distribution in the ratio Mw / Mn, the above range is defined as an index showing monomolecularity.

[0145] The compounds used in the organic film-forming compositions obtained by these methods can be manufactured by controlling the introduction ratio or by using multiple R2 structures to meet the required performance requirements. Furthermore, the manufacturing method for the compounds can be modified to meet the required performance requirements. For example, compounds having a side chain structure that contributes to improved planarization characteristics, or a fluorine-containing substituent that controls surface tension and other properties to change the surfactant properties can be arbitrarily combined. Therefore, these compounds not only have excellent surfactant properties that contribute to improved film-forming properties, but also achieve high levels of compatibility between film-forming properties, embedding properties, and other properties when used in an underlayer film as an organic film-forming composition.

[0146] [Composition for organic film formation] The composition for forming an organic film contains the organic film-forming resin or compound (A), the compound (B) explained above, and the solvent (C).

[0147] In the composition for forming an organic film of the present invention, the (B) compound, the (A) organic film-forming resin or compound, and the (C) solvent can each be used alone or in combination of two or more.

[0148] The compound (B) of the present invention functions as a surfactant that imparts excellent film-forming properties and high leveling performance. Its applications are not limited to organic underlayer films, but can be used in general photolithography coating materials, such as photosensitive resist materials and materials for forming top coats on resist films. Furthermore, it can be applied not only to organic film-forming materials but also to silicon-containing resist intermediate films, and can be used as a surfactant suitable for expressing versatile film-forming properties that can be applied to various film-forming materials.

[0149] The compound (B) of the present invention can be used alone or in combination of two or more. The amount of these compounds added is preferably such that the content of the heavy compound (B) is 0.01 to 5 parts by mass per 100 parts by mass of the organic film-forming resin or compound (A).

[0150] [(A) Organic film-forming resin or compound] The organic film-forming resin or compound (A) used in the organic film-forming composition of the present invention is not particularly limited as long as it is a resin or compound that satisfies the film-forming properties and curing properties of spin coating. However, from the viewpoints of etching resistance, optical properties, heat resistance, etc., a resin or compound containing an aromatic skeleton is more preferred.

[0151] Examples of the aromatic skeleton include benzene, naphthalene, anthracene, pyrene, indene, fluorene, furan, pyrrole, thiophene, phosphole, pyrazole, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, carbazole, etc. Among these, benzene, naphthalene, fluorene, and carbazole are particularly preferred.

[0152] Examples of the organic film-forming resin or compound (A) used in the present invention include resins containing the following structures described in JP-A Nos. 2012-001687 and 2012-077295.

[0153] [ka] (In formula (1), the ring structures Ar1 and Ar2 represent a benzene ring or a naphthalene ring. X represents a single bond or an alkylene group having 1 to 20 carbon atoms. m represents 0 or 1. n represents any natural number such that the molecular weight is 100,000 or less. Note that the symbols in the formula apply only within this formula.)

[0154] [ka] (In formula (2), the ring structures Ar1 and Ar2 represent a benzene ring or a naphthalene ring. n represents any natural number such that the weight average molecular weight, as calculated using polystyrene standards by gel permeation chromatography, is 100,000 or less. Note that the symbols in the formula are used only within this formula.)

[0155] Further examples of the (A) organic film-forming resin or compound used in the present invention include resins containing the following structures described in JP-A Nos. 2004-264710, 2005-043471, 2005-250434, 2007-293294, and 2008-065303.

[0156] [ka] (In formula (3) and formula (4), R 1 and R 2 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an aryl group; R 3 represents an alkyl group having 1 to 3 carbon atoms, a vinyl group, an allyl group, or an aryl group which may be substituted, n represents 0 or 1, and m represents 0, 1, or 2. The symbols in the formulae apply only within the formulae.

[0157] [ka] (In formula (5), R1 is a monovalent atom or group other than a hydrogen atom, and n is an integer of 0 to 4. However, when n is 2 to 4, multiple R1s may be the same or different. R2 and R3 are independently a monovalent atom or group. X is a divalent group. Note that the symbols in the formula apply only within this formula.)

[0158] [ka] In formula (6), R1 is a hydrogen atom or a methyl group. R2 is a single bond, a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 10 carbon atoms, and may have any of ether, ester, lactone, and amide. R 3 , R 4 are each a hydrogen atom or a glycidyl group. X represents a polymer of any one of hydrocarbons containing an indene skeleton, cycloolefins having 3 to 10 carbon atoms, and maleimide, and may have any one of ethers, esters, lactones, and carboxylic acid anhydrides. R 5 , R6 R is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 7 is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a hydroxy group, or an alkoxycarbonyl group. p and q are each an integer of 1 to 4. r is an integer of 0 to 4. a, b, and c are in the ranges of 0.5≦a+b+c≦1, 0≦a≦0.8, 0≦b≦0.8, 0.1≦a+b≦0.8, and 0.1≦c≦0.8, respectively. Note that the symbols in the formula apply only within this formula.

[0159] [ka] (In formula (7), R1 represents a hydrogen atom or a monovalent organic group, and R2 and R3 each independently represent a monovalent atom or a monovalent organic group. Note that the symbols in the formula apply only within this formula.)

[0160] Specific examples of the organic film-forming resin or compound (A) used in the present invention include resins containing the following structures described in JP-A Nos. 2004-205685, 2007-171895, and 2009-014816.

[0161] [ka] (In formula (8) and formula (9), R 1 ~R 8 are each independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group having 1 to 6 carbon atoms, an optionally substituted alkoxy group having 1 to 6 carbon atoms, an optionally substituted alkoxycarboxyl group having 2 to 6 carbon atoms, an optionally substituted aryl group having 6 to 10 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, an isocyanate group, or a glycidyl group. m and n are positive integers. Note that the symbols in the formula apply only within this formula.

[0162] [ka] (In formula (10), R 1 , R 6is a hydrogen atom or a methyl group. R 2 and R 3 and R 4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a hydroxy group, an acetoxy group or an alkoxycarbonyl group, or an aryl group having 6 to 10 carbon atoms, and R 5 is a condensed polycyclic hydrocarbon group having 13 to 30 carbon atoms, -O-R 7 , -C(=O)-O-R 7 , -O-C(=O)-R 7 , or -C(=O)-NR 8 -R 7 where m is 1 or 2, n is an integer of 0 to 4, and p is an integer of 0 to 6. R 7 is an organic group having 7 to 30 carbon atoms, and R 8 is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Z is any one of a methylene group, -O-, -S-, and -NH-. a, b, c, d, and e are respectively in the ranges of 0 < a < 1.0, 0 ≤ b ≤ 0.8, 0 ≤ c ≤ 0.8, 0 ≤ d ≤ 0.8, 0 ≤ e ≤ 0.8, and 0 < b + c + d + e < 1.0. The symbols in the formula are applicable only within this formula.)

[0163] [Chemical Formula] (In Formula (11), n represents 0 or 1. R 1 represents an optionally substituted methylene group, an optionally substituted alkylene group having 2 to 20 carbon atoms, or an optionally substituted arylene group having 6 to 20 carbon atoms. R 2 represents a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms. R 3 to R 7 represent a hydroxyl group, an optionally substituted alkyl group having 1 to 6 carbon atoms, an optionally substituted alkoxy group having 1 to 6 carbon atoms, an optionally substituted alkoxycarbonyl group having 2 to 10 carbon atoms, an optionally substituted aryl group having 6 to 14 carbon atoms, or an optionally substituted glycidyl ether group having 2 to 6 carbon atoms. R 9represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic alkyl ether group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Note that the symbols in the formulae apply only within this formula.)

[0164] Examples of the formula (11) include the following resins:

[0165] [ka]

[0166] [ka]

[0167] Examples of the organic film-forming resin or compound (A) used in the present invention include resins containing the following structures described in JP-A Nos. 2007-199653, 2008-274250, and 2010-122656.

[0168] [ka] (In formula (12), R 1 and R 2 are independently the same or different hydrogen atoms, linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, or alkenyl groups having 2 to 10 carbon atoms, and R 3 is a single bond or an alkylene group having a linear, branched or cyclic structure and having 1 to 30 carbon atoms, which may have a bridged cyclic hydrocarbon group, a double bond, a heteroatom or an aromatic group having 6 to 30 carbon atoms; R 4 and R 5 are each independently a hydrogen atom or a glycidyl group, and n is an integer of 1 to 4. The symbols in the formula are applicable only within this formula.

[0169] [ka] (In formula (13), R 1 and R 2 are independently the same or different hydrogen atoms, linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, or alkenyl groups having 2 to 10 carbon atoms, and R 3 is a single bond or an alkylene group having a linear, branched or cyclic structure and having 1 to 30 carbon atoms, which may have a bridged cyclic hydrocarbon group, a double bond, a heteroatom or an aromatic group having 6 to 30 carbon atoms; R 4 and R 5 are each independently a hydrogen atom or a glycidyl group, and R 6 is a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms. The symbols in the formula are only applicable within this formula.

[0170] [ka] (In formula (14), ring Z 1 and ring Z 2 is a fused polycyclic aromatic hydrocarbon ring, R 1a , R 1b , R 2a , and R 2b are the same or different and represent a substituent. k1 and k2 are the same or different and represent an integer of 0 or 1 to 4, m1 and m2 are each an integer of 0 or 1 or more, and n1 and n2 are each an integer of 0 or 1 or more, provided that n1+n2≧1. The symbols in the formulae are only applicable within this formula.

[0171] [ka] (In formula (15), R 1 , R 2 R are the same or different and are hydrogen atoms, linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, or alkenyl groups having 2 to 10 carbon atoms. 3 , R 4 are hydrogen atoms or glycidyl groups, and R 5 is a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms, and R 6 , R7 is a benzene ring or a naphthalene ring. p and q are each 1 or 2. n is 0 < n ≤ 1. The symbols in the formula are applicable only within this formula.)

[0172] Examples of the resin represented by formula (15) include, for example, the following resins.)

[0173] [Chemical formula]

[0174] [Chemical formula]

[0175] [Chemical formula]

[0176] [Chemical formula]

[0177] Examples of the resin or compound (A) for forming an organic film used in the present invention include resins containing the following structures described in JP-A-2012-214720.)

[0178] [Chemical formula] (In formula (16), the ring structures Ar1 and Ar2 represent a benzene ring or a naphthalene ring. x and z each independently represent 0 or 1. The symbols in the formula are applicable only within this formula.)

[0179] Examples of the resin or compound (A) for forming an organic film used in the present invention include resins described in JP-A-2014-29435.)

[0180] [Chemical formula] (In formula (17), A represents a structure having carbazole, B represents a structure having an aromatic ring, and C represents a structure having a hydrogen atom, an alkyl group, or an aromatic ring, and B and C may form a ring together. The combined structure of A, B, and C contains 1 to 4 carboxyl groups or salts thereof, or carboxylate ester groups. Note that the symbols in the formula apply only within this formula.)

[0181] Furthermore, examples of the organic film-forming resin or compound (A) used in the present invention include polymers containing a unit structure represented by the following formula (18) and a unit structure represented by the following formula (19) described in WO 2012 / 077640, in which the molar ratio of the unit structure represented by formula (18) to the unit structure represented by formula (19) is 3 to 97:97 to 3.

[0182] [ka] In formula (18), R1 and R2 each independently represent a hydrogen atom, a halogen atom, a nitro group, an amino group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination of these groups which may contain an ether bond, a ketone bond, or an ester bond. R3 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination of these groups which may contain an ether bond, a ketone bond, or an ester bond. represents a combination of these groups. R4 represents a hydrogen atom, or an aryl group having 6 to 40 carbon atoms which may be substituted with a halogen atom, a nitro group, an amino group, or a hydroxy group, or a heterocyclic group; R5 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, a nitro group, an amino group, or a hydroxy group, or an aryl group having 6 to 40 carbon atoms, or a heterocyclic group; R4 and R5 may together form a ring; n1 and n2 each represent an integer of 1 to 3; and the symbols in the formula are applicable only within this formula.

[0183] [ka] In formula (19), Ar represents an aromatic ring group having 6 to 20 carbon atoms, R6 represents a hydroxy group, R7 represents a hydrogen atom, a halogen atom, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination of these groups which may contain an ether bond, a ketone bond, or an ester bond, and R8 may be substituted with a hydrogen atom, a halogen atom, a nitro group, an amino group, or a hydroxy group. R8 represents an aryl group or heterocyclic group having 6 to 40 carbon atoms, R9 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, a nitro group, an amino group, or a hydroxy group, or an aryl group or heterocyclic group having 6 to 40 carbon atoms, and R8 and R9 may together form a ring. n6 represents an integer of 1 to p, and n7 represents an integer of p-n6, where p represents the maximum number of substituents that can be substituted on the aromatic ring group Ar. The symbols in the formula are only applicable within this formula.

[0184] Examples of the organic film-forming resin or compound (A) used in the present invention include polymers containing a unit structure represented by the following formula (20) described in WO 2010 / 147155.

[0185] [ka] (In formula (20), R1 and R2 are each selected from the group consisting of a hydrogen atom, a halogen group, a nitro group, an amino group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, or the aryl group represents a group which may contain an ether bond, a ketone bond, or an ester bond; R3 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group Alternatively, the aryl group represents a group which may contain an ether bond, a ketone bond, or an ester bond; R4 represents an aryl group or heterocyclic group having 6 to 40 carbon atoms which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxy group; R5 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an aryl group or a heterocyclic group having 6 to 40 carbon atoms which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxy group; R4 and R5 may form a ring together with the carbon atoms to which they are bonded; and n1 and n2 are each an integer of 1 to 3. Note that the symbols in the formula apply only within this formula.

[0186] Examples of the (A) organic film-forming resin or compound used in the present invention include novolak resins obtained by reacting one or more phenols, such as phenol, cresol, xylenol, catechol, resorcinol, hydroquinone, pyrogallol, hydroxyquinol, and phloroglucinol, with one or more aldehyde sources, such as formaldehyde, paraformaldehyde, and trioxane, using an acidic catalyst; and resins containing a repeating unit structure represented by the following formula (21), which are described in WO 2012 / 176767.

[0187] [ka] (In formula (21), A represents a hydroxy-substituted phenylene group derived from polyhydroxybenzene, and B represents a monovalent fused aromatic hydrocarbon ring group in which 2 to 6 benzene rings are fused. Note that the symbols in the formula apply only within this formula.)

[0188] Examples of the organic film-forming resin or compound (A) used in the present invention include novolak resins having a fluorene or tetrahydrospirobiindene structure described in JP-A Nos. 2005-128509, 2006-259249, 2006-259482, 2006-293298, and 2007-316282, which contain a repeating unit structure represented by the following formula (22-1) or (22-2):

[0189] [ka] (In formula (22-1) and formula (22-2), R 1 , R 2 , R 6 , R 7 are independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an allyl group, or a halogen atom; R 3 , R 4 , R 8 , R 9 are independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms or a glycidyl group, and R 5 , R 14 are independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. n, m, p and q are integers of 1 to 3. R 10 ~R 13 are independently a hydrogen atom, a halogen atom, a hydroxy group, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms. Note that the symbols in the formula apply only within this formula.)

[0190] The organic film-forming resin or compound (A) used in the present invention can be, for example, a reaction product obtained by the method described in JP 2012-145897 A. More specifically, a polymer obtained by condensing one or more compounds represented by the following general formula (23-1) and / or (23-2) with one or more compounds represented by the following general formula (24-1) and / or (24-2) and / or their equivalents can be exemplified.

[0191] [ka] (In the general formula (23-1) and the general formula (23-2), R 1 ~R 8 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an isocyanato group, a glycidyloxy group, a carboxyl group, an amino group, an alkoxy group having 1 to 30 carbon atoms, an alkoxycarbonyl group having 1 to 30 carbon atoms, an alkanoyloxy group having 1 to 30 carbon atoms, or an optionally substituted saturated or unsaturated organic group having 1 to 30 carbon atoms. 1 ~R 4 or R 5 ~R 8 Two substituents arbitrarily selected from the following may be bonded to form a cyclic substituent. The symbols in the formula are applicable only within this formula.)

[0192] [ka] (In general formula (24-1) and general formula (24-2), Q is an organic group having 1 to 30 carbon atoms which may be substituted, and two Qs arbitrarily selected in the molecule may be bonded to form a cyclic substituent. n1 to n6 are the numbers of each substituent, and n1 to n6 = 0, 1, 2, and hydroxybenzaldehyde is excluded in formula (24-1). In addition, in formula (24-2), the relationships 0≦n3+n5≦3, 0≦n4+n6≦4, 1≦n3+n4≦4 are satisfied. Note that the symbols in the formulas apply only within this formula.)

[0193] Further, examples of the polymers include those obtained by condensing one or more compounds represented by the above general formula (23-1) and / or (23-2), one or more compounds represented by the above general formula (24-1) and / or (24-2) and / or equivalents thereof, and one or more compounds represented by the following general formula (25) and / or equivalents thereof.

[0194] [ka] (In formula (25), Y represents a hydrogen atom or a monovalent organic group having 30 or less carbon atoms which may have a substituent, and formula (25) is different from general formula (24-1) and general formula (24-2). Note that the symbols in the formula apply only within this formula.)

[0195] Examples of the organic film-forming resin or compound (A) used in the present invention include compounds containing the following structure described in JP-A-2017-119671.

[0196] [ka] (In formula (26-1), R is a single bond or an organic group having 1 to 50 carbon atoms, X is a group represented by the following general formula (26-2), and m1 is an integer satisfying 2≦m1≦10. Note that the symbols in the formula apply only within this formula.)

[0197] [ka] (In the formula, X 2 is a divalent organic group having 1 to 10 carbon atoms, n1 is 0 or 1, n2 is 1 or 2, and X 3 is a group represented by the following general formula (26-3), and n5 is 0, 1, or 2. The symbols in the formula apply only within this formula. [ka] (In the formula, R 10is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom on the benzene ring in the formula may be substituted with a methyl group or a methoxy group. Note that the symbols in the formula apply only within this formula.

[0198] Examples of compounds containing the above structure include the following compounds.

[0199] [ka]

[0200] Examples of the organic film-forming resin or compound (A) used in the present invention include polymers having a repeating unit represented by the following general formula (27-1), which are described in JP-A-2019-044022.

[0201] [ka] In formula (27-1), AR1 and AR2 are benzene rings or naphthalene rings which may have a substituent, and R 1 , R 2 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R 1 and R 2 If is an organic group, R 1 and R 2 may form a cyclic organic group by bonding intramolecularly. n is 0 or 1, and when n=0, AR1 and AR2 do not form a bridged structure between the aromatic rings of AR1 and AR2 via Z, and when n=1, AR1 and AR2 form a bridged structure between the aromatic rings of AR1 and AR2 via Z, and Z is either a single bond or the following formula (27-2). Y is a group represented by the following formula (27-3). Note that the symbols in the formula apply only within this formula. [ka] [ka] (In the formula, R 3is a single bond or a divalent organic group having 1 to 20 carbon atoms, and R 4 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and the dashed line represents a bond. Note that the symbols in the formula are only applicable within this formula.

[0202] Examples of polymers having a repeating unit represented by the above general formula (27-1) include the following polymers.

[0203] [ka]

[0204] [ka]

[0205] (A) The organic film-forming resin or compound may be synthesized by a known method, or a commercially available product may be used.

[0206] The amount of the (A) organic film-forming resin or compound is not particularly limited as long as the organic film-forming composition satisfies the film-forming properties of spin coating. Preferably, the amount of the (A) organic film-forming resin or compound is 10 to 40 parts by weight, more preferably 10 to 30 parts by weight, and even more preferably 10 to 25 parts by weight, per 100 parts by weight of the organic film-forming composition. For example, when filling holes or trenches with extremely high aspect ratios in 3D NAND memory architecture with an organic film-forming composition, a large amount of the organic film-forming resin is required. However, such organic film-forming compositions have high viscosity, which can degrade the in-plane uniformity and filling properties after spin coating. Even with the above-mentioned (A) organic film-forming resin blend ratio, the organic film-forming composition of the present invention can be suitably applied because it can form organic films with excellent in-plane uniformity and filling properties.

[0207] Furthermore, the content of the (B) polymer is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the (A) organic film-forming resin or compound. When the organic film-forming composition contains the polymer in such a content, the formed organic film has better in-plane uniformity.

[0208] [(C) Solvent] The solvent (C) that can be used in the organic film-forming material of the present invention is not particularly limited as long as it can dissolve the (A) organic film-forming resin or compound and the (B) compound, and is preferably one that can also dissolve the acid generator, crosslinking agent, surfactant, etc., which will be described later. Specifically, solvents with a boiling point of less than 180°C, such as those described in paragraphs (0091) and (0092) of JP-A No. 2007-199653, can be used. Among these, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclopentanone, cyclohexanone, and mixtures of two or more of these are preferably used.

[0209] The content of the (C) solvent is 200 to 10,000 parts by mass, more preferably 300 to 5,000 parts by mass, per 100 parts by mass of the (A) organic film-forming resin or compound. By setting the content within this range, the concentration can be adjusted according to the film thickness to be consumed.

[0210] Furthermore, in the organic film-forming material of the present invention, a high-boiling solvent having a boiling point of 180° C. or higher can be added to the above-mentioned solvent having a boiling point of less than 180° C. (a mixture of a solvent having a boiling point of less than 180° C. and a solvent having a boiling point of 180° C. or higher). The high-boiling organic solvent is not particularly limited as long as it can dissolve the organic film-forming compound, and may be any of hydrocarbons, alcohols, ketones, esters, ethers, chlorinated solvents, etc., but specific examples include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, 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 diacetate, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, propylene glycol diacetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,Examples of the diester include 6-hexanediol diacetate, triethylene glycol diacetate, γ-butyrolactone, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, and dibutyl adipate, and these may be used alone or in combination.

[0211] The boiling point of the high-boiling solvent may be appropriately selected according to the temperature at which the organic film-forming material is heat-treated, and the boiling point of the high-boiling solvent to be added is preferably 180°C to 300°C, and more preferably 200°C to 300°C. Such a boiling point prevents the solvent from volatilizing too quickly during baking (heat treatment) due to a boiling point that is too low, thereby ensuring sufficient thermal fluidity. Furthermore, such a boiling point is so high that the solvent does not remain in the film after baking without volatilizing, and therefore does not adversely affect film properties such as etching resistance.

[0212] Furthermore, when a high-boiling point solvent is used, the blending amount of the high-boiling point solvent is preferably 1 to 30 parts by mass per 100 parts by mass of a solvent having a boiling point of less than 180° C. If the blending amount is within this range, there is no risk that the blending amount is too small to impart sufficient thermal fluidity during baking, or that the blending amount is too large to remain in the film and lead to deterioration of film properties such as etching resistance.

[0213] In the case of such an organic film-forming material, the addition of a high-boiling point solvent to the above-mentioned organic film-forming resin or compound gives it thermal fluidity, thereby making it an organic film-forming material that also has high-level filling / planarizing properties.

[0214] [Other ingredients] In addition, an acid generator or crosslinking agent can be added to the organic film-forming composition of the present invention to further promote the crosslinking reaction. Acid generators include those that generate acid upon thermal decomposition and those that generate acid upon light irradiation, and either can be added. Specific examples of acid generators include those described in paragraphs

[0061] to

[0085] of JP 2007-199653 A. The above acid generators can be used alone or in combination of two or more. When an acid generator is added, the amount added is preferably 0.05 to 50 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the (A) organic film-forming resin or compound. This amount promotes the crosslinking reaction and enables the formation of a dense film.

[0215] Specific examples of crosslinking agents include those described in paragraphs

[0055] to

[0060] of JP 2007-199653 A. Crosslinking agents can be used singly or in combination of two or more. The amount of crosslinking agent added is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, per 100 parts by mass of (A) organic film-forming resin or compound. This amount enhances curability and further suppresses intermixing with the overlying film.

[0216] To further improve the in-plane uniformity during spin coating, a surfactant other than the compound (B) of the present invention may be added to the organic film-forming composition of the present invention. Specific examples of surfactants include those described in paragraphs

[0142] to

[0147] of JP 2009-269953 A. The above surfactants can be used alone or in combination of two or more. When a surfactant is added, the amount added is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the organic film-forming resin or compound. This amount enables the formation of an organic film with excellent in-plane uniformity.

[0217] Furthermore, a basic compound can be added to the organic film-forming composition of the present invention to improve storage stability. The basic compound acts as an acid quencher to prevent a small amount of acid generated by the acid generator from promoting a crosslinking reaction. Specific examples of such basic compounds include those described in paragraphs

[0086] to

[0090] of JP 2007-199653 A. The basic compounds can be used alone or in combination of two or more. When an acid generator is added, the amount added is preferably 0.05 to 50 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the (A) organic film-forming resin or compound. This amount can improve the storage stability of the organic film-forming composition.

[0218] As described above, the organic film-forming composition of the present invention is an organic film-forming composition that is excellent in suppressing humps during the EBR process. Therefore, the organic film-forming composition of the present invention is extremely useful as a resist underlayer film material (organic film material) for multilayer resist processes such as a two-layer resist process, a three-layer resist process using a silicon-containing resist interlayer or a silicon-containing inorganic hard mask interlayer, and a four-layer resist process using a silicon-containing resist interlayer or a silicon-containing inorganic hard mask interlayer and an organic antireflective film or adhesive film.

[0219] [Organic film formation method] The present invention provides a method for forming an organic film used in the manufacturing process of a semiconductor device, which comprises spin-coating the above-described composition for forming an organic film of the present invention onto a substrate to be processed, and then heat-treating the substrate coated with the composition for forming an organic film at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds to harden the composition, thereby forming an organic film.

[0220] In this organic film formation method, the organic film-forming composition of the present invention is first spin-coated onto a substrate to be processed. By using the spin-coating method, excellent embedding properties can be obtained. After removing the coating from the edges in the EBR process, baking (heat treatment) is performed to promote the crosslinking reaction. This baking process also evaporates the solvent in the composition, preventing mixing even when forming a resist top layer or a silicon-containing resist intermediate layer on the organic film.

[0221] Baking is performed at a temperature of 100°C to 600°C for 10 to 600 seconds, preferably at a temperature of 200°C to 500°C for 10 to 300 seconds. Considering the effect on device damage and wafer deformation, the upper limit of the heating temperature in the lithography wafer process is preferably 600°C or less, more preferably 500°C or less. Heat treatment under these conditions promotes the crosslinking reaction, making it possible to form an organic film that does not mix with the film formed on top.

[0222] [Pattern formation method] A pattern forming method using the organic film-forming composition of the present invention will be described below.

[0223] [Trilayer resist process using silicon-containing resist interlayer] In the present invention, there is provided a pattern forming method, comprising the steps of: forming an organic film on a workpiece using the organic film-forming composition described above; 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 resist upper layer film material comprising 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 circuit pattern has been formed as a mask; transferring the pattern to the organic film by etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; Furthermore, the present invention provides a pattern forming method in which the organic film onto which the pattern has been transferred is used as a mask to transfer the pattern onto the workpiece by etching.

[0224] The workpiece is preferably a semiconductor device substrate, or the semiconductor device substrate on which any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal carbide oxide film, and a metal oxynitride film is formed. More specifically, although not particularly limited, substrates such as Si, α-Si, p-Si, SiO, SiN, SiON, W, TiN, and Al, and the substrate on which the above-mentioned metal film or the like is formed as a workpiece layer, can be used.

[0225] The work layer may be a low-k film or a stopper film thereof, such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, or Al-Si, and may be formed to a thickness of typically 50 to 10,000 nm, particularly 100 to 5,000 nm. When forming the work layer, the substrate and the work layer are made of different materials.

[0226] It is preferable to use silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof as the metal constituting the workpiece.

[0227] When forming an organic film on a workpiece using the organic film-forming composition of the present invention, the above-described organic film-forming method of the present invention may be applied.

[0228] Next, a resist interlayer (silicon-containing resist interlayer) is formed on the organic film using a resist interlayer material containing silicon atoms. A polysiloxane-based interlayer material is preferred as the silicon-containing resist interlayer material. By imparting anti-reflective properties to the silicon-containing resist interlayer, reflection can be reduced. For 193 nm exposure, in particular, using a material containing many aromatic groups as the organic film-forming composition and exhibiting high etching selectivity with the substrate increases the k value and increases substrate reflection. However, by providing the silicon-containing resist interlayer with an absorption that results in an appropriate k value, reflection can be reduced, reducing substrate reflection to 0.5% or less. For silicon-containing resist interlayers with anti-reflective properties, anthracene is preferred for 248 nm and 157 nm exposure, while for 193 nm exposure, polysiloxanes with pendant light-absorbing groups having phenyl groups or silicon-silicon bonds and crosslinkable by acid or heat are preferred.

[0229] Next, a resist top layer film is formed on the silicon-containing resist intermediate film using a resist top layer film material composed of a photoresist composition. The resist top layer film material may be either positive or negative, and the same materials as commonly used photoresist compositions can be used. After spin-coating the resist top layer film material, it is preferable to prebake 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 top layer film pattern. The thickness of the resist top layer film is not particularly limited, but is preferably 30 to 500 nm, and particularly preferably 50 to 400 nm.

[0230] Next, a circuit pattern (resist upper layer film pattern) is formed on the resist upper layer film, preferably by lithography using light with a wavelength of 10 nm or more and 300 nm or less, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[0231] Examples of exposure light include high-energy rays with a wavelength of 300 nm or less, specifically far ultraviolet rays, KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F2 laser light (157 nm), Kr2 laser light (146 nm), Ar2 laser light (126 nm), soft X-rays (EUV) of 3 to 20 nm, electron beams (EB), ion beams, X-rays, and the like.

[0232] In forming the circuit pattern, it is preferable to develop the circuit pattern using an alkali developer or an organic solvent.

[0233] Next, the circuit pattern is formed on the resist upper layer film as a mask, and the pattern is transferred to the silicon-containing resist intermediate film by etching. The etching of the silicon-containing resist intermediate film using the resist upper layer film pattern as a mask is preferably carried out using a fluorocarbon gas. This allows the silicon-containing resist intermediate film pattern to be transferred.

[0234] Next, the pattern is transferred to the organic film by etching using the silicon-containing resist intermediate film with the transferred pattern as a mask. Because the silicon-containing resist intermediate film exhibits etching resistance to oxygen gas or hydrogen gas, the etching of the organic film using the silicon-containing resist intermediate film pattern as a mask is preferably carried out using an etching gas mainly composed of oxygen gas or hydrogen gas. This allows the organic film pattern to be transferred.

[0235] Next, the pattern is transferred to the workpiece by etching using the organic film with the transferred pattern as a mask. The subsequent etching of the workpiece (layer to be processed) can be performed using standard methods. For example, if the workpiece is made of SiO2, SiN, or a silica-based low-k dielectric insulating film, etching is performed primarily with fluorocarbon-based gases; if the workpiece is made of p-Si, Al, or W, etching is performed primarily with chlorine- or bromine-based gases. If the substrate is processed using fluorocarbon-based etching, the silicon-containing resist intermediate film pattern is stripped simultaneously with the substrate processing. On the other hand, if the substrate is processed using chlorine- or bromine-based etching, a separate dry etching stripping process using fluorocarbon-based gases is required after substrate processing to strip the silicon-containing resist intermediate film pattern.

[0236] An organic film obtained by using the organic film-forming composition of the present invention can have excellent etching resistance when etching the workpiece as described above.

[0237] [Four-layer resist process using silicon-containing resist interlayer and organic anti-reflective or adhesive coating] Further, the present invention provides a pattern forming method, comprising the steps of: forming an organic film on a workpiece using the organic film-forming composition described above; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material; forming an organic anti-reflective film or an adhesion film on the silicon-containing resist intermediate film; forming a resist upper layer film on the organic antireflective film or the adhesion film using a resist upper layer film material comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; a resist upper layer film on which the circuit pattern is formed is used as a mask to transfer the pattern to the organic anti-reflective film or the adhesive film and the silicon-containing resist intermediate film by etching; transferring the pattern to the organic film by etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; Furthermore, the present invention provides a pattern forming method in which the organic film onto which the pattern has been transferred is used as a mask to transfer the pattern onto the workpiece by etching.

[0238] This method can be performed in the same manner as the three-layer resist process using the silicon-containing resist intermediate film described above, except that an organic antireflective coating (BARC) or an adhesive film is formed between the silicon-containing resist intermediate film and the resist top layer film.

[0239] The organic anti-reflection film and the adhesive film can be formed by spin coating using known organic anti-reflection film materials.

[0240] [Trilayer resist process using inorganic hard mask] Further, the present invention provides a pattern forming method, comprising the steps of: forming an organic film on a workpiece using the organic film-forming composition described above; 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 resist upper layer film material comprising 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 circuit pattern has been formed as a mask; transferring the pattern to the organic film by etching using the inorganic hard mask to which the pattern has been transferred as a mask; Furthermore, the present invention provides a pattern forming method in which the organic film onto which the pattern has been transferred is used as a mask to transfer the pattern onto the workpiece by etching.

[0241] This method can be carried out in the same manner as the three-layer resist process using the silicon-containing resist intermediate film described above, except that an inorganic hard mask is formed on the organic film instead of the silicon-containing resist intermediate film.

[0242] An inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film (SiON film) can be formed by a CVD method, an ALD method, or the like. Methods for forming a silicon nitride film are described, for example, in JP-A No. 2002-334869 and WO 2004 / 066377. The thickness of the inorganic hard mask is preferably 5 to 200 nm, more preferably 10 to 100 nm. As the inorganic hard mask, a SiON film is most preferably used because of its high anti-reflection effect.

[0243] [Four-layer resist process using inorganic hard mask and organic anti-reflective or adhesive film] Further, the present invention provides a pattern forming method, comprising the steps of: forming an organic film on a workpiece using the organic film-forming composition described above; 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 anti-reflective film or an adhesion film on the inorganic hard mask; forming a resist upper layer film on the organic antireflective film or the adhesion film using a resist upper layer film material comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the organic anti-reflective film or the adhesive film 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 the pattern to the organic film by etching using the inorganic hard mask to which the pattern has been transferred as a mask; Furthermore, the present invention provides a pattern forming method in which the organic film onto which the pattern has been transferred is used as a mask to transfer the pattern onto the workpiece by etching.

[0244] This method can be performed in the same manner as the above-mentioned three-layer resist process using an inorganic hard mask, except that an organic antireflective coating (BARC) or an adhesive film is formed between the inorganic hard mask and the resist top layer film.

[0245] In particular, when a SiON film is used as the inorganic hard mask, the two-layer anti-reflection coating of the SiON film and BARC makes it possible to suppress reflection even in immersion lithography with a high NA exceeding 1.0. Another benefit of forming a BARC is that it reduces the footing of the resist top layer pattern directly above the SiON film.

[0246] An example of a pattern formation method using the three-layer resist process of the present invention is shown in Figures 3(A) to 3(F). In the three-layer resist process, as shown in Figure 3(A), an organic film 3 is formed on a processable layer 2 formed on a substrate 1 using the organic film-forming composition of the present invention, followed by the formation of a silicon-containing resist intermediate film 4, and then a resist upper layer film 5 is formed thereon. Next, as shown in Figure 3(B), the exposed portion 6 of the resist upper layer film 5 is exposed and subjected to PEB (post-exposure bake). Next, as shown in Figure 3(C), development is performed to form a resist upper layer film pattern 5a. Next, as shown in Figure 3(D), using the resist upper layer film pattern 5a as a mask, the silicon-containing resist intermediate film 4 is dry-etched using a fluorocarbon-based gas to form a silicon-containing resist intermediate film pattern 4a. Next, as shown in Figure 3(E), after removing the resist upper layer film pattern 5a, the organic film 3 is oxygen-plasma etched using the silicon-containing resist intermediate film pattern 4a as a mask to form an organic film pattern 3a. 3(F), after removing the silicon-containing resist intermediate film pattern 4a, the workpiece layer 2 is etched using the organic film pattern 3a as a mask to form a pattern 2a. By suppressing the formation of humps during the formation of the organic film, it is possible to reduce defects caused by humps in the organic film during the dry etching process shown in Figures (D), (E), and (F).

[0247] When forming an inorganic hard mask, the silicon-containing resist intermediate film 4 can be replaced with an inorganic hard mask, and when forming a BARC or an adhesion film, the BARC or adhesion film can be formed between the silicon-containing resist intermediate film 4 and the resist upper layer film 5. Etching of the BARC or adhesion film can be performed consecutively prior to etching of the silicon-containing resist intermediate film 4, or etching of the silicon-containing resist intermediate film 4 can be performed after etching of the BARC or adhesion film alone, by changing the etching apparatus, for example.

[0248] As described above, the pattern formation method of the present invention makes it possible to form a fine pattern on a workpiece with high precision by a multilayer resist process, and also to reduce defects resulting from humps in the organic film by suppressing hump formation in the organic film. [Example]

[0249] The present invention will be explained in more detail below with reference to Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited thereto. The molecular weight was measured specifically as follows: The weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene were determined by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent (solvent), and the polydispersity (Mw / Mn) was also determined.

[0250] [Synthesis of compounds (A1) to (A41)] The fluorine-containing compounds (A1) to (A41) used in the examples of the present invention were synthesized using the thiol compounds (a1) to (a5) and modifying agents (b1) to (b18) shown below.

[0251] [Thiol compounds] [ka]

[0252] [Modifying agents] [ka]

[0253] [ka]

[0254] [Synthesis of compound (A1)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a1), 8.96 g of potassium carbonate, and 40 g of DMF were added to form a uniform dispersion at an internal temperature of 50°C. 16.1 g of modifying agent (b1) was slowly added, and the reaction was carried out for 24 hours at an internal temperature of 50°C. 300 ml of methyl isobutyl ketone and 300 g of pure water were added to the reaction solution to dissolve the precipitated salt, after which the separated aqueous layer was removed and the mixture was washed six times with 100 g of 3% aqueous nitric acid solution and 100 g of pure water. The organic layer was then evaporated to dryness under reduced pressure to obtain compound (A1). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A1): Mw = 700, Mw / Mn = 1.01

[0255] [Synthesis of compound (A2)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a1), 8.96 g of potassium carbonate, and 40 g of DMF were added to form a uniform dispersion at an internal temperature of 50°C. 16.5 g of modifying agent (b2) was slowly added, and the reaction was carried out at an internal temperature of 50°C for 24 hours. 300 ml of methyl isobutyl ketone and 300 g of pure water were added to the reaction solution to dissolve the precipitated salt, after which the separated aqueous layer was removed and the mixture was washed six times with 100 g of 3% aqueous nitric acid solution and 100 g of pure water. The organic layer was then evaporated to dryness under reduced pressure to obtain compound (A2). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A2): Mw = 720, Mw / Mn = 1.02

[0256] [Synthesis of compound (A3)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a1), 8.96 g of potassium carbonate, and 40 g of DMF were added to form a uniform dispersion at an internal temperature of 50°C. 22.1 g of modifying agent (b3) was slowly added, and the reaction was carried out for 24 hours at an internal temperature of 50°C. 300 ml of methyl isobutyl ketone and 300 g of pure water were added to the reaction solution to dissolve the precipitated salt, after which the separated aqueous layer was removed. The mixture was washed six times with 100 g of 3% aqueous nitric acid solution and 100 g of pure water, and the organic layer was evaporated to dryness under reduced pressure to obtain compound (A3). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A3): Mw = 840, Mw / Mn = 1.02

[0257] [Synthesis of compound (A4)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a1), 32.6 g of modifying agent (b4), and 100 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 0.75 g of dimethyl 2,2'-azobis(isobutyrate) was slowly added, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent were distilled off, and the mixture was dried under reduced pressure to obtain compound (A4). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A4): Mw = 1190, Mw / Mn = 1.03

[0258] [Synthesis of compound (A5)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a2), 32.6 g of modifying agent (b5), and 100 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 0.77 g of dimethyl 2,2'-azobis(isobutyrate) was slowly added, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A5). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A5): Mw = 1180, Mw / Mn = 1.02

[0259] [Synthesis of compound (A6)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a1), 31.8 g of modifying agent (b5), and 100 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 0.75 g of dimethyl 2,2'-azobis(isobutyrate) was slowly added, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A6). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A6): Mw = 1160, Mw / Mn = 1.02

[0260] [Synthesis of compound (A7)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a3), 48.9 g of modifying agent (b5), and 150 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 1.15 g of dimethyl 2,2'-azobis(isobutyrate) was slowly added, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent were distilled off, and the mixture was dried under reduced pressure to obtain compound (A7). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A7): Mw = 2260, Mw / Mn = 1.03

[0261] [Synthesis of compound (A8)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a4), 17.4 g of modifying agent (b5), and 80 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 0.41 g of dimethyl 2,2'-azobis(isobutyrate) was slowly added, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A8). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A8): Mw = 1360, Mw / Mn = 1.03

[0262] [Synthesis of compound (A9)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a5), 18.8 g of modifying agent (b5), and 100 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 0.44 g of dimethyl 2,2'-azobis(isobutyrate) was slowly added, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A9). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A9): Mw = 3860, Mw / Mn = 1.05

[0263] [Synthesis of compound (A10)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a1), 21.7 g of modifying agent (b6), and 100 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 0.75 g of dimethyl 2,2'-azobis(isobutyrate) was slowly added, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A10). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A10): Mw = 860, Mw / Mn = 1.01

[0264] [Synthesis of compound (A11)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a2), 38.1 g of modifying agent (b7), and 150 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 0.77 g of dimethyl 2,2'-azobis(isobutyrate) was slowly added, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A11). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A11): Mw = 1310, Mw / Mn = 1.02

[0265] [Synthesis of compound (A12)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a1), 37.2 g of modifying agent (b7), and 150 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 0.75 g of dimethyl 2,2'-azobis(isobutyrate) was slowly added, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A12). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A12): Mw = 1330, Mw / Mn = 1.03

[0266] [Synthesis of compound (A13)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a3), 57.3 g of modifying agent (b7), and 200 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 1.15 g of dimethyl 2,2'-azobis(isobutyrate) was slowly added, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A13). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A13): Mw = 2580, Mw / Mn = 1.04

[0267] [Synthesis of compound (A14)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a4), 20.3 g of modifying agent (b7), and 80 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 0.41 g of dimethyl 2,2'-azobis(isobutyrate) was slowly added, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A14). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A14): Mw = 1410, Mw / Mn = 1.02

[0268] [Synthesis of compound (A15)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a2), 46.2 g of modifying agent (b8), and 80 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 0.77 g of dimethyl 2,2'-azobis(isobutyrate) was slowly added, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A15). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A15): Mw = 1540, Mw / Mn = 1.03

[0269] [Synthesis of compound (A16)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a1), 45.0 g of modifying agent (b8), and 150 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 0.75 g of dimethyl 2,2'-azobis(isobutyrate) was slowly added, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A16). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A16): Mw = 1560, Mw / Mn = 1.02

[0270] [Synthesis of compound (A17)] Under a nitrogen atmosphere, 3.0 g of thiol compound (a3), 41.6 g of modifying agent (b8), and 150 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 0.69 g of dimethyl 2,2'-azobis(isobutyrate) was slowly added, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A17). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A17): Mw = 3240, Mw / Mn = 1.05

[0271] [Synthesis of compound (A18)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a1), 45.0 g of modifying agent (b9), and 150 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 0.75 g of dimethyl 2,2'-azobis(isobutyrate) was slowly added, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A18). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A18): Mw = 1620, Mw / Mn = 1.02

[0272] [Synthesis of compound (A19)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a2), 46.1 g of modifying agent (b10), and 150 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 0.77 g of dimethyl 2,2'-azobis(isobutyrate) was slowly added, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A19). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A19): Mw = 1520, Mw / Mn = 1.03

[0273] [Synthesis of compound (A20)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a1), 44.9 g of modifying agent (b10), and 150 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 0.75 g of dimethyl 2,2'-azobis(isobutyrate) was slowly added, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A20). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A20): Mw = 1560, Mw / Mn = 1.03

[0274] [Synthesis of compound (A21)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a1), 12.1 g of modifying agent (b11), and 80 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 1.31 g of triethylamine, previously diluted with 5 ml of THF, was slowly added dropwise, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent and catalyst were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A21). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A21): Mw = 560, Mw / Mn = 1.01

[0275] [Synthesis of compound (A22)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a2), 15.4 g of modifying agent (b12), and 80 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 1.35 g of triethylamine, pre-diluted with 5 ml of THF, was slowly added dropwise, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent and catalyst were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A22). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A22): Mw = 620, Mw / Mn = 1.01

[0276] [Synthesis of compound (A23)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a1), 15.1 g of modifying agent (b12), and 80 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 1.31 g of triethylamine, previously diluted with 5 ml of THF, was slowly added dropwise, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent and catalyst were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A23). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A23): Mw = 620, Mw / Mn = 1.01

[0277] [Synthesis of compound (A24)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a3), 23.2 g of modifying agent (b12), and 100 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 2.02 g of triethylamine, previously diluted with 5 ml of THF, was slowly added dropwise, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent and catalyst were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A24). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A24): Mw = 1160, Mw / Mn = 1.03

[0278] [Synthesis of compound (A25)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a4), 8.2 g of modifying agent (b12), and 80 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 0.72 g of triethylamine, previously diluted with 5 ml of THF, was slowly added dropwise, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent and catalyst were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A25). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A25): Mw = 770, Mw / Mn = 1.02

[0279] [Synthesis of compound (A26)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a5), 8.9 g of modifying agent (b12), and 80 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 0.78 g of triethylamine, previously diluted with 5 ml of THF, was slowly added dropwise, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent and catalyst were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A26). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A26): Mw = 2330, Mw / Mn = 1.05

[0280] [Synthesis of compound (A27)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a2), 23.0 g of modifying agent (b13), and 120 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 1.35 g of triethylamine, previously diluted with 5 ml of THF, was slowly added dropwise, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent and catalyst were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A27). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A27): Mw = 880, Mw / Mn = 1.02

[0281] [Synthesis of compound (A28)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a1), 22.5 g of modifying agent (b13), and 120 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 1.31 g of triethylamine, previously diluted with 5 ml of THF, was slowly added dropwise, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent and catalyst were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A28). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A28): Mw = 850, Mw / Mn = 1.01

[0282] [Synthesis of compound (A29)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a2), 26.8 g of modifying agent (b14), and 120 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 1.35 g of triethylamine, previously diluted with 5 ml of THF, was slowly added dropwise, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent and catalyst were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A29). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A29): Mw = 1010, Mw / Mn = 1.03

[0283] [Synthesis of compound (A30)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a1), 26.1 g of modifying agent (b14), and 120 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 1.31 g of triethylamine, previously diluted with 5 ml of THF, was slowly added dropwise, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent and catalyst were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A30). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A30): Mw = 1040, Mw / Mn = 1.02

[0284] [Synthesis of compound (A31)] Under a nitrogen atmosphere, 3.0 g of thiol compound (a3), 24.1 g of modifying agent (b14), and 120 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 1.21 g of triethylamine, previously diluted with 5 ml of THF, was slowly added dropwise, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent and catalyst were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A31). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A31): Mw = 1990, Mw / Mn = 1.04

[0285] [Synthesis of compound (A32)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a4), 14.2 g of modifying agent (b14), and 100 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 0.72 g of triethylamine, previously diluted with 5 ml of THF, was slowly added dropwise, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent and catalyst were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A32). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A32): Mw = 1120, Mw / Mn = 1.03

[0286] [Synthesis of compound (A33)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a5), 15.4 g of modifying agent (b14), and 80 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 0.78 g of triethylamine, previously diluted with 5 ml of THF, was slowly added dropwise, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent and catalyst were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A33). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A33): Mw = 3490, Mw / Mn = 1.06

[0287] [Synthesis of compound (A34)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a1), 23.9 g of modifying agent (b15), and 80 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 1.31 g of triethylamine, previously diluted with 5 ml of THF, was slowly added dropwise, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent and catalyst were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A34). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A34): Mw = 890, Mw / Mn = 1.01

[0288] [Synthesis of compound (A35)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a2), 18.4 g of modifying agent (b16), and 80 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 1.35 g of triethylamine, previously diluted with 5 ml of THF, was slowly added dropwise, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent and catalyst were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A35). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A35): Mw = 700, Mw / Mn = 1.01

[0289] [Synthesis of compound (A36)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a1), 17.9 g of modifying agent (b16), and 80 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 1.31 g of triethylamine, previously diluted with 5 ml of THF, was slowly added dropwise, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent and catalyst were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A36). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A36): Mw = 720, Mw / Mn = 1.01

[0290] [Synthesis of compound (A37)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a1), 19.7 g of modifying agent (b17), and 100 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 1.31 g of triethylamine, pre-diluted with 5 ml of THF, was slowly added dropwise, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent and catalyst were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A37). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A37): Mw = 820, Mw / Mn = 1.02

[0291] [Synthesis of compound (A38)] Under a nitrogen atmosphere, 3.0 g of thiol compound (a2), 26.4 g of modifying agent (b18), and 100 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 0.81 g of triethylamine, previously diluted with 5 ml of THF, was slowly added dropwise, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent and catalyst were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A38). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A38): Mw = 1540, Mw / Mn = 1.03

[0292] [Synthesis of compound (A39)] Under a nitrogen atmosphere, 3.0 g of thiol compound (a1), 25.7 g of modifying agent (b18), and 100 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 0.79 g of triethylamine, previously diluted with 5 ml of THF, was slowly added dropwise, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent and catalyst were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A39). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A39): Mw = 1570, Mw / Mn = 1.02

[0293] [Synthesis of compound (A40)] Under a nitrogen atmosphere, 2.0 g of thiol compound (a3), 26.4 g of modifying agent (b18), and 100 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 0.81 g of triethylamine, previously diluted with 5 ml of THF, was slowly added dropwise, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent and catalyst were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A40). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A40): Mw = 3120, Mw / Mn = 1.05

[0294] [Synthesis of compound (A41)] Under a nitrogen atmosphere, 5.0 g of thiol compound (a4), 23.4 g of modifying agent (b18), and 100 g of THF were added and the mixture was heated to an internal temperature of 60°C to form a homogeneous solution. 0.72 g of triethylamine, previously diluted with 5 ml of THF, was slowly added dropwise, and the reaction was carried out under reflux for 24 hours. After the reaction, low-boiling components such as the reaction solvent and catalyst were distilled off, and the mixture was evaporated to dryness under reduced pressure to obtain compound (A41). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (A41): Mw = 1700, Mw / Mn = 1.04

[0295] The structural formulae of the compounds (A1) to (A41) obtained in the above synthesis examples are shown below.

[0296]

change

[0297]

change

[0298]

change

[0299]

change

[0300]

change

[0301]

change

[0302]

change

[0303]

change

[0304]

change

[0305]

change

[0306]

change

[0307] [ka]

[0308] [ka]

[0309] [ka]

[0310] [ka]

[0311] [Synthesis of comparative polymers (R1) to (R5)] The comparative polymers (R1) to (R5) used in preparing the organic film-forming compositions were synthesized using the following monomers (c1) to (c6).

[0312] [ka]

[0313] [Comparative Synthesis Example 1] Synthesis of Comparative Polymer (R1) [ka] Under a nitrogen atmosphere, 6.0 g of PGMEA was heated and stirred at 80°C. To this was added dropwise a mixture of 3.44 g (0.011 mol) of monomer (c1), 7.46 g (0.034 mol) of monomer (c3), 0.473 g of dimethyl 2,2-azobis(2-methylpropionate), and 34 g of PGMEA over 4 hours. After further heating and stirring for 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (R1). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (R1): Mw = 9500, Mw / Mn = 1.20

[0314] [Comparative Synthesis Example 2] Synthesis of Comparative Polymer (R2) [ka] Under a nitrogen atmosphere, 6.0 g of PGMEA was heated and stirred at 80°C. To this was added dropwise a mixture of 1.43 g (0.005 mol) of monomer (c1), 5.76 g (0.041 mol) of monomer (c4), 0.473 g of dimethyl 2,2-azobis(2-methylpropionate), and 34 g of PGMEA over 4 hours. After further heating and stirring for 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (R2). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (R2): Mw = 5800, Mw / Mn = 1.42

[0315] [Comparative Synthesis Example 3] Synthesis of Comparative Polymer (R3) [ka] Under a nitrogen atmosphere, 6.0 g of PGMEA was heated and stirred at 80°C. To this was added dropwise a mixture of 7.00 g (0.032 mol) of monomer (c2), 1.92 g (0.014 mol) of monomer (c4), 0.473 g of dimethyl 2,2-azobis(2-methylpropionate), and 34 g of PGMEA over 4 hours. After further heating and stirring for 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (R3). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (R3): Mw = 6200, Mw / Mn = 1.33

[0316] [Comparative Synthesis Example 4] Synthesis of Comparative Polymer (R4) [ka] Under a nitrogen atmosphere, 6.0 g of PGMEA was heated and stirred at 80°C. To this was added dropwise a mixture of 5.00 g (0.023 mol) of (c2), 3.20 g (0.023 mol) of (c5), 0.473 g of dimethyl 2,2-azobis(2-methylpropionate), and 34 g of PGMEA over 4 hours. After further heating and stirring for 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (R4). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (R4): Mw = 8300, Mw / Mn = 1.33

[0317] [Comparative Synthesis Example 5] Synthesis of Comparative Polymer (R5) [ka] Under a nitrogen atmosphere, 6.0 g of PGMEA was heated and stirred at 80°C. To this was added dropwise a mixture of 2.00 g (0.009 mol) of (c2), 5.41 g (0.036 mol) of (c6), 0.473 g of dimethyl 2,2-azobis(2-methylpropionate), and 34 g of PGMEA over 4 hours. After further heating and stirring for 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (R5). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (R5): Mw = 3800, Mw / Mn = 1.44

[0318] [Resin or compound for forming organic film] C1: Resin represented by the following formula (C1): C2: Resin represented by the following formula (C2) C3: A compound represented by the following formula (C3): C4: A compound represented by the following formula (C4): C5: Resin represented by the following formula (C5): C6: Resin represented by the following formula (C6):

[0319] [ka]

[0320] [ka]

[0321] [solvent] (D1): Propylene glycol monomethyl ether acetate (D2): Propylene glycol monoethyl ether

[0322] [Preparation of Organic Film-Forming Compositions (UDL-1 to 121, Comparative UDL-1 to 16)] The polymers (A1) to (A41), (R1) to (R5), organic film-forming resins (C1) to (C6), and solvents were dissolved in the proportions shown in Tables 1-1 to 1-4, and the resulting solution was filtered through a 0.1 μm fluororesin filter to prepare organic film-forming compositions (resist underlayer film materials: UDL-1 to 121, and comparative examples UDL-1 to 16).

[0323] [Table 1-1]

[0324] [Table 1-2]

[0325] [Table 1-3]

[0326] [Table 1-4]

[0327] [Preparation of Silicon Wafers with Organic Cured Films Formed Using Organic Film-Forming Compositions (UDL-1 to 121, Comparative UDL-1 to 16)] Using a Tokyo Electron Limited coater / developer "CLEAN TRACK LITHIUS Pro AP," 2 mL of each of the organic film-forming compositions (UDL-1 to UDL-16) prepared above was dispensed onto the center of a 300 mm silicon wafer. After baking, the wafer was rotated at a rotation speed sufficient to achieve the average film thickness listed in Tables 2-1 to 2-4. While the silicon wafer was rotated at 1000 rpm, the remover nozzle was moved at a speed of 5 mm / s from the outer periphery of the silicon wafer to a position 3 mm toward the center, discharging the remover (a mixture of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether (30:70, mass ratio)) at a rate of 2 mL / s. At this position, the remover was further dispensed at a rate of 2 mL / s for 5 seconds. Dispensing of the dispensed solution was then stopped, and the wafer was rotated at 1000 rpm for an additional 30 seconds. Next, the silicon wafer on which the organic film-forming composition was formed was heated at 350° C. for 60 seconds to obtain a silicon wafer on which a cured organic film was formed.

[0328] [Solvent Resistance Evaluation: Examples 1-1 to 1-121, Comparative Examples 1-1 to 1-16] Using the method described above, organic film-forming compositions (UDL-1 to 121, Comparative UDL-1 to 16) were deposited on silicon wafers, the film thickness was measured, PGMEA solvent was dispensed onto the film, the film was left for 30 seconds, spin-dried, and baked at 100°C for 60 seconds to evaporate the PGMEA, and the film thickness was measured. The film thickness before dispensing the PGMEA solvent was defined as X, and the film thickness after dispensing the PGMEA solvent was defined as X1. The absolute value of the value calculated by (X1 - X) / X x 100 was used as the film thickness change rate (%). A film thickness change rate of less than 0.5% was considered good, and a film thickness change rate of 0.5% or more was considered poor.

[0329] [In-plane uniformity evaluation: Examples 1-1 to 1-121, Comparative Examples 1-1 to 1-16] The organic film-forming compositions (UDL-1 to 121, comparative UDL-1 to 16) were formed on silicon wafers using the above method, and the thickness of the organic cured film was measured at 225 concentric points within a radius of 145 mm from the center of the wafer using an optical film thickness meter. max , minimum Xmin , average value X average As, (X max -X min ) / X average The value obtained by the above was taken as the in-plane uniformity (%). When the in-plane uniformity was less than 2%, it was rated as A (good), when it was 2% or more but less than 3%, it was rated as B, and when it was 3% or more, it was rated as C (poor).

[0330] [Table 2-1]

[0331] [Table 2-2]

[0332] [Table 2-3]

[0333] [Table 2-4]

[0334] [Hump suppression evaluation: Examples 2-1 to 2-121, Comparative Examples 2-1 to 2-10] Using the method described above, organic film-forming compositions (UDL-1 to 121, comparative UDL-1 to 10) were deposited on silicon wafers, and the height change from the outer edge of the organic film to 1000 μm toward the center of the silicon wafer was measured using an Alpha-Step D-600 (contact profiler) manufactured by KLA-Tencor. Assuming the height of the silicon wafer was 0, a case in which the maximum height was less than 110% of the film thickness, as shown in Figure 1, was evaluated as good, and a case in which the height was 150% or more, as shown in Figure 2, was evaluated as poor.

[0335] [Embedding Evaluation-1: Examples 2-1 to 2-121, Comparative Examples 2-1 to 2-10] As shown in Figure 4, organic film-forming compositions (UDL-1 to 121, Comparative UDL-1 to 10) were deposited by the above method on a SiO2 wafer substrate having a dense hole pattern (hole diameter 0.2 μm, hole depth 1.0 μm, center-to-center distance between adjacent two holes 0.4 μm) to form a resist underlayer film 8. The substrate used was a base substrate (SiO2 wafer substrate) 7 having a dense hole pattern as shown in Figure 4(G) (overhead view) and (H) (cross-sectional view). The cross-sectional shape of each wafer substrate was observed using a scanning electron microscope (SEM) to confirm whether the holes were filled with the resist underlayer film without any voids. When a resist underlayer film material with poor filling properties was used, voids were generated within the holes. When a resist underlayer film material with good filling properties was used, the holes were filled with the resist underlayer film without any voids, as shown in Figure 4(I). A sample was rated as good if no voids were generated, and as poor if voids were generated.

[0336] [Embedding Evaluation-2: Examples 2-81 to 2-121] As shown in Figure 4, organic film-forming compositions (UDL-81 to 121) were deposited by the above method on a SiO2 wafer substrate with a dense hole pattern (hole diameter 0.2 μm, hole depth 2.0 μm, center-to-center distance between adjacent holes 0.4 μm) to form a resist underlayer film 8. The substrate used was a base substrate (SiO2 wafer substrate) 7 with a dense hole pattern as shown in Figure 4(G) (overhead view) and (H) (cross-sectional view). The cross-sectional shape of each wafer substrate was observed using a scanning electron microscope (SEM) to confirm whether the holes were filled with the resist underlayer film without any voids. When a resist underlayer film material with poor filling properties was used, voids were generated within the holes. When a resist underlayer film material with good filling properties was used, the holes were filled with the resist underlayer film without any voids, as shown in Figure 4(I). A sample was rated as good if no voids were generated, and as poor if voids were generated. In addition, in order to evaluate the quality of filling performance, the evaluation conditions are strict, making it easier for voids to be filled, even with a rating of -1.

[0337] [Table 3-1]

[0338] [Table 3-2]

[0339] [Table 3-3]

[0340] [Table 3-4]

[0341] As shown in Tables 2-1 to 2-4 and Tables 3-1 to 3-4, it was confirmed that the organic film-forming compositions of the present invention (UDL-1 to 121) are excellent in solvent resistance, in-plane uniformity, hump suppression, and filling properties.

[0342] [Pattern formation test: Examples 3-1 to 3-80] Using the above method, an organic cured film was formed on a SiO2 wafer substrate using an organic film-forming composition (UDL-1 to 80). The following silicon-containing resist intermediate film material (SOG1) was then applied on top of the organic cured film and baked at 200°C for 60 seconds to form a 35 nm thick silicon-containing resist intermediate film. The following ArF single-layer resist was then applied on top of the organic cured film as a resist top layer material and baked at 105°C for 60 seconds to form a 100 nm thick photoresist film. The following immersion protective film material (TC-1) was then applied on top of the photoresist film and baked at 90°C for 60 seconds to form a 50 nm thick protective film.

[0343] The silicon-containing resist intermediate film material (SOG1) was prepared by dissolving the polymer (SP1), crosslinking catalyst, and acid in an organic solvent and water in the proportions shown in Table 4, and filtering the resultant mixture through a 0.1 μm fluororesin filter.

[0344] [Table 4]

[0345] The polymer (SP1) is shown below. [ka]

[0346] TMPANO3: Trimethylphenylammonium nitrate PGEE: Propylene glycol ethyl ether

[0347] The resist top layer material (ArF single-layer resist) was prepared by dissolving the polymer (RP1), acid generator (PAG-A), and basic compound (Amine1) in a solvent containing 0.1 mass% FC-430 (manufactured by Sumitomo 3M Limited) in the proportions shown in Table 5, and filtering the solution through a 0.1 μm fluororesin filter.

[0348] [Table 5]

[0349] The polymer (RP1), acid generator (PAG-A), and basic compound (Amine1) are shown below. [ka]

[0350] The immersion protective film material (TC-1) was prepared by dissolving the polymer (PP1) in an organic solvent in the ratio shown in Table 6 and filtering the solution through a 0.1 μm fluororesin filter.

[0351] [Table 6]

[0352] The polymer (PP1) is shown below. [ka]

[0353] The resist was then exposed using an ArF immersion exposure system (Nikon Corporation; NSR-S610C, NA 1.30, σ 0.98 / 0.65, 35-degree dipole s-polarized illumination, 6% halftone phase-shift mask), baked at 100°C for 60 seconds (PEB), and developed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds to obtain a 55 nm 1:1 positive line-and-space pattern (resist upper layer film pattern).

[0354] Next, using the resist upper layer film pattern as a mask, the silicon-containing resist intermediate film was dry-etched (pattern transferred) using a Tokyo Electron etching system Telius, and using the resulting silicon-containing resist intermediate film pattern as a mask, the organic film was dry-etched (pattern transferred), and using the resulting organic film pattern as a mask, the SiO2 wafer substrate (SiO2 film) was dry-etched (pattern transferred). The etching conditions are as shown below.

[0355] (Conditions for transferring the resist top layer pattern to the silicon-containing resist intermediate film) Chamber pressure 10.0Pa RF power 1,500W CF4 gas flow rate: 75mL / min O2 gas flow rate 15mL / min Time 15sec

[0356] (Conditions for transferring silicon-containing resist intermediate film patterns to organic films) Chamber pressure 2.0Pa RF power 500W Ar gas flow rate: 75 mL / min O2 gas flow rate: 45mL / min Time 120sec

[0357] (Conditions for transferring organic film patterns onto SiO2 wafer substrates) Chamber pressure 2.0Pa RF power 2,200W C5F 12 Gas flow rate: 20 mL / min C2F6 gas flow rate 10mL / min Ar gas flow rate: 300 mL / min O2 gas flow rate 60mL / min Time 90sec

[0358] The cross section of the obtained pattern was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd. The results are shown in Tables 7-1 and 7-2.

[0359] [Table 7-1]

[0360] [Table 7-2]

[0361] As shown in Tables 7-1 to 7-2, in Examples 3-1 to 3-80 in which the organic film-forming compositions (UDL-1 to 80) of the present invention were used, the resist upper layer film pattern was ultimately transferred successfully to the SiO2 wafer substrate, confirming that the organic film-forming compositions of the present invention are suitable for use in microfabrication using the multilayer resist method.

[0362] [Preparation of resist top layer materials (PR1 to 41, comparative PR)] Resist top layer film materials (PR1 to 41, comparative PR) were prepared by dissolving polymer (P-1), acid generator (PAG-1), quencher (Q-1), and compounds (A1 to A41) in a solvent in the proportions shown in Tables 8-1 to 8-2 and filtering the solution through a 0.1 μm fluororesin filter.

[0363] [Table 8-1]

[0364] [Table 8-2]

[0365] The polymer (P-1), acid generator (PAG-1), quencher (Q-1), and solvent are shown below.

[0366] [ka]

[0367] [ka] PGMEA: Propylene glycol monomethyl ether acetate EL: Ethyl lactate

[0368] [Preparation of silicon wafers with resist top layer films formed using resist top layer film materials (PR1-41, comparative PR)] Using a Tokyo Electron Co., Ltd. coater / developer "CLEAN TRACK LITHIUS Pro AP," 2 ml of the resist top layer material (PR1-41, comparative PR) prepared above was dispensed onto the center of a silicon wafer, and the wafer was rotated and spread at a rotation speed that resulted in an average film thickness of 45 nm after baking. Next, the silicon wafer coated with the resist top layer film was heated at 110°C for 30 seconds to obtain a silicon wafer with a resist top layer film formed thereon.

[0369] [Evaluation of in-plane uniformity of resist top layer film: Examples 4-1 to 4-41, Comparative Example 4-1] The thickness of the resist top layer films (PR1 to 41, comparative PR) formed on the silicon wafers by the above method was measured at 225 concentric points within a radius of 145 mm from the center of the wafer using an optical film thickness meter. The maximum value Xmax, minimum value Xmin, and average value X average As, (X max -X min ) / X averageThe value obtained by the above formula was taken as the in-plane uniformity (%). In-plane uniformity of less than 3% was considered good, and in-plane uniformity of 3% or more was considered poor. The results are shown in Table 9.

[0370] [Table 9]

[0371] As shown in Table 9, the resist top layer film materials (PR1 to 41) of the present invention have excellent in-plane uniformity, which indicates that the compounds of the present invention function as surfactants that impart excellent leveling performance and can be used in a variety of organic film-forming compositions regardless of the type of resin combined.

[0372] [Preparation of silicon-containing resist intermediate film materials (SOG2-42, comparative SOG1)] Silicon-containing resist interlayer materials (SOG2 to 42, comparative SOG1) were prepared by dissolving the polymer (SP1), crosslinking catalyst, and acid in an organic solvent and water in the proportions shown in Tables 10-1 and 10-2, and then filtering the mixture through a 0.1 μm fluororesin filter.

[0373] [Table 10-1]

[0374] [Table 10-2] PGEE: Propylene glycol monoethyl ether

[0375] [Evaluation of Coatability of Silicon-Containing Resist Interlayer: Examples 5-1 to 5-41, Comparative Example 5-1] Using the above method, an organic cured film was formed on a silicon wafer substrate using an organic film-forming composition (Comparative UDL-1), and the following silicon-containing resist intermediate film materials (SOG2-42, Comparative SOG1) were applied thereon and baked at 200°C for 60 seconds to form a silicon-containing resist intermediate film. The state of the silicon-containing resist intermediate film coating was then visually observed and evaluated. If the coating condition was good, it was rated as good, and if pinholes were found, it was rated as bad.

[0376] In this evaluation, in order to evaluate the superiority or inferiority of the coating properties of the silicon-containing resist interlayer, the thickness of the silicon-containing resist interlayer was set to 5 nm, which was a special and strict evaluation condition.

[0377] [Table 11]

[0378] As shown in Table 11, the silicon-containing resist intermediate film materials (SOG2 to 42) have excellent film-forming properties without generating pinholes. This indicates that the compounds of the present invention can be used as surfactants that impart high film-forming properties to various film-forming compositions, not just organic films.

[0379] From the above, the organic film-forming composition of the present invention has excellent film-forming properties, high-level filling characteristics, and hump-suppressing properties, and is therefore extremely useful as an organic film material for use in multilayer resist processes. Furthermore, the pattern formation method of the present invention using this composition is capable of filling holes and trenches with very high aspect ratios without voids, and is also capable of forming fine patterns with high precision. In addition, it is possible to form an organic film with suppressed humps, and therefore semiconductor elements and the like can be efficiently manufactured. Furthermore, the compound of the present invention can be widely used as a surfactant, as it exhibits high film-forming properties.

[0380] This specification includes the following inventions.

[0381] [1]: A composition for forming an organic film, comprising an organic film-forming resin or compound (A), a compound (B) represented by the following general formula (1), and a solvent (C). [ka] (In the formula, R1 is a terminal group represented by the following general formula (2), X is an n1-valent organic group having 2 to 50 carbon atoms, and n1 is an integer of 2 to 8.) [ka] (In the formula, R2 is a monovalent organic group, and the monovalent organic group contains a structure having at least a fluorine atom represented by any of the following general formulas (3). m1 is 1 or 2, and when m1 is 1, Z represents a single bond or a divalent organic group which may contain a heteroatom, and when m1 is 2, Z represents a trivalent organic group which may contain a heteroatom. * represents a bond.) [ka] (In the formula, * represents a bond.)

[0382] [2]: The composition for forming an organic film according to the above [1], wherein the terminal group represented by the general formula (2) of the compound (B) is any one or more of the following general formulae (4) to (8): [ka] (wherein R2 is the same as above, and n2 represents an integer of 2 to 6.)

[0383] [3]: The composition for forming an organic film according to the above [1] or [2], wherein R2 of the compound (B) is any one of the following general formulas (9): [ka]

[0384] [4]: The composition for forming an organic film according to any one of the above [1] to [3], wherein the weight average molecular weight of the compound (B) is 300 to 4,000.

[0385] [5]: The composition for forming an organic film according to any one of the above [1] to [4], characterized in that the ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn of the compound (B) in terms of polystyrene, as determined by gel permeation chromatography, is 1.00≦Mw / Mn≦1.20.

[0386] [6]: The composition for forming an organic film according to any one of the above [1] to [5], characterized in that the content of the compound (B) is 0.01 to 5 parts by mass when the resin for forming an organic film or the compound (A) is taken as 100 parts by mass.

[0387] [7]: A method for forming an organic film used in the manufacturing process of a semiconductor device, comprising spin-coating the composition for forming an organic film according to any one of [1] to [6] above onto a substrate to be processed, and heat-treating the substrate coated with the composition for forming an organic film at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds, thereby forming a cured film.

[0388] [8]: A pattern forming method comprising the steps of forming an organic film on a workpiece using the organic film-forming composition according to any one of [1] to [6] above, forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms, forming a resist upper layer film on the resist intermediate film using a resist upper layer film material consisting of a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the resist intermediate film on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0389] [9]: A pattern forming method comprising the steps of forming an organic film on a workpiece using the organic film-forming composition according to any one of [1] to [6] above, forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms, forming an organic antireflective film or an adhesive film on the resist intermediate film, forming a resist upper layer film on the organic antireflective film or adhesive film using a resist upper layer film material comprising a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern by etching onto the organic antireflective film or adhesive film and the resist intermediate film using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern by etching onto the organic film using the resist intermediate film on which the pattern has been transferred as a mask, and further transferring the pattern onto the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0390]

[10] : A pattern forming method comprising the steps of forming an organic film on a workpiece using the organic film-forming composition according to any one of [1] to [6] above, 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 resist upper layer film material comprising 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 circuit 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 transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0391]

[11] : A pattern formation method comprising the steps of forming an organic film on a workpiece using the organic film-forming composition according to any one of [1] to [6] above, 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 film or an adhesive film on the inorganic hard mask, forming a resist upper layer film on the organic antireflective film or the adhesive film using a resist upper layer film material comprising a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the organic antireflective film or the adhesive film 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 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 transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0392]

[12] : The pattern forming method according to the above

[10] or

[11] , wherein the inorganic hard mask is formed by a CVD method or an ALD method.

[0393]

[13] : The pattern forming method according to any one of [8] to

[12] above, characterized in that in forming the circuit pattern, the circuit pattern is formed by lithography using light having a wavelength of 10 nm or more and 300 nm or less, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[0394]

[14] : The pattern forming method according to any one of the above [8] to

[13] , wherein in forming the circuit pattern, the circuit pattern is developed using an alkali developer or an organic solvent.

[0395]

[15] : The pattern forming method according to any one of [8] to

[14] above, wherein the workpiece is a semiconductor device substrate, or a semiconductor device substrate on which any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film is formed.

[0396]

[16] : The pattern forming method according to

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

[0397]

[17] : A compound represented by the following general formula (1): [ka] (In the formula, R1 is a terminal group represented by the following general formula (2), X is an n1-valent organic group having 2 to 50 carbon atoms, and n1 is an integer of 2 to 8.) [ka] (In the formula, R2 is a monovalent organic group, and the monovalent organic group contains a structure having at least a fluorine atom represented by any of the following general formulas (3). m1 is 1 or 2, and when m1 is 1, Z represents a single bond or a divalent organic group which may contain a heteroatom, and when m1 is 2, Z represents a trivalent organic group which may contain a heteroatom. * represents a bond.) [ka] (In the formula, * represents a bond.)

[0398]

[18] : The compound according to the above

[17] , wherein the terminal group represented by the general formula (2) is any one or more of the following general formulae (4) to (8): [ka] (wherein R2 is the same as above, and n2 represents an integer of 2 to 6.)

[0399]

[19] : The compound according to the above

[17] or

[18] , wherein R2 is any one of the following general formulas (9): [ka]

[0400] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention. [Explanation of symbols]

[0401] 1...substrate, 2...processed layer, 2a...pattern formed on the processed layer, 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 upper layer film pattern, 6...exposed portion, 7...Base substrate (SiO2 wafer substrate), 8...Resist underlayer film.

Claims

1. A composition for forming an organic film, comprising an organic film-forming resin or compound (A), a compound (B) represented by the following general formula (1), and a solvent (C): 【Chemistry 1】 (In the formula, R １ is a terminal group represented by the following general formula (2), X is an n1-valent organic group having 2 to 50 carbon atoms, and n1 represents an integer of 2 to 8. 【Chemistry 2】 (In the formula, R ２ is a monovalent organic group, and the monovalent organic group contains a structure having at least a fluorine atom represented by any of the following general formulas (3). m1 is 1 or 2, and when m1 is 1, Z represents a single bond or a divalent organic group which may contain a heteroatom, and when m1 is 2, Z represents a trivalent organic group which may contain a heteroatom. * represents a bond. 【Transformation 3】 (In the formula, * represents a bond.)

2. The composition for forming an organic film according to claim 1, wherein the terminal group represented by the general formula (2) of the compound (B) is any one or more of the following general formulas (4) to (8): 【Chemistry 4】 (In the formula, R ２ is the same as above, and n2 represents an integer of 2 to 6.

3. R of the compound (B) ２ The composition for forming an organic film according to claim 1, wherein is any one of the following general formulas (9): 【Transformation 5】

4. 2. The organic film-forming composition according to claim 1, wherein the compound (B) has a weight average molecular weight of 300 to 4,000.

5. 2. The organic film-forming composition according to claim 1, wherein the ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn of the compound (B) in terms of polystyrene as determined by gel permeation chromatography is 1.00≦Mw / Mn≦1.

20.

6. 2. The composition for forming an organic film according to claim 1, wherein the content of the compound (B) is 0.01 to 5 parts by mass when the resin for forming an organic film or the compound (A) is 100 parts by mass.

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

8. 10. A pattern forming method comprising the steps of: forming an organic film on a workpiece using the organic film-forming composition according to claim 1; forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms; forming a resist upper layer film on the resist intermediate film using a resist upper layer film material consisting of a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern to the organic film by etching using the resist intermediate film on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

9. a resist intermediate film material containing silicon atoms formed on the organic film; an organic antireflective film or an adhesive film formed on the resist intermediate film; a resist upper layer film formed on the organic antireflective film or the adhesive film using a resist upper layer film material comprising a photoresist composition; a circuit pattern formed on the resist upper layer film; a pattern transferred by etching to the organic antireflective film or the adhesive film and the resist intermediate film using the resist upper layer film on which the circuit pattern has been formed as a mask; a pattern transferred by etching to the organic film using the resist intermediate film on which the pattern has been transferred as a mask; and a pattern transfer method comprising the steps of:

10. 10. A pattern formation method comprising: forming an organic film on a workpiece using the organic film-forming composition according to claim 1; 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 resist upper layer film material comprising 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 circuit 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 transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

11. a resist upper layer film formed on the organic antireflective film or the adhesive film using a resist upper layer film material comprising a photoresist composition; a circuit pattern formed on the resist upper layer film; transferring the pattern by etching the organic antireflective film or the adhesive film and the inorganic hard mask using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern by etching the organic antireflective film or the adhesive film and the inorganic hard mask using the inorganic hard mask on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

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

13. 12. The pattern formation method according to claim 8, wherein the circuit pattern is formed by lithography using light having a wavelength of 10 nm or more and 300 nm or less, direct writing with an electron beam, nanoimprinting, or a combination thereof.

14. 12. The pattern forming method according to claim 8, wherein the circuit pattern is developed using an alkali developer or an organic solvent.

15. 12. The pattern forming method according to claim 8, wherein the workpiece is a semiconductor device substrate, or a semiconductor device substrate on which any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film is formed.

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

17. A compound represented by the following general formula (1): 【Transformation 6】 (In the formula, R １ is a terminal group represented by the following general formula (2), X is an n1-valent organic group having 2 to 50 carbon atoms, and n1 represents an integer of 2 to 8. 【Transformation 7】 (In the formula, R ２ is a monovalent organic group, and the monovalent organic group contains a structure having at least a fluorine atom represented by any of the following general formulas (3). m1 is 1 or 2, and when m1 is 1, Z represents a single bond or a divalent organic group which may contain a heteroatom, and when m1 is 2, Z represents a trivalent organic group which may contain a heteroatom. * represents a bond. 【Transformation 8】 (In the formula, * represents a bond.)

18. The compound according to claim 17, wherein the terminal group represented by the general formula (2) is any one or more of the following general formulae (4) to (8): 【Chemistry 9】 (In the formula, R ２ is the same as above, and n2 represents an integer of 2 to 6.

19. The R ２ is any one of the following general formulas (9): 【Chemistry 10】

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