Composition for forming organic film, method for forming organic film, pattern forming method, monomer, and polymer

Abstract

To provide a composition for forming an organic film that exhibits superior film formability (in-plane uniformity) and embedding characteristics on a substrate (wafer), suppresses hump formation during an EBR process, and offers excellent process latitude when employed as an organic underlayer for multilayer resist, and to provide a method for forming an organic film, a pattern forming method, a monomer, and a polymer using the composition.SOLUTION: A composition for forming an organic film comprises an organic film-forming resin and / or compound (A), a polymer (B) having a repeating unit represented by the following general formula (1) and / or a specific formula, and a solvent (C). In formula (1), R1 represents a hydrogen atom or a methyl group, and R2 represents a saturated or unsaturated monovalent organic group having 7 to 50 carbon atoms, having at least one trifluoromethoxybenzyl group, and the substituent OR2 and OH group on the cyclohexane ring being adjacent to each other on carbon atoms on the cyclohexane ring.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an organic film-forming composition for forming an organic film for a multilayer resist for microfabrication in the manufacture of semiconductor devices and the like, or an organic film for planarization in the manufacture of semiconductor devices and the like, a method for forming an organic film using the composition, and a pattern formation method, monomer, and polymer using the composition. [Background technology]

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

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

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

[0005] 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.

[0006] 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 deposited even on substrates or materials with complex shapes, and that have filling properties that enable the necessary patterns to be filled without voids.

[0007] 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).

[0008] 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.

[0009] Furthermore, after forming a spin-coated organic underlayer film, it is baked to form a hardened film for use in a multilayer resist process. This is because the organic underlayer film must be insoluble and infusible so that a silicon-containing resist interlayer can be applied as an upper layer. The organic film surface formed by the bake process has a hydrophobic surface due to the surfactant contained in the organic film-forming composition, which can cause coating abnormalities in the silicon-containing resist interlayer. Control of the contact angle of the organic underlayer film surface is required to improve the coatability of the silicon-containing resist interlayer and expand the process tolerance.

[0010] As mentioned above, surfactants play a major role in ensuring the film-forming properties of organic film-forming materials. Surfactants are commonly used containing fluorine-substituted organic groups, such as perfluoroalkyl groups, to fully demonstrate their surface-active effects. However, in recent years, the health effects of perfluoroalkyl substances (PFAS) have been highlighted, and there are moves to impose restrictions on the manufacture and sale of PFAS compounds under the European REACH regulations. Therefore, there is an urgent need to develop surfactants that do not contain PFAS structures.

[0011] As examples of such surfactants, surfactants having a trifluoromethoxy group or a pentafluorosulfanyl group and their use have been proposed (Patent Document 4). [Prior art documents] [Patent documents]

[0012] [Patent Document 1] Japanese Unexamined Patent Publication No. 6-118651, etc. [Patent Document 2] Patent No. 4355943 etc. [Patent Document 3] Japanese Patent Application Laid-Open No. 2004-205685 [Patent Document 4] Special Publication No. 2008-526792 Summary of the Invention [Problem to be solved by the invention]

[0013] 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 using the composition, a pattern formation method, a monomer, and a polymer. [Means for solving the problem]

[0014] In order to solve the above problems, the present invention provides a composition for forming an organic film, characterized in that it contains an organic film-forming resin and / or compound (A), a polymer (B) having repeating units represented by the following general formula (1) and / or (2), and a solvent (C): [ka] (In formula (1), R1 represents a hydrogen atom or a methyl group, R2 represents a saturated or unsaturated monovalent organic group having 7 to 50 carbon atoms, and has at least one fluorine-containing structure represented by formula (3) below, and the substituent OR2 and the OH group on the cyclohexane ring are adjacent substituents on the carbon atoms on the cyclohexane ring.) [ka] (In formula (2), R1 and R2 are the same as above.) [ka] ((3) is a partial structure contained in R2, and * represents a bond in the structure in R2. R2 may have two or more types of structures represented by (3) or two or more identical structures.)

[0015] An organic film-forming composition containing a polymer containing such a partial structure has an appropriate fluorine structure and polar structure, that is, has a trifluoromethoxy group on the aromatic ring and an OH group as a substituent on the carbon adjacent to the carbon to which OR2 is bonded, thereby simultaneously introducing a hydrophilic group and a hydrophobic group, thereby imparting the surfactant effect required for organic film formation and improving film formability during application.In addition, the trifluoromethoxybenzene structure represented by R2 of the present invention does not belong to the PFAS classification under REACH, so it is advantageous from the perspective of preventing environmental pollution and can be expected to be a highly versatile material as a surfactant for organic films.

[0016] Furthermore, it is preferable that R2 in the general formulas (1) and (2) contains a partial structure represented by the following general formula (4). [ka] (* represents a bond.)

[0017] In an organic film-forming composition containing a polymer having such a structure, the trifluoromethoxybenzene structure is not directly attached to the main chain, but is introduced at a position away from the main chain via a linker of several carbon atoms. This facilitates the formation of an aggregate structure through the interaction between the trifluoromethoxy group and the benzene ring, enhancing the behavior of the hydrophobic group, and as a result, it is believed to exhibit excellent surfactant properties. Therefore, the organic film-forming material of the present invention can provide an organic film-forming material with excellent film-forming properties that can be applied to a variety of polymers and compounds.

[0018] The polymer (B) is preferably a copolymer having repeating units of either or both of the general formulae (1) and (2) and the following general formula (5). [ka] (In the formula, R3 represents a hydrogen atom or a methyl group, R4 and R5 each represent a linear or branched divalent alkylene group having 1 to 4 carbon atoms, R6 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, m1 represents an integer of 0 to 23, n1 represents an integer of 0 to 23, and 2≦m1+n1≦23.)

[0019] As mentioned above, this organic film-forming material has excellent film-forming properties, but by forming a copolymer containing a repeating unit with a linking group such as (5), the repeating unit (5) contributes to the relaxation of the aggregation structure to an appropriate extent, making it possible to adjust the surface activity. Therefore, it is possible to provide an organic film-forming material that can accommodate a variety of film thicknesses (independent of solution concentration) and that combines filling properties and film-forming properties.

[0020] The weight average molecular weight of the polymer (B) is preferably 1,500 to 30,000.

[0021] 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, making it possible to form an organic underlayer film suitable for use in a multilayer resist process.

[0022] Furthermore, when the organic film-forming resin and / or compound (A) is taken as 100 parts by mass, the content of the polymer (B) is preferably 0.01 to 5 parts by mass.

[0023] A composition for forming an organic film containing the polymer in such an amount is preferable because the formed organic film has better in-plane uniformity.

[0024] 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 then heat-treating the substrate to which the organic film-forming composition has been applied at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds to harden the composition and form an organic film.

[0025] 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.

[0026] The present invention also provides a pattern formation method, comprising: forming an organic film on a workpiece using the above-described organic film-forming composition; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material; forming a resist upper layer film on the silicon-containing resist intermediate film using a 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 silicon-containing resist intermediate film using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern by etching onto the organic film using the silicon-containing 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.

[0027] The present invention also provides a pattern formation method, comprising: forming an organic film on a workpiece using the above-described organic film-forming composition; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material; forming an organic antireflective film or an adhesive film on the silicon-containing resist intermediate film; 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; using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic antireflective film or the adhesive film and the silicon-containing resist intermediate film by etching; using the silicon-containing resist intermediate film on which the pattern has been transferred as a mask, transferring the pattern to the organic film by etching; and further using the organic film on which the pattern has been transferred as a mask, transferring the pattern to the workpiece by etching.

[0028] The present invention also provides a pattern formation method, comprising: forming an organic film on a workpiece using the above-described organic film-forming composition; forming an inorganic hard mask intermediate film 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 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 inorganic hard mask 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 inorganic hard mask 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.

[0029] The present invention also provides a pattern formation method, comprising: forming an organic film on a workpiece using the above-described organic film-forming composition; forming an inorganic hard mask intermediate film 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 intermediate film; 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 by etching to the organic antireflective film or the adhesive film and the inorganic hard mask intermediate film using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern by etching to the organic film using the inorganic hard mask 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.

[0030] 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 intermediate film, or a four-layer resist process using an organic antireflective 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.

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

[0032] In the pattern formation method of the present invention, for example, an inorganic hard mask intermediate film can be formed by such a method.

[0033] 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.

[0034] In forming the circuit pattern, it is preferable to develop the circuit pattern using an alkali developer or an organic solvent.

[0035] In the pattern forming method of the present invention, such circuit pattern forming means and developing means can be suitably used.

[0036] Furthermore, it is preferable to use, as the workpiece, a semiconductor device substrate, or a semiconductor device substrate having 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 formed thereon.

[0037] Furthermore, it is preferable to use silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof as the metal constituting the workpiece.

[0038] The pattern forming method of the present invention makes it possible to form a pattern by processing the above-mentioned workpiece.

[0039] The present invention also provides a monomer characterized by being represented by the following general formula (6) or (7): [ka] (In formula (6), R1 represents a hydrogen atom or a methyl group, R2 represents a saturated or unsaturated monovalent organic group having 7 to 50 carbon atoms, and has at least one fluorine-containing structure represented by formula (3) below, and the substituent OR2 and the OH group on the cyclohexane ring are adjacent substituents on the carbon atoms on the cyclohexane ring.) [ka] (In formula (7), R1 and R2 are the same as above.) [ka] ((3) is a partial structure contained in R2, and * represents a bond in the structure in R2. R2 may have two or more types of structures represented by (3) or two or more identical structures.)

[0040] Such a monomer having a linker with a trifluoromethoxybenzene and hydroxyl group at the terminal structure between the polymerizable functional group and the monomer is useful for producing surfactant polymers. Furthermore, it can reduce the environmental load and can be used as a candidate for an industrially useful monomer not only for surfactant applications.

[0041] Furthermore, it is preferable that R2 in the general formulas (6) and (7) contains a partial structure represented by the following general formula (4). [ka] (* represents a bond.)

[0042] The structure described above can be used as a monomer that can control the surface active effect to a high degree by utilizing the interaction between the trifluoromethoxy group and the benzene ring.

[0043] The present invention also provides a polymer characterized by having repeating units represented by the following general formula (1) and / or (2): [ka] (In formula (1), R1 represents a hydrogen atom or a methyl group, R2 represents a saturated or unsaturated monovalent organic group having 7 to 50 carbon atoms, and has at least one fluorine-containing structure represented by formula (3) below, and the substituent OR2 and the OH group on the cyclohexane ring are adjacent substituents on the carbon atoms on the cyclohexane ring.) [ka] (In formula (2), R1 and R2 are the same as above.) [ka] ((3) is a partial structure contained in R2, and * represents a bond in the structure in R2. R2 may have two or more types of structures represented by (3) or two or more identical structures.)

[0044] Since the side chains of the polymer have suitable linking groups and terminal structures as described above, the polymer is not only useful as a surfactant for organic film-forming compositions, but is also expected to be an environmentally friendly material.

[0045] Furthermore, it is preferable that R2 in the general formulas (1) and (2) contains a partial structure represented by the following general formula (4). [ka] (* represents a bond.)

[0046] By forming a polymer having the partial structure as described above, the polymer is useful as a surfactant polymer that realizes high film-forming properties.

[0047] The polymer is preferably a copolymer having repeating units of either or both of the general formulae (1) and (2) and the following general formula (5). [ka] (In the formula, R3 represents a hydrogen atom or a methyl group, R4 and R5 each represent a linear or branched divalent alkylene group having 1 to 4 carbon atoms, R6 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, m1 represents an integer of 0 to 23, n1 represents an integer of 0 to 23, and 2≦m1+n1≦23.)

[0048] By forming a copolymer having the partial structure as described above, it can be used as a surfactant that can form various films independently of film thickness.

[0049] The weight average molecular weight of the polymer is preferably 1,500 to 30,000.

[0050] By adjusting the weight average molecular weight to fall within the above range, the polymer becomes suitable as a surfactant that can realize film-forming properties with excellent process tolerance. [Effects of the Invention]

[0051] 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 units to form a copolymer, 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, the composition is extremely useful as an organic film material for use 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 interlayer, or a four-layer resist process using a silicon-containing resist interlayer or an inorganic hard mask interlayer and an organic anti-reflective coating, 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 efficient production of semiconductor devices, etc. Furthermore, monomers and polymers useful as surfactants, which are necessary to achieve high film-forming properties, can be provided. [Brief explanation of the drawings]

[0052] [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

[0053] 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.

[0054] 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. 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. The present inventors have conducted extensive research into the above-mentioned problems and have found that by incorporating a polymer having a repeating unit with a specific substituent into a composition for forming an organic film, a composition for forming an organic film with 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 using trifluoromethoxybenzene to reduce the environmental load, it is expected that the composition will be developed not only as a surfactant but also as an industrially useful monomer and polymer.

[0055] That is, the present invention provides a composition for forming an organic film, characterized in that it contains an organic film-forming resin and / or compound (A), a polymer (B) having repeating units represented by the following general formula (1) and / or (2), and a solvent (C). [ka] (In formula (1), R1 represents a hydrogen atom or a methyl group, R2 represents a saturated or unsaturated monovalent organic group having 7 to 50 carbon atoms, and has at least one fluorine-containing structure represented by formula (3) below, and the substituent OR2 and the OH group on the cyclohexane ring are adjacent substituents on the carbon atoms on the cyclohexane ring.) [ka] (In formula (2), R1 and R2 are the same as above.) [ka] ((3) is a partial structure contained in R2, and * represents a bond in the structure in R2. R2 may have two or more types of structures represented by (3) or two or more identical structures.)

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

[0057] [Monomer] The monomer used in the production of the organic film-forming polymer of the present invention is a monomer represented by the following general formula (6) or (7). [ka] (In formula (6), R1 represents a hydrogen atom or a methyl group, R2 represents a saturated or unsaturated monovalent organic group having 7 to 50 carbon atoms, and has at least one fluorine-containing structure represented by formula (3) below, and the substituent OR2 and the OH group on the cyclohexane ring are adjacent substituents on the carbon atoms on the cyclohexane ring.) [ka] (In formula (7), R1 and R2 are the same as above.) [ka] ((3) is a partial structure contained in R2, and * represents a bond in the structure in R2. R2 may have two or more types of structures represented by (3) or two or more identical structures.)

[0058] Preferred examples of the monomer represented by the above general formula (6) include the following. [ka]

[0059] [ka]

[0060] Preferred examples of the monomer represented by the above general formula (7) include the following. [ka]

[0061] The monomers represented by the general formulas (6) and (7) are very useful as raw materials for polymers used as surfactants for forming organic films, i.e., as monomers. These allow for high-level control of surface tension by arranging the polar hydroxyl group and the hydrophobic trifluoromethoxybenzene group in the linking and terminal groups of the monomers.

[0062] It is preferable that R2 in the general formulas (6) and (7) contains a partial structure represented by the following general formula (4). [ka] (* represents a bond.)

[0063] Among these, those in which the trifluoromethoxy group is substituted para to the substituent having the bond * are particularly preferred from the viewpoint of surfactant effect. As a monomer having a trifluoromethoxy group at the para position, for example, those in which R2 in the above general formulas (6) and (7) contains a partial structure represented by the following general formula (8) are preferred. [ka]

[0064] Preferred examples of monomers having the above structure include the following. Among these, those in which R2 is an ester bond between trifluoromethoxybenzene and a side chain having a polymerizable group are preferred. The interaction between the hydroxyl groups in the polymer or between the aromatic ring of trifluoromethoxybenzene and the trifluoromethoxy group becomes more efficient, which can efficiently lower the surface tension, enhance the surfactant effect, and improve film-forming properties. Among these, those having a partial structure represented by general formula (2) are more preferred from the perspective of hump suppression, and among these, it is even more preferred that R1 is a methyl group from the perspective of the toxicity of the raw materials. [ka]

[0065] [ka]

[0066] [ka]

[0067] By introducing a hydroxyl group into the monomer of the present invention together with a suitable substituent containing a fluorine structure, the polymer synthesized using the monomer of the present invention functions as a surfactant and has the ability to reduce surface tension, making it possible to achieve excellent uniform coating properties (leveling properties) of organic films.

[0068] [Method for producing monomer] The means for obtaining the monomers represented by general formulas (6) and (7) used in the present invention is not particularly limited, but they can be obtained by an addition reaction between an epoxy compound and a compound having a hydroxyl group with R2 as a substituent (carboxylic acid, alcohol, phenol, etc.) as shown in the following reaction formula. In this case, the monomer having a cyclohexane structure represented by (6) does not have a reaction selectivity with epoxycyclohexane as shown in the following reaction formula, so the monomer obtained is a mixture of the two. [ka] [ka]

[0069] In the reaction of the epoxy compound with the compound having a hydroxyl group shown above, when the molar amount of epoxy in the epoxy compound is taken as 1 mole, the amount of the compound having a hydroxyl group charged is preferably 0.3 to 2.0 moles, more preferably 0.5 to 1.5 moles, and even more preferably 0.75 to 1.25 moles.

[0070] If the amount of the compound having a hydroxyl group charged relative to the epoxy units is not insufficient, no unreacted epoxy groups will remain, and storage stability will not be affected.If the amount of the compound having a hydroxyl group charged relative to the epoxy units is not greatly excessive, no unreacted compound will remain, and outgassing will not occur.

[0071] The compound synthesized from the above-mentioned raw materials can usually be obtained by reacting an epoxy compound with a compound having a hydroxyl group in a solvent or in a solvent and in the presence of a reaction catalyst at room temperature or, if necessary, with cooling or heating.

[0072] Examples of the solvent (solvent) to be used include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ethers such as diethyl ether, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and 1,4-dioxane; chlorine-based solvents such as methylene chloride, chloroform, dichloroethane, and trichloroethylene; hydrocarbons such as hexane, heptane, benzene, toluene, xylene, and cumene; nitriles such as acetonitrile; ketones such as acetone, ethyl methyl ketone, and isobutyl methyl ketone; esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate; lactones such as γ-butyrolactone; and aprotic polar solvents such as dimethyl sulfoxide, N,N-dimethylformamide, and hexamethylphosphoric triamide. These can be used alone or in combination of two or more. These solvents can be used in an amount of 0 to 2000 parts by mass per 100 parts by mass of the reaction raw materials.

[0073] Examples of reaction catalysts include benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltrimethylammonium chloride, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium hydroxide, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, tributylbenzylammonium chloride, trimethylbenzylammonium chloride, Examples of suitable quaternary ammonium salts include tetrabutyl phosphonium chloride, tetrabutyl phosphonium bromide, tetraphenyl phosphonium chloride, and tertiary amines such as tris[2-(2-methoxyethoxy)ethyl]amine, tris(3,6-dioxaheptyl)amine, and tris(3,6-dioxaoctyl)amine. The amount used is 0.001 to 100% by weight, preferably 0.005 to 50% by weight, based on the raw materials.

[0074] 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.

[0075] The reaction method may be a method in which the epoxy compound, the compound having a hydroxyl group, and the catalyst are charged all at once, a method in which the epoxy compound and the compound having a hydroxyl group are dispersed or dissolved, and then the catalyst is added all at once or diluted with a solvent and added dropwise, or a method in which the catalyst is dispersed or dissolved, and then the epoxy compound and the compound having a hydroxyl group are added all at once or diluted with a solvent and added dropwise. After the reaction is complete, the product may be used as is without purification, or it may be recovered by diluting with an organic solvent and then separating and washing to remove unreacted raw materials, catalyst, etc. present in the system.

[0076] The organic solvent used here is not particularly limited as long as it can dissolve the reaction product and separate into two layers when mixed with water. Examples include hydrocarbons such as hexane, heptane, benzene, toluene, and xylene; esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate; ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, and methyl isobutyl ketone; ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, and ethyl cyclopentyl methyl ether; chlorinated solvents such as methylene chloride, chloroform, dichloroethane, and trichloroethylene; and mixtures thereof. The washing water used here is typically what is known as deionized water or ultrapure water. While washing may be performed at least once, washing 10 or more times does not necessarily provide the desired effect, so washing is preferably performed 1 to 5 times.

[0077] During separation and washing, washing with a basic aqueous solution may be performed to remove unreacted compounds having hydroxyl groups or acidic components. Examples of bases include alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates, ammonia, and organic ammonium.

[0078] Furthermore, in order to remove metal impurities or basic components from the system during separation and washing, washing with an acidic aqueous solution may be performed. Examples of acids 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.

[0079] Separation washing with either a basic aqueous solution or an acidic aqueous solution may be carried out alone or in combination. From the viewpoint of removing metal impurities, it is preferable to carry out separation washing with a basic aqueous solution first and then with an acidic aqueous solution.

[0080] After the separation washing with the basic aqueous solution or acidic aqueous solution, washing with neutral water may be carried out subsequently. The washing may be carried out once or more times, preferably about 1 to 5 times. The neutral water may be deionized water or ultrapure water as described above. The washing may be carried out once or more times, but washing 10 or more times does not necessarily provide the effect of washing alone, so it is preferably about 1 to 5 times.

[0081] Furthermore, the reaction product after the separation operation can be recovered as a powder by concentrating the solvent to dryness or crystallizing it under reduced pressure or normal pressure. Furthermore, if a boiling point exists, it can also be produced by vacuum distillation. To improve operability when using the reaction product as a highly viscous liquid monomer in polymerization, it can also be kept in a solution state of moderate concentration. In this case, if the concentration is not excessively high, the viscosity will not be too high and operability will not be impaired. If the concentration is not excessively low, the amount of solvent will not be excessive, which is economical. The concentration in this case is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by weight.

[0082] The solvent used in this case is not particularly limited as long as it can dissolve the resulting monomer and does not adversely affect storage stability or the polymerization of the monomer. 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.

[0083] [Polymer] The polymer for forming an organic film of the present invention is a polymer having repeating units represented by the following general formula (1) and / or (2). [ka] (In formula (1), R1 represents a hydrogen atom or a methyl group, R2 represents a saturated or unsaturated monovalent organic group having 7 to 50 carbon atoms, and has at least one fluorine-containing structure represented by formula (3) below, and the substituent OR2 and the OH group on the cyclohexane ring are adjacent substituents on the carbon atoms on the cyclohexane ring.) [ka] (In formula (2), R1 and R2 are the same as above.) [ka] ((3) is a partial structure contained in R2, and * represents a bond in the structure in R2. R2 may have two or more types of structures represented by (3) or two or more identical structures.)

[0084] The side chains of the polymers described above have a hydroxyl group, which is a hydrophilic group, on the linking group, and a trifluoromethoxybenzene structure, which is a hydrophobic group, at the terminal. Therefore, when the polymers are used as surfactants, it becomes possible to appropriately control the surface tension, and when used as surfactants for forming organic films, it becomes possible to impart excellent film-forming properties.

[0085] A preferred example of a polymer having a repeating unit represented by the general formula (1) is a polymer obtained using a monomer represented by the general formula (6). Similarly, a preferred example of a polymer having a repeating unit represented by the general formula (2) is a polymer obtained using a monomer represented by the general formula (7). A specific reaction scheme is shown below, and the unsaturated bonds of the monomers described in paragraphs

[0058] to

[0060] can be polymerized using a polymerization method such as radical polymerization. From the perspective of exhibiting a surfactant effect, the structure represented by the general formula (2) is more preferred. [ka]

[0086] Furthermore, it is preferable that R2 in the general formulas (1) and (2) of the present invention contains a partial structure represented by the following general formula (4). [ka] (* represents a bond.)

[0087] Preferred examples of polymers having the partial structure represented by the general formula (4) above include polymers obtained by polymerizing the monomers described in the above paragraph

[0064] . Among these, polymers having the repeating units shown below are more preferred from the viewpoint of surfactant effect. In order to efficiently exhibit the fluorophilic effect, which is the interaction between compounds having fluorine substituents, it is preferable that a trifluoromethoxy group be present at the para-position on the aromatic ring, and it is even more preferable that R1 be a methyl group from the viewpoint of ease of raw material availability. [ka]

[0088] Furthermore, the polymer is preferably a copolymer having repeating units of either or both of the general formulae (1) and (2) and the following general formula (5). [ka] (In the formula, R3 represents a hydrogen atom or a methyl group, R4 and R5 each represent a linear or branched divalent alkylene group having 1 to 4 carbon atoms, R6 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, m1 represents an integer of 0 to 23, n1 represents an integer of 0 to 23, and 2≦m1+n1≦23.)

[0089] By forming a copolymer having the partial structure as described above, it can be used as a surfactant that can form various films independently of film thickness.

[0090] The above R4 and R5 each represent a divalent alkylene group having 1 to 4 carbon atoms, which may be linear or branched. Specific examples of the divalent alkylene group having 1 to 4 carbon atoms, which may be linear or branched, include methylene, ethylene, propylene, butylene, trimethylene, and tetramethylene. Among these, an ethylene group is more preferred from the viewpoint of eliminating voids in film formation. The arrangement of (R4O) and (R5O) may be random, block, or multiblock.

[0091] The above R6 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an allyl group, an n-butyl group, an s-butyl group, a t-butyl group, and an isobutyl group. Among these, a hydrogen atom, a methyl group or an ethyl group, and a phenyl group are more preferred. A hydrogen atom or a methyl group is preferred from the viewpoint of ease of obtaining raw materials.

[0092] The above m1 is 0 to 23, n1 is 0 to 23, and 2≦m1+n1≦23. Here, m1 and n1 represent the average number of repetitions. The upper limit of m1+n1 is 23, and from the viewpoint of low-temperature storage stability, 9≦m1+n1≦13 is more preferable.

[0093] More specific examples of the repeating unit represented by the above general formula (5) include the following. [ka]

[0094] [ka]

[0095] Furthermore, the polymer can be prepared by combining one or more monomers each of the structural units represented by general formulas (1) and (2) and the structural unit represented by general formula (5). For example, to improve film-forming properties, it is possible to combine monomers that yield multiple repeating units of (1) and (2), to use multiple combinations of monomers that yield the repeating unit represented by (5), or to use multiple monomers that yield repeating units of (1), (2), and (5). This allows for appropriate selection based on the properties of the resins and compounds used in the organic film to be applied. This allows for performance adjustments to obtain the desired film-forming properties for single compounds, such as phenolic resins, polymethacrylates obtained by radical polymerization, polyacrylates, polystyrenes, polyimides, polyimines, polycarbonates, and other polyfunctional phenolic compounds, depending on the resins and compounds used in the organic film-forming material.

[0096] When a copolymer is used, where X represents the proportion of repeating units represented by general formula (1) and / or (2) and Y represents the proportion of repeating units represented by formula (5), and X+Y=1, the proportion is preferably such that X is 0.5 or more and Y is less than 0.5, and more preferably X is 0.6 or more. Such a proportion allows the copolymer to fully function as a surfactant, and the copolymer can be applied to organic film-forming materials regardless of resin or compound and regardless of film thickness, making it a highly versatile organic film-forming material.

[0097] The weight-average molecular weight of the polymer is preferably 1,500 to 30,000, more preferably 3,000 to 25,000, and even more preferably 5,000 to 23,000. By controlling the weight-average molecular weight within this range, the polymer can stably exhibit a sufficient surfactant effect as an organic film-forming material. Furthermore, it becomes possible to prevent poor film-forming properties due to a decrease in affinity for the solvent used in the organic film-forming material.

[0098] The molecular weight distribution (Mw / Mn) is preferably 1.0 to 5.0, and more preferably 1.1 to 3.0. A broad Mw / Mn (molecular weight distribution) allows a wide range of ultra-high molecular weight polymers and low molecular weight polymers close to the monomer to be mixed in the polymer, preventing a decrease in the surfactant effect. The molecular weight was specifically measured by the following method. 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 the eluent (solvent), and the dispersity (Mw / Mn) was also determined.

[0099] Furthermore, in the present invention, monomers that provide repeating units other than (1), (2), and (5) can be used in combination depending on the resin or compound used in the organic film-forming material. In this way, by introducing not only the specific repeating units of the present invention but also other repeating units, the range of application as an organic film-forming material can be further expanded.

[0100] [Method for producing polymer] Examples of methods for producing the polymer include a method in which the monomer is polymerized by heating in an organic solvent with the addition of a radical polymerization initiator.

[0101] Examples of organic solvents used during polymerization include toluene, benzene, tetrahydrofuran (THF), diethyl ether, dioxane, cyclohexane, cyclopentane, methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), and γ-butyrolactone (GBL). Examples of the polymerization 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, and lauroyl peroxide. The amount of these initiators added is preferably 0.01 to 25 mol% based on the total amount of monomers to be polymerized. The reaction temperature is preferably 50 to 150°C, and more preferably 60 to 100°C. The reaction time is preferably 2 to 24 hours, and more preferably 2 to 18 hours from the viewpoint of production efficiency.

[0102] The polymerization initiator may be added to the monomer solution and then fed to the reaction vessel. Alternatively, an initiator solution may be prepared separately from the monomer solution and then fed to the reaction vessel independently. Because radicals generated from the initiator during the waiting time may cause the polymerization reaction to proceed, resulting in the formation of ultra-high molecular weight polymers, it is preferable to prepare the monomer solution and the initiator solution independently and add them dropwise from the perspective of quality control. Furthermore, known chain transfer agents such as dodecyl mercaptan and 2-mercaptoethanol may be used in combination to adjust the molecular weight. In this case, the amount of these chain transfer agents added is preferably 0.01 to 20 mol % of the total amount of monomers to be polymerized.

[0103] The amount of each monomer in the monomer solution may be appropriately set so that the content of each repeating unit is in a preferred ratio depending on the required performance of the polymer.

[0104] The polymer obtained by the above-described production method may be a reaction solution obtained by a polymerization reaction as a final product, or a powder obtained through a purification step such as a reprecipitation method in which a polymerization solution is added to a poor solvent to obtain a powder, and the resulting powder may be handled as a final product. However, from the viewpoint of work efficiency and quality stability, it is preferable to handle a polymer solution obtained by dissolving the powder obtained by the purification step in a solvent as a final product.

[0105] Specific examples of the solvent used in this case include ketones such as cyclohexanone and methyl-2-n-pentyl ketone, as described in paragraphs

[0144] to

[0145] of JP-A No. 2008-111103; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; propylene glycol monomethyl ether (PGME), ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether. esters such as PGMEA, 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; lactones such as GBL; alcohols such as diacetone alcohol (DAA); high-boiling alcohol solvents such as diethylene glycol, propylene glycol, glycerin, 1,4-butanediol, and 1,3-butanediol; and mixed solvents thereof.

[0106] When the polymer is used as a polymer solution, the concentration of the polymer in the solution is preferably 0.1 to 60% by mass, more preferably 1 to 50% by mass. Within this range, the concentration is not too high, which increases the viscosity and reduces the handling performance, and the concentration is not too low, which increases the dilution amount of the polymer and compound solution when the polymer and compound are used as a solution and the amount of surfactant added to the product is required to narrow the film thickness range that can be produced.

[0107] The polymer solution is preferably filtered through a filter, which is effective in stabilizing the quality by removing foreign matter and gels that may cause film formation defects.

[0108] Examples of filter materials used for the filter filtration include fluorocarbon, cellulose, nylon, polyester, and hydrocarbon-based materials. However, in the filtration process for chemically amplified resist compositions, filters made of fluorocarbons, such as Teflon (registered trademark), hydrocarbons such as polyethylene and polypropylene, or nylon are preferred. The pore size of the filter can be selected appropriately depending on the desired cleanliness, but is preferably 100 nm or less, more preferably 20 nm or less. These filters may be used alone or in combination. The filtration method may involve passing the solution through the filter only once, but it is more preferable to circulate the solution and filter it multiple times. The filtration process can be performed in any order and any number of times during the production process of the polymer solution. However, it is preferable to filter the reaction solution after the polymerization reaction, the polymer solution, or both.

[0109] [Alternative method for producing polymer] As an alternative method for producing the polymer, a monomer having an epoxycyclohexane group or an epoxy group is polymerized by adding a radical polymerization initiator in an organic solvent and heating (Step 1), followed by an addition reaction (Step 2) with a compound having a hydroxyl group with R2 as a substituent (carboxylic acid, alcohol, phenol, etc.).

[0068] When a polymer having an epoxycyclohexane structure is used as a raw material as in paragraph

[0068] , there is no reaction selectivity, so the structure after substitution of R2 of the polymer becomes a polymer having repeating units with two types of partial structures. [ka]

[0110] The above polymer can be obtained by the methods described in

[0100] to

[0108] for the polymerization in Step 1, simply by changing the monomer to a compound having an epoxycyclohexane structure or an epoxy structure. Furthermore, the addition reaction in Step 2 can be produced by the methods described in

[0068] to

[0082] , simply by changing the raw material used from a monomer having an epoxycyclohexane structure or an epoxy structure to the polymer obtained in Step 1. Furthermore, the obtained polymer can also be used by filtering the obtained polymerization solution, as described in

[0107] and

[0108] .

[0111] In producing the polymers used in the organic film-forming compositions obtained by these methods, various compounds having hydroxyl groups can be used, allowing the compound structure and the proportion of terminal group structures to be appropriately adjusted to suit the required performance. For example, compounds having a side chain structure that contributes to improving planarization characteristics, or a fluorine-containing substituent that controls surface tension and other properties to change the surface activity can be arbitrarily combined. Therefore, these polymers not only have excellent surface activity that contributes to improving film-forming properties, but also enable high levels of compatibility between various properties such as film-forming properties and embedding properties when used in an underlayer film as an organic film-forming composition.

[0112] [Composition for organic film formation] The composition for forming an organic film of the present invention comprises an organic film-forming resin and / or compound (A), a polymer (B) having repeating units represented by the following general formula (1) and / or (2), and a solvent (C). [ka] (In formula (1), R1 represents a hydrogen atom or a methyl group, R2 represents a saturated or unsaturated monovalent organic group having 7 to 50 carbon atoms, and has at least one fluorine-containing structure represented by formula (3) below, and the substituent OR2 and the OH group on the cyclohexane ring are adjacent substituents on the carbon atoms on the cyclohexane ring.) [ka] (In formula (2), R1 and R2 are the same as above.) [ka] ((3) is a partial structure contained in R2, and * represents a bond in the structure in R2. R2 may have two or more types of structures represented by (3) or two or more identical structures.)

[0113] In the organic film-forming composition of the present invention, the (B) polymer, the (A) organic film-forming resin and / or compound, and the (C) solvent can each be used alone or in combination of two or more. The (B) polymer 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 also 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 achieving highly versatile film-forming properties that can be applied to a variety of film-forming materials.

[0114] The polymer (B) having the repeating units (1) and / or (2) 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 polymer (B) is 0.01 to 5 parts by mass per 100 parts by mass of the organic film-forming resin and / or compound (A).

[0115] [(A) Organic film-forming resin and / or compound] The organic film-forming resin and / 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 and / 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., it is more preferable that the resin and / or compound contain an aromatic skeleton.

[0116] 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.

[0117] Examples of the (A) organic film-forming resin and / or compound used in the present invention include resins containing the following structures described in JP-A Nos. 2012-001687 and 2012-077295. [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.)

[0118] [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.)

[0119] Further examples of the (A) organic film-forming resin and / 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. [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.

[0120] [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.)

[0121] [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 , R4 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 , R 6 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.

[0122] [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.)

[0123] Specific examples of the (A) organic film-forming resin and / or compound used in the present invention include resins containing the following structures described in JP-A Nos. 2004-205685, 2007-171895, and 2009-014816. [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.

[0124]

Chem.

[0125]

Chem.

[0126] Examples of the formula (11) include the following resins: [ka]

[0127] [ka]

[0128] Examples of the organic film-forming resin and / 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. [ka] (In formula (12), R 1 and R 2 are independently the same or different and are 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, or an alkenyl group having 2 to 10 carbon atoms; 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 5are 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.

[0129] [ka] (In formula (13), R 1 and R 2 are independently the same or different and are 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, or an alkenyl group having 2 to 10 carbon atoms; 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.

[0130] [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 1≦n1+n2. Note that the symbols in the formulae apply only within this formula.

[0131] [ka] (In formula (15), R1 and R2 are the same or different and are 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, or an alkenyl group having 2 to 10 carbon atoms. R 3 , R 4 are each a hydrogen atom or a glycidyl group, and R 5 is a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms, and R 6 , R 7 are a benzene ring and a naphthalene ring. p and q are each 1 or 2. n is 0 < n ≤ 1. Note that the symbols in the formula are applicable only within this formula.)

[0132] As formula (15), for example, the following resins are exemplified.

Chemical formula

[0133]

Chemical formula

[0134]

Chemical formula

[0135]

Chemical formula

[0136] Examples of the resin and / 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.

Chemical formula

[0137] Examples of the organic film-forming resin and / or compound (A) used in the present invention include resins described in JP-A-2014-29435. [ka] (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.)

[0138] Furthermore, examples of the organic film-forming resin and / 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. [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.

[0139] [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.

[0140] Examples of the organic film-forming resin and / 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. [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.

[0141] Examples of the (A) organic film-forming resin and / 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. [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.)

[0142] Examples of the organic film-forming resin and / 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): [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.)

[0143] The organic film-forming resin and / or compound (A) used in the present invention may 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 may be used. [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.)

[0144] [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.)

[0145] 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. [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.)

[0146] Examples of the organic film-forming resin and / or compound (A) used in the present invention include compounds containing the following structure described in JP-A-2017-119671. [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.) [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 10 is 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.

[0147] Examples of compounds containing the above structure include the following compounds. [ka]

[0148] Examples of the organic film-forming resin and / or compound (A) used in the present invention include polymers having a repeating unit represented by the following general formula (27-1) described in JP-A-2019-044022. [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 3 is 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.

[0149] Examples of polymers having a repeating unit represented by the above general formula (27-1) include the following polymers. [ka]

[0150] [ka]

[0151] (A) The organic film-forming resin and / or compound may be synthesized by a known method, or a commercially available product may be used.

[0152] The amount of the (A) organic film-forming resin and / 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 and / 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 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.

[0153] 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 and / or compound, and an organic film-forming composition containing such a polymer content can form an organic film with better in-plane uniformity.

[0154] 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 and / or compound and the (B) polymer, 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.

[0155] The content of the (C) solvent is preferably 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 and / or compound. By setting the content within this range, the concentration can be adjusted according to the film thickness to be consumed.

[0156] 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.

[0157] 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.

[0158] 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.

[0159] 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 and / or compound gives it thermal fluidity, thereby making it an organic film-forming material that also has high-level filling / planarizing properties.

[0160] [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 and / or compound. This amount promotes the crosslinking reaction and enables the formation of a dense film.

[0161] 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 and / or compound. This amount enhances curability and further suppresses intermixing with the overlying film.

[0162] Furthermore, a surfactant other than the polymer (B) of the present invention can be added to the organic film-forming composition of the present invention to further improve in-plane uniformity during spin coating. 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 and / or compound. This amount enables the formation of an organic film with excellent in-plane uniformity.

[0163] 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 and / or compound. This amount can improve the storage stability of the organic film-forming composition.

[0164] 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.

[0165] [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-mentioned organic film-forming composition of the present invention onto a substrate to be processed, and then heat-treating the substrate to which the organic film-forming composition has been applied 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.

[0166] 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.

[0167] 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.

[0168] [Pattern formation method] A pattern forming method using the organic film-forming composition of the present invention will be described below.

[0169] [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; using the resist upper layer film on which the circuit pattern has been formed as a mask to transfer the pattern to the silicon-containing resist intermediate film by etching; the silicon-containing resist intermediate film onto which the pattern has been transferred is used as a mask to transfer the pattern to the organic film by etching; Furthermore, the present invention provides a pattern forming method in which the pattern is transferred onto the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

[0170] 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.

[0171] 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.

[0172] 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.

[0173] 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.

[0174] 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.

[0175] 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.

[0176] 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.

[0177] 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.

[0178] In forming the circuit pattern, it is preferable to develop the circuit pattern using an alkali developer or an organic solvent.

[0179] 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.

[0180] 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.

[0181] 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 gases for 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 gases for 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.

[0182] 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.

[0183] [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 coating or an adhesion coating 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; using the resist upper layer film on which the circuit pattern has been formed as a mask, to transfer the pattern to the organic antireflective film or the adhesive film and the silicon-containing resist intermediate film by etching; the silicon-containing resist intermediate film onto which the pattern has been transferred is used as a mask to transfer the pattern to the organic film by etching; Furthermore, the present invention provides a pattern forming method in which the pattern is transferred onto the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

[0184] 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 adhesion film is formed between the silicon-containing resist intermediate film and the resist top layer film.

[0185] The organic anti-reflection film and the adhesive film can be formed by spin coating using known organic anti-reflection film materials.

[0186] [Trilayer resist process using inorganic hard mask intermediate 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 intermediate film 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 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 inorganic hard mask intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; the pattern is transferred to the organic film by etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; Furthermore, the present invention provides a pattern forming method in which the pattern is transferred onto the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

[0187] This method can be performed in the same manner as the three-layer resist process using the silicon-containing resist interlayer described above, except that an inorganic hard mask interlayer is formed on the organic film instead of the silicon-containing resist interlayer.

[0188] The inorganic hard mask intermediate film 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 intermediate film is preferably 5 to 200 nm, more preferably 10 to 100 nm. As the inorganic hard mask intermediate film, a SiON film is most preferably used because of its high anti-reflection effect.

[0189] [Four-layer resist process using inorganic hard mask intermediate film 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 intermediate film 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 adhesion film on the inorganic hard mask 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; using the resist upper layer film on which the circuit pattern has been formed as a mask, to transfer the pattern to the organic anti-reflective film or the adhesion film and the inorganic hard mask intermediate film by etching; the pattern is transferred to the organic film by etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; Furthermore, the present invention provides a pattern forming method in which the pattern is transferred onto the workpiece by etching using the organic film onto which the pattern has been transferred as a mask.

[0190] This method can be performed in the same manner as the above-mentioned three-layer resist process using an inorganic hard mask intermediate film, except that an organic antireflective coating (BARC) or an adhesion film is formed between the inorganic hard mask intermediate film and the resist top layer film.

[0191] In particular, when a SiON film is used as the inorganic hard mask intermediate film, 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.

[0192] 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).

[0193] When an inorganic hard mask intermediate film is formed, the silicon-containing resist intermediate film 4 can be replaced with an inorganic hard mask intermediate film, and when a BARC or adhesion film is formed, 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.

[0194] 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]

[0195] 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.

[0196] [Synthesis of Monomers (M1) to (M12)] The compounds (M1) to (M12) used in preparing the organic film-forming composition were synthesized using the epoxy compounds (E1) to (E3) and hydroxyl group-containing compounds (alcohol compounds or carboxylic acid compounds) (F1) to (F8) shown below.

[0197] Epoxy compounds [ka]

[0198] Hydroxyl-containing compounds (phenols or carboxylic acid compounds) [ka]

[0199] [Synthesis Example 1] Synthesis of (M1) [ka] Under a nitrogen atmosphere, 50.0 g (274.4 mmol) of epoxy compound (E1), 48.9 g (274.4 mmol) of hydroxyl-containing compound (F1), 2.0 g (8.8 mmol) of benzyltriethylammonium chloride, and 200 g of 2-methoxy-1-propanol were added and the mixture was heated to an internal temperature of 80 °C to form a homogeneous solution, followed by stirring at an internal temperature of 100 °C for 24 hours. After cooling to room temperature, 500 mL of diisopropyl ether was added. The mixture was washed twice with 100 g of 3% aqueous NaHCO3 solution, 100 g of ultrapure water, once with 100 g of 3% aqueous nitric acid solution, and five times with 100 g of ultrapure water. The organic layer was then evaporated to dryness under reduced pressure to obtain monomer (M1). The isomer ratio calculated by LC (liquid chromatography) was 50:50.

[0200] Monomers (M2) to (M12) were obtained as products under the same reaction conditions as in Synthesis Example 1, except that the epoxy compounds and hydroxyl group-containing compounds were changed to those shown in Table 1. The synthesis method (Synthesis Example 1) used to synthesize the compounds is also shown in the table. When a hydroxyl group-containing compound was used, the reaction was carried out using a small excess of carboxylic acid relative to the epoxy compound to improve reaction efficiency. [Table 1]

[0201] The structural formulas and isomer ratios of the monomers (M1) to (M12) obtained in Synthesis Examples 1 to 12 are shown below. [ka]

[0202] In synthesizing the polymers (A1) to (A19) used as polymers for organic film-forming materials, the monomers (M1) to (M12) synthesized in the above synthesis examples and the following monomers (m1) to (m4) were used. [ka]

[0203] [Synthesis Example 13] Synthesis of polymer (A1) 10.0 g of propylene glycol monomethyl ether acetate (PGMEA) was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 3.60 g (15.0 mmol) of monomer (M1), 0.173 g (0.75 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (A1). Analysis revealed that the weight-average molecular weight (Mw) of polymer (A1) was 12,900 and the polydispersity (Mw / Mn) was 1.45. [ka]

[0204] [Synthesis Examples 14-31] Polymers (A2)-(A19) Polymers (A2) to (A19) shown below were obtained by the same method as in Synthesis Example 13, except that the types and molar ratios of the monomers used were changed according to the structure of each polymer. The weight average molecular weight (Mw) and dispersity (Mw / Mn) determined by GPC are also shown. [ka]

[0205] [ka]

[0206] [Synthesis Example 32] Synthesis of polymer (A20) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 2.13 g (15.0 mmol) of glycidyl methacrylate, 0.103 g (0.45 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 10 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature, and then 10.0 g of propylene glycol monomethyl ether (PGME), 3.24 g (15.75 mmol) of 4-(trifluoromethoxy)benzoic acid, and 0.17 g (0.75 mmol) of benzyltriethylammonium chloride were added. The mixture was heated at 100°C under a nitrogen atmosphere for 16 hours. After cooling to room temperature, 100 ml of methyl isobutyl ketone was added, and the mixture was washed twice with 30 g of 3% NaHCO3 aqueous solution, once with 30 g of ultrapure water, once with 30 g of 3% nitric acid aqueous solution, and five times with 30 g of ultrapure water. The organic layer was then evaporated to dryness under reduced pressure, and PGMEA was added for further concentration and solvent substitution to obtain polymer (A20) as a 30 wt% polymer solution. Analysis of polymer (A20) showed that the weight-average molecular weight (Mw) was 24,100 and the polydispersity (Mw / Mn) was 2.25.

[0207] [Synthesis Example 33] Synthesis of polymer (A21) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 2.13 g (15.0 mmol) of glycidyl methacrylate, 0.069 g (0.30 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 10 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature, and then 10.0 g of PGME, 3.24 g (15.75 mmol) of 4-(trifluoromethoxy)benzoic acid, and 0.17 g (0.75 mmol) of benzyltriethylammonium chloride were added. The mixture was heated at 100°C under a nitrogen atmosphere for 16 hours. After cooling to room temperature, 100 ml of methyl isobutyl ketone was added, and the mixture was washed twice with 30 g of 3% NaHCO3 aqueous solution, once with 30 g of ultrapure water, once with 30 g of 3% nitric acid aqueous solution, and five times with 30 g of ultrapure water. The organic layer was then evaporated to dryness under reduced pressure, and PGMEA was added for further concentration and solvent substitution to obtain polymer (A21) as a 30 wt% polymer solution. Analysis of polymer (A21) showed that the weight-average molecular weight (Mw) was 31,200 and the dispersity (Mw / Mn) was 2.87.

[0208] [Synthesis Example 34] Synthesis of polymer (A22) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 2.13 g (15.0 mol) of glycidyl methacrylate, 0.345 g (1.5 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 10 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature, and then 10.0 g of PGME, 3.47 g (15.75 mmol) of 4-(trifluoromethoxy)phenylacetic acid, and 0.17 g (0.75 mmol) of benzyltriethylammonium chloride were added. The mixture was heated at 100°C under a nitrogen atmosphere for 16 hours. After cooling to room temperature, 100 ml of methyl isobutyl ketone was added, and the mixture was washed twice with 30 g of 3% NaHCO3 aqueous solution, once with 30 g of ultrapure water and 30 g of 3% nitric acid aqueous solution, and five times with 30 g of ultrapure water. The organic layer was then evaporated to dryness under reduced pressure, and PGMEA was added for further concentration and solvent substitution to obtain polymer (A22) as a 30 wt% polymer solution. Analysis of polymer (A22) showed that the weight average molecular weight (Mw) was 6800 and the polydispersity (Mw / Mn) was 2.57.

[0209] [Synthesis Example 35] Synthesis of polymer (A23) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 2.13 g (15.0 mol) of glycidyl methacrylate, 0.518 g (22.5 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 10.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature, and then 10.0 g of PGME, 3.47 g (15.75 mmol) of 4-(trifluoromethoxy)phenylacetic acid, and 0.17 g (0.75 mmol) of benzyltriethylammonium chloride were added. The mixture was heated at 100°C under a nitrogen atmosphere for 16 hours. After cooling to room temperature, 100 ml of methyl isobutyl ketone was added, and the mixture was washed twice with 30 g of 3% NaHCO3 aqueous solution, once with 30 g of ultrapure water and 30 g of 3% nitric acid aqueous solution, and five times with 30 g of ultrapure water. The organic layer was then evaporated to dryness under reduced pressure, and PGMEA was added for further concentration and solvent substitution to obtain polymer (A23) as a 30 wt% polymer solution. Analysis of polymer (A23) showed that the weight average molecular weight (Mw) was 4800 and the polydispersity (Mw / Mn) was 2.87.

[0210] [Synthesis of comparative polymers (R1) to (R9)] The comparative polymers (R1) to (R9) used to prepare the organic film-forming compositions were synthesized using the following monomers (b1) to (b10). [ka]

[0211] [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 (b1), 7.46 g (0.034 mol) of monomer (b3), 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

[0212] [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 (b1), 5.76 g (0.041 mol) of monomer (b4), 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

[0213] [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 (b2), 1.92 g (0.014 mol) of monomer (b3), 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

[0214] [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 (b2), 3.20 g (0.023 mol) of (b5), 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

[0215] [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 (b2), 5.41 g (0.036 mol) of (b6), 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

[0216] [Comparative Synthesis Example 6] Synthesis of Comparative Polymer (R6) [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 5.31 g (15.0 mmol) of monomer (b7), 0.173 g (0.75 mmol) 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 (R6). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (R6): Mw = 12000, Mw / Mn = 1.48

[0217] [Comparative Synthesis Example 7] Synthesis of Comparative Polymer (R7) [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 4.25 g (12.0 mmol) of monomer (b7), 2.02 g (3.0 mmol) of monomer (b8), 0.173 g (0.75 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 34 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (R7). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (R7): Mw = 10400, Mw / Mn = 1.50

[0218] [Comparative Synthesis Example 8] Synthesis of Comparative Polymer (R8) [ka] Under a nitrogen atmosphere, 10.0 g of PGMEA was heated and stirred at 80°C. To this was added dropwise a mixture of 4.77 g (15.0 mmol) of monomer (b9), 0.173 g (0.75 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 10.0 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 (R8). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (R8): Mw = 11500, Mw / Mn = 1.94

[0219] [Comparative Synthesis Example 9] Synthesis of Comparative Polymer (R9) [ka] Under a nitrogen atmosphere, 10.0 g of PGMEA was heated and stirred at 80°C. To this was added dropwise a mixture of 3.34 g (10.5 mmol) of monomer (b9), 2.17 g (4.5 mmol) of monomer (b10), 0.173 g (0.75 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 10.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (R9). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (R9): Mw = 12500, Mw / Mn = 1.92

[0220] [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):

[0221] [ka]

[0222] [solvent] (D1): Propylene glycol monomethyl ether acetate (D2): Propylene glycol monoethyl ether

[0223] [Preparation of Organic Film-Forming Compositions (UDL-1 to 79, Comparative UDL-1 to 20)] The polymers (A1) to (A23), (R1) to (R9), organic film-forming resins or compounds (C1) to (C6), and solvents were dissolved in the proportions shown in Tables 2 to 5, and the resulting solution was filtered through a 0.1 μm fluororesin filter to prepare organic film materials (resist underlayer film materials: UDL-1 to 79, comparative examples UDL-1 to 20). [Table 2]

[0224] [Table 3]

[0225] [Table 4]

[0226] [Table 5]

[0227] [Preparation of Silicon Wafers with Organic Cured Films Formed Using Organic Film-Forming Compositions (UDL-1 to 79, Comparative UDL-1 to 20)] 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 79, comparative UDL-1 to 20) 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 shown in Tables 6 to 9. 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.

[0228] [Solvent Resistance Evaluation: Examples 1-1 to 1-79, Comparative Examples 1-1 to 1-20] Using the method described above, organic film-forming compositions (UDL-1 to 79, Comparative UDL-1 to 20) 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 again. 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.

[0229] [In-plane uniformity evaluation: Examples 1-1 to 1-79, Comparative Examples 1-1 to 1-20] The organic film-forming compositions (UDL-1 to 79, comparative UDL-1 to 20) were formed on silicon wafers by the above method, and the film thickness was measured within a radius of 145 mm from the center of the organic cured film. The maximum film thickness was designated as X max , the minimum film thickness is X min , the average film thickness is Xaverage 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).

[0230] [Contact Angle Evaluation: Examples 1-1 to 1-79, Comparative Examples 1-1 to 1-10, and Comparative Examples 1-13 to 1-14] Using the method described above, compositions for forming organic films (UDL-1 to 79, Comparative UDL-1 to 10, Comparative UDL-13 to 14) were formed on silicon wafers, and the contact angles with pure water were measured. Comparative UDL-11 to 12 and Comparative UDL-15 to 20 were not measured due to poor in-plane uniformity.

[0231] [Table 6]

[0232] [Table 7]

[0233] [Table 8]

[0234] [Table 9]

[0235] [Hump suppression evaluation: Examples 2-1 to 2-79, Comparative Examples 2-1 to 2-12] Using the method described above, organic film-forming compositions (UDL-1 to 79, Comparative UDL-1 to 10, Comparative UDL-13 to 14) were deposited on silicon wafers, and the height change from the outer periphery 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, the maximum height was rated A (good) if it was less than 110% of the film thickness, as shown in Figure 1; B if it was 110% or more but less than 150%; and C (poor) if there was a region where the height was 150% or more, as shown in Figure 2.

[0236] [Embedding Evaluation-1: Examples 2-1 to 2-79, Comparative Examples 2-1 to 2-12] As shown in Figure 4, organic film-forming compositions (UDL-1 to 79, Comparative UDL-1 to 10, and Comparative UDL-13 to 14) were deposited by the above method on a SiO2 wafer substrate with a dense hole pattern (hole diameter 0.2 μm, hole depth 1.0 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). If no voids were generated, the sample was evaluated as good, and if voids were generated, the sample was evaluated as poor.

[0237] [Embedding Evaluation-2: Examples 2-57 to 2-79] As shown in Figure 4, organic film-forming compositions (UDL-57 to 79) 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), forming 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.

[0238] [Evaluation of Coatability of Silicon-Containing Resist Interlayer: Examples 2-1 to 2-79, Comparative Examples 2-1 to 2-12] Using the above method, an organic cured film was formed on a silicon wafer substrate using an organic film-forming composition (UDL-1 to 79, Comparative UDL-1 to 10, Comparative UDL-13 to 14), and the following silicon-containing resist interlayer material (SOG1) was applied thereon and baked at 200°C for 60 seconds to form a silicon-containing resist interlayer. The state of the silicon-containing resist interlayer coating was then visually observed and evaluated. If the coating film was in good condition, it was rated as good, and if dewetting occurred, it was rated as poor. 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.

[0239] 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 10, and filtering the resultant mixture through a 0.1 μm fluororesin filter. [Table 10]

[0240] The polymer (SP1) is shown below. [ka]

[0241] TMPANO3: Trimethylphenylammonium nitrate PGEE: Propylene glycol ethyl ether

[0242] [Table 11]

[0243] [Table 12]

[0244] [Table 13]

[0245] [Table 14]

[0246] As shown in Tables 6 to 9 and 11 to 14, the organic film-forming compositions of the present invention (UDL-1 to 79) were confirmed to be excellent in solvent resistance, in-plane uniformity, hump suppression, filling properties, and coating properties of silicon-containing resist intermediate films. Furthermore, UDL-69 to 75 were found to be even more excellent from Filling Evaluation-2.

[0247] [Pattern formation test: Examples 3-1 to 3-56] Using the above method, an organic cured film was formed on a SiO2 wafer substrate using an organic film-forming composition (UDL-1 to 56). The following silicon-containing resist intermediate film material (SOG2) 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.

[0248] The silicon-containing resist intermediate film material (SOG2) was prepared by dissolving the polymer (SP1), crosslinking catalyst, and acid in an organic solvent and water in the proportions shown in Table 15, and filtering the resultant mixture through a 0.1 μm fluororesin filter. [Table 15]

[0249] The resist top layer material (ArF single-layer resist) was prepared by dissolving a polymer (RP1), an acid generator (PAG1), and a basic compound (Amine1) in a solvent containing 0.1 mass% of FC-430 (manufactured by Sumitomo 3M Limited) in the proportions shown in Table 16, and filtering the solution through a 0.1 μm fluororesin filter. [Table 16]

[0250] The polymer (RP1), acid generator (PAG1), and basic compound (Amine1) are shown below. [ka]

[0251] The immersion protective film material (TC-1) was prepared by dissolving the polymer (PP1) in an organic solvent in the ratio shown in Table 17 and filtering the solution through a 0.1 μm fluorine resin filter. [Table 17]

[0252] The polymer (PP1) is shown below. [ka]

[0253] 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).

[0254] 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.

[0255] (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

[0256] (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

[0257] (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

[0258] 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 18 and 19. [Table 18]

[0259] [Table 19]

[0260] As shown in Tables 18 and 19, in Examples 3-1 to 3-56 in which the organic film-forming compositions (UDL-1 to 56) of the present invention were used, the resist upper layer film pattern was successfully transferred to the SiO2 wafer substrate in the end, confirming that the organic film-forming compositions of the present invention are suitable for use in microfabrication using the multilayer resist method.

[0261] [Preparation of resist top layer materials (ArFPR1-23, comparative ArFPR)] The polymer (RP1), acid generator (PAG1), basic compound (Amine1), and compound were dissolved in a solvent in the proportions shown in Table 20, and the resulting mixture was filtered through a 0.1 μm fluororesin filter to prepare resist top layer film materials (ArFPR1 to 23, comparative ArFPR). [Table 20]

[0262] [Preparation of silicon wafers with resist top layer films formed using resist top layer film materials (ArFPR1-23, comparative ArFPR)] Using a Tokyo Electron Co., Ltd. coater / developer "CLEAN TRACK LITHIUS Pro AP," 2 ml of the resist top layer material (ArFPR1-23, comparative ArFPR) prepared above was dispensed onto the center of a silicon wafer and spread by rotating it at a rotation speed that would result in an average film thickness of 100 nm after baking. Next, the silicon wafer coated with the resist top layer film was heated at 105°C for 60 seconds to obtain a silicon wafer with a resist top layer film formed thereon.

[0263] [Evaluation of in-plane uniformity of resist top layer film: Examples 4-1 to 4-23, Comparative Example 4-1] The thickness of the resist top layer (ArFPR1-23, comparative ArFPR) formed on the silicon wafer by the above method was measured within a radius of 145 mm from the center, and the maximum thickness was calculated as X max , the minimum film thickness is X min , the average film thickness is X average As, (X max -X min ) / X average The value obtained by the above formula was taken as the in-plane uniformity (%). In-plane uniformity of less than 3% was considered good, and 3% or more was considered poor. [Table 21]

[0264] As shown in Table 21, the resist top layer film materials of the present invention (ArFPR1 to 23) have excellent in-plane uniformity, which indicates that the polymers 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.

[0265] [Preparation of silicon-containing resist intermediate film materials (SOG3-25)] Silicon-containing resist interlayer materials (SOG3 to SOG25) were prepared by dissolving the polymer (SP1), crosslinking catalyst, and acid in an organic solvent and water in the proportions shown in Table 22, and then filtering the mixture through a 0.1 μm fluororesin filter. [Table 22]

[0266] [Evaluation of Coatability of Silicon-Containing Resist Interlayer: Examples 5-1 to 5-23, 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 interlayer film materials (SOG1, 3-25) were applied thereon and baked at 200°C for 60 seconds to form silicon-containing resist interlayer films. The state of the silicon-containing resist interlayer film coating was then visually observed and evaluated. If the coating film was in good condition, it was rated as good, and if dewetting occurred, it was rated as poor. 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. [Table 23]

[0267] As shown in Table 23, the silicon-containing resist intermediate film materials (SOG3 to SOG25) exhibit excellent film-forming properties without dewetting, which indicates that the polymers of the present invention can be used as surfactants to impart high film-forming properties to various film-forming compositions.

[0268] From the above, the organic film-forming composition of the present invention has excellent film-forming properties, high-level filling properties, and hump suppression properties, and is excellent in coatability for silicon-containing resist intermediate films, making it 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. Furthermore, it is possible to form an organic film in which humps are suppressed, making it possible to efficiently manufacture semiconductor elements and the like. Furthermore, the polymer of the present invention can be widely used as a surfactant, as it exhibits high film-forming properties.

[0269] The present specification includes the following aspects. [1]: A composition for forming an organic film, comprising an organic film-forming resin and / or compound (A), a polymer (B) having repeating units represented by the following general formula (1) and / or (2), and a solvent (C): [ka] (In formula (1), R1 represents a hydrogen atom or a methyl group, R2 represents a saturated or unsaturated monovalent organic group having 7 to 50 carbon atoms, and has at least one fluorine-containing structure represented by formula (3) below, and the substituent OR2 and the OH group on the cyclohexane ring are adjacent substituents on the carbon atoms on the cyclohexane ring.) [ka] (In formula (2), R1 and R2 are the same as above.) [ka] ((3) is a partial structure contained in R2, and * represents a bond in the structure in R2. R2 may have two or more types of structures represented by (3) or two or more identical structures.) [2]: The composition for forming an organic film according to [1] above, wherein R2 in the general formulas (1) and (2) contains a partial structure represented by the following general formula (4): [ka] (* represents a bond.) [3]: The organic film-forming composition according to [1] or [2], wherein the polymer (B) is a copolymer having repeating units of either or both of the general formulae (1) and (2) and the following general formula (5): [ka] (In the formula, R3 represents a hydrogen atom or a methyl group, R4 and R5 each represent a linear or branched divalent alkylene group having 1 to 4 carbon atoms, R6 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, m1 represents an integer of 0 to 23, n1 represents an integer of 0 to 23, and 2≦m1+n1≦23.) [4]: The composition for forming an organic film according to any one of [1] to [3] above, wherein the polymer (B) has a weight average molecular weight of 1,500 to 30,000. [5]: The composition for forming an organic film according to any one of [1] to [4], characterized in that the content of the polymer (B) is 0.01 to 5 parts by mass when the resin for forming an organic film and / or the compound (A) is taken as 100 parts by mass. [6]: A method for forming an organic film used in the manufacturing process of a semiconductor device, comprising spin-coating a composition for forming an organic film according to any one of [1] to [5] above onto a substrate to be processed, and then heat-treating the substrate to which the composition for forming an organic film has been applied 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. [7]: A pattern formation method, comprising: forming an organic film on a workpiece using any one of the organic film-forming compositions [1] to [5] 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 consisting of a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern by etching to the silicon-containing resist intermediate film using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern by etching to the organic film using the silicon-containing resist intermediate film on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask. [8]: A pattern formation method, comprising: forming an organic film on a workpiece using any one of the organic film-forming compositions [1] to [5] above; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material; forming an organic antireflective film or an adhesive film on the silicon-containing resist intermediate film; forming a resist upper layer film on the organic antireflective film or the adhesive film using a resist upper layer film material consisting of a photoresist composition; forming a circuit pattern on the resist upper layer film; using the resist upper layer film on which the circuit pattern has been formed as a mask to transfer the pattern to the organic antireflective film or the adhesive film and the silicon-containing resist intermediate film by etching; using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask to transfer the pattern to the organic film by etching; and further using the organic film to which the pattern has been transferred as a mask to transfer the pattern to the workpiece by etching. [9]: A pattern formation method, comprising: forming an organic film on a workpiece using the organic film-forming composition according to any one of [1] to [5] above; forming an inorganic hard mask intermediate film 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 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 inorganic hard mask 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 inorganic hard mask 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.

[10] : A pattern formation method, comprising: forming an organic film on a workpiece using the organic film-forming composition according to any one of [1] to [5] above; forming an inorganic hard mask intermediate film 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 intermediate film; 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 by etching the organic antireflective film or the adhesive film and the inorganic hard mask intermediate film using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern by etching the organic film using the inorganic hard mask 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.

[11] : The pattern forming method according to [9] or

[10] above, wherein the inorganic hard mask intermediate film is formed by a CVD method or an ALD method.

[12] : The pattern formation method according to any one of [7] to

[10] 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.

[13] : The pattern forming method according to any one of [7] to

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

[14] : The pattern formation method according to any one of [7] to

[10] above, characterized in that the workpiece is a semiconductor device substrate, or a semiconductor device substrate having 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 formed thereon.

[15] : The pattern formation method according to

[14] 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.

[16] : A monomer represented by the following general formula (6) or (7): [ka] (In formula (6), R1 represents a hydrogen atom or a methyl group, R2 represents a saturated or unsaturated monovalent organic group having 7 to 50 carbon atoms, and has at least one fluorine-containing structure represented by formula (3) below, and the substituent OR2 and the OH group on the cyclohexane ring are adjacent substituents on the carbon atoms on the cyclohexane ring.) [ka] (In formula (7), R1 and R2 are the same as above.) [ka] ((3) is a partial structure contained in R2, and * represents a bond in the structure in R2. R2 may have two or more types of structures represented by (3) or two or more identical structures.)

[17] : The monomer according to the above

[16] , wherein R2 in the general formulae (6) and (7) contains a partial structure represented by the following general formula (4): [ka] (* represents a bond.)

[18] : A polymer characterized by having repeating units represented by the following general formula (1) and / or (2): [ka] (In formula (1), R1 represents a hydrogen atom or a methyl group, R2 represents a saturated or unsaturated monovalent organic group having 7 to 50 carbon atoms, and has at least one fluorine-containing structure represented by formula (3) below, and the substituent OR2 and the OH group on the cyclohexane ring are adjacent substituents on the carbon atoms on the cyclohexane ring.) [ka] (In formula (2), R1 and R2 are the same as above.) [ka] ((3) is a partial structure contained in R2, and * represents a bond in the structure in R2. R2 may have two or more types of structures represented by (3) or two or more identical structures.)

[19] : The polymer according to the above

[18] , wherein R2 in the general formulae (1) and (2) contains a partial structure represented by the following general formula (4): [ka] (* represents a bond.)

[20] : The polymer according to

[18] or

[19] above, characterized in that the polymer is a copolymer having repeating units of either or both of the general formulae (1) and (2) and the following general formula (5): [ka] (In the formula, R3 represents a hydrogen atom or a methyl group, R4 and R5 each represent a linear or branched divalent alkylene group having 1 to 4 carbon atoms, R6 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, m1 represents an integer of 0 to 23, n1 represents an integer of 0 to 23, and 2≦m1+n1≦23.)

[21] : The polymer according to any one of

[18] to

[20] above, wherein the weight-average molecular weight of the polymer is 1,500 to 30,000.

[0270] The present invention is not limited to the above-described embodiments, which 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 provides similar effects is included within the technical scope of the present invention. [Explanation of symbols]

[0271] 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, 8...Resist underlayer film

Claims

1. A composition for forming an organic film, comprising: a resin and / or compound (A) for forming an organic film; a polymer (B) having repeating units represented by the following general formula (1) and / or (2); and a solvent (C): 【Chemical 1】 ((1), where R １ represents a hydrogen atom or a methyl group, R ２ is a saturated or unsaturated monovalent organic group having 7 to 50 carbon atoms, and has at least one fluorine-containing structure represented by the following formula (3), and a substituent OR on the cyclohexane ring ２ and OH groups are adjacent substituents on the carbon atoms of the cyclohexane ring. 【Chemistry 2】 ((2), where R １ , R ２ is the same as above.) 【Chemistry 3】 ((3) is R ２ is a partial structure included in R ２ represents a bond in the structure, and R ２ (3) may contain two or more types of structures or two or more identical structures.)

2. R in the general formulas (1) and (2) ２ The organic film-forming composition according to claim 1, characterized in that the organic film-forming composition according to claim 1 contains a partial structure represented by the following general formula (4): 【Chemistry 4】 (* represents a bond.)

3. 2. The organic film-forming composition according to claim 1, wherein the polymer (B) is a copolymer having repeating units represented by either or both of the general formulas (1) and (2) and the following general formula (5): 【Chemistry 5】 (In the formula, R ３ represents a hydrogen atom or a methyl group, R ４ and R ５ are each a linear or branched divalent alkylene group having 1 to 4 carbon atoms, R ６ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, m1 is 0 to 23, n1 is 0 to 23, and 2≦m1+n1≦23.

4. 2. The organic film-forming composition according to claim 1, wherein the polymer (B) has a weight average molecular weight of 1,500 to 30,000.

5. The composition for forming an organic film according to claim 1, characterized in that the content of the polymer (B) is 0.01 parts by mass to 5 parts by mass when the resin for forming an organic film and / or the compound (A) is 100 parts by mass.

6. 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 5 onto a substrate to be processed, and heat-treating the substrate to which the composition for forming an organic film has been applied at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds, thereby curing the composition and forming an organic film.

7. 10. A pattern formation method comprising: forming an organic film on a workpiece using the organic film-forming composition according to claim 1; 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 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.

8. 10. A pattern formation method comprising: forming an organic film on a workpiece using the organic film-forming composition according to claim 1; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material; forming an organic antireflective film or an adhesive film on the silicon-containing resist intermediate film; 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; using the resist upper layer film on which the circuit pattern has been formed as a mask to transfer the pattern to the organic antireflective film or the adhesive film and the silicon-containing resist intermediate film by etching; using the silicon-containing resist intermediate film on which the pattern has been transferred as a mask to transfer the pattern to the organic film by etching; and further using the organic film on which the pattern has been transferred as a mask to transfer the pattern to the workpiece by etching.

9. 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 intermediate film 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 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 inorganic hard mask 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 inorganic hard mask 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.

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 intermediate film 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 intermediate film; 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 by etching to the organic antireflective film or the adhesive film and the inorganic hard mask intermediate film using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern by etching to the organic film using the inorganic hard mask 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.

11. 10. The pattern formation method according to claim 9, wherein the inorganic hard mask intermediate film is formed by a CVD method or an ALD method.

12. 8. The pattern forming method according to claim 7, 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.

13. 8. The pattern forming method according to claim 7, wherein the circuit pattern is developed using an alkali developer or an organic solvent.

14. 8. The pattern forming method according to claim 7, wherein the workpiece is a semiconductor device substrate, or a semiconductor device substrate having 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 formed thereon.

15. 15. The pattern formation method according to claim 14, 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.

16. A monomer characterized by being represented by the following general formula (6) or (7): 【Chemistry 6】 ((6), where R １ represents a hydrogen atom or a methyl group, R ２ is a saturated or unsaturated monovalent organic group having 7 to 50 carbon atoms, and has at least one fluorine-containing structure represented by the following formula (3), and a substituent OR on the cyclohexane ring ２ and OH groups are adjacent substituents on the carbon atoms of the cyclohexane ring. 【Chemistry 7】 (In formula (7), R １ , R ２ is the same as above.) 【Chemistry 8】 ((3) is R ２ is a partial structure included in R ２ represents a bond in the structure, and R ２ (3) may contain two or more types of structures or two or more identical structures.)

17. R in the general formulas (6) and (7) ２ The monomer according to claim 16, characterized in that it contains a partial structure represented by the following general formula (4): 【Chemistry 9】 (* represents a bond.)

18. A polymer characterized by having repeating units represented by the following general formula (1) and / or (2): 【Chemistry 10】 ((1), where R １ represents a hydrogen atom or a methyl group, R ２ is a saturated or unsaturated monovalent organic group having 7 to 50 carbon atoms, and has at least one fluorine-containing structure represented by the following formula (3), and a substituent OR on the cyclohexane ring ２ and OH groups are adjacent substituents on the carbon atoms of the cyclohexane ring. 【Chemistry 11】 ((2), where R １ , R ２ is the same as above.) 【Chemistry 12】 ((3) is R ２ is a partial structure included in R ２ represents a bond in the structure, and R ２ (3) may contain two or more types of structures or two or more identical structures.)

19. R in the general formulas (1) and (2) ２ The polymer according to claim 18, characterized in that it contains a partial structure represented by the following general formula (4): 【Chemistry 13】 (* represents a bond.)

20. The polymer according to claim 18, wherein the polymer is a copolymer having repeating units represented by either or both of the general formulas (1) and (2) and the following general formula (5): 【Chemistry 14】 (In the formula, R ３ represents a hydrogen atom or a methyl group, R ４ and R ５ are each a linear or branched divalent alkylene group having 1 to 4 carbon atoms, R ６ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, m1 is 0 to 23, n1 is 0 to 23, and 2≦m1+n1≦23.

21. The polymer according to any one of claims 18 to 20, wherein the weight average molecular weight of the polymer is 1,500 to 30,000.

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