Organic film forming benzenesulfonate compound, organic film forming composition, organic film forming method, and pattern forming method

Abstract

To provide an organic film forming composition employing a benzenesulfonate that is not classified as a perfluoroalkyl compound (PFAS), the composition enabling formation of a film with excellent coating properties when used as an organic underlayer film for a multilayer resist and being useful as a photoresist material.SOLUTION: An organic film forming composition contains an organic film forming resin and / or compound (A), a benzenesulfonate compound (B) represented by the following formula (1), in which an anion moiety in the formula (1) has a molecular weight of 200 or more and which does not contain a perfluoroalkyl group, and a solvent (C).SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

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

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

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

[0005] Although many technologies for the organic underlayer film described above are already known (for example, Patent Document 2), with the recent advances in miniaturization, there is an increasing need for excellent filling properties in addition to dry etching properties. There is a need for organic underlayer film materials that can be uniformly formed on the underlying substrate to be processed, even on substrates or materials with complex shapes, and that have filling properties that enable the necessary patterns to be filled without voids.

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

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

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

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

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

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

[0012] As an example of the above-mentioned materials using perfluoroalkyl compounds, thermal acid generators and photoacid generators using perfluoroalkylsulfonic acids have high acidity and are widely used in resist materials, underlayer films, and anti-reflective films (Patent Documents 3 and 4).

[0013] In view of future tightening of regulations, it is necessary to use materials that do not fall under the PFAS regulations. For example, thermal acid generators containing 5-sulfosalicylic acid or p-phenolsulfonic acid and their use have been proposed as the thermal acid generators mentioned above (Patent Document 4). [Prior art documents] [Patent documents]

[0014] [Patent Document 1] Patent No. 4355943 etc. [Patent Document 2] Japanese Patent Application Laid-Open No. 2004-205685 [Patent Document 3] Japanese Patent Application Publication No. 2018-173521 [Patent Document 4] Japanese Patent Application Laid-Open No. 2024-1185 Summary of the Invention [Problem to be solved by the invention]

[0015] The present invention, conceived in light of the above circumstances, provides a film-forming material using a benzenesulfonate salt that is not classified as a perfluoroalkyl compound (PFAS). The use of this organic film material composition containing this benzenesulfonate salt enables the formation of a film with excellent coating properties, such as reduced pinhole and other coating defects on substrates (wafers), film-forming properties (in-plane uniformity), and embedding properties. Furthermore, the use of this organic film-forming composition as an organic underlayer film material enables the formation of an organic film with excellent process margins when used as an organic underlayer film for multilayer resists. The present invention also provides an organic film-forming method and a pattern-forming method using this organic film-forming composition. Furthermore, the organic film-forming composition is also useful as a photoresist material, providing excellent film flatness after coating and fewer defects not only after coating but also after development. The present invention also provides a pattern-forming method using this composition. The above aims to provide a film-forming material that is not classified as a PFAS and has a low environmental impact. [Means for solving the problem]

[0016] To solve the above problems, the present invention provides the following.

[0017] 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 benzenesulfonate compound (B) represented by the following formula (1), in which the molecular weight of the anion moiety in formula (1) is 200 or more and which does not contain a perfluoroalkyl group, and a solvent (C): [ka] (wherein R1 represents a linear, cyclic, or branched alkyl group having 1 to 20 carbon atoms, which may have a substituent not including a perfluoroalkyl group, an alkenyl group, an oxoalkyl group, an aryl group, an aralkyl group, or -P(R)2 (wherein R is an alkyl group or an aryl group having 1 to 20 carbon atoms), or a halogen atom or a nitro group; n represents an integer of 1 to 5; A +represents an ammonium cation, a pyridinium cation, a sulfonium cation, a phosphonium cation, an imidazolium cation, a piperidinium cation, or a pyrrolidinium cation.

[0018] Such an organic film-forming composition can be imparted with photosensitivity and can be used as an organic film-forming material as a resist material for photolithography and the like. Furthermore, an organic film-forming composition containing a benzenesulfonate compound of this molecular weight can function satisfactorily as a thermal acid generator or photoacid generator, and by specifying the molecular weight, it can prevent sublimation during heat treatment, providing good in-plane uniformity and sufficient edge curing. Therefore, the film-forming material of the present invention can provide a film-forming material that can be applied not only to film-forming materials using only various polymers, but also to film-forming materials using organic polymers and compounds, or inorganic materials such as silicon, titanium, and zirconium.

[0019] The benzenesulfonate compound (B) is preferably one represented by the following general formula (2-1), (2-2) or (2-3). [ka] (A + is A in the above formula (1) + is equivalent to [ka] (In the formula, R2 represents a chlorine atom or an iodine atom. m represents an integer of 1 to 5. A + is A in the above formula (1) + is equivalent to [ka] (In the formula, R3 is an alkyl group having 1 to 20 carbon atoms which may have a substituent but does not contain a perfluoroalkyl group. A + is A in the above formula (1) + is equivalent to

[0020] A benzenesulfonate having the above-described substituent functions as an acid generator and prevents sublimation during heat treatment, making it possible to provide an excellent film-forming material.

[0021] The benzenesulfonate compound (B) is preferably one in which the molecular weight of the anion moiety in the general formula (2-1), (2-2) or (2-3) is 245 or more.

[0022] Such a composition for forming an organic film can reliably prevent sublimation during heat treatment, and can also provide better in-plane uniformity in the formation of an organic film.

[0023] The benzenesulfonate compound (B) is represented by the general formula (2-3), in which R3 is an alkyl group having 3 to 20 carbon atoms and having a branched or cyclic structure, and does not contain a perfluoroalkyl group; + is more preferably a triethylammonium cation or a tributylammonium cation.

[0024] Such an organic film-forming composition can be more preferably used from the viewpoint of ease of production of the material and the wide range of combinations with polymers and compounds for forming organic films.

[0025] The organic film-forming resin or compound (A) preferably has any one of a methylol group, an epoxy group, or a phenolic hydroxyl group.

[0026] Use of such an organic film-forming resin or compound (A) enhances curability, making it possible to provide a more excellent organic film-forming composition.

[0027] Furthermore, 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 organic film-forming composition described above onto a substrate to be processed, and then heat-treating the substrate coated with the organic film-forming composition at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds, thereby forming a cured film.

[0028] This organic film formation method can fill complex patterns on the substrate to be processed by spin coating, form an organic film with excellent in-plane uniformity, and remove the organic film from the edges while suppressing humps in the EBR process.

[0029] The present invention also provides a pattern formation method, comprising: forming an organic film on a workpiece using the organic film-forming composition described above; forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms; forming a resist upper layer film on the resist intermediate film using a resist upper layer film material consisting of a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern to the organic film by etching using the resist intermediate film on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0030] 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 layer film or an inorganic hard mask, 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 present invention provides a pattern formation method comprising the steps of forming an organic film on a workpiece using the organic film-forming composition described above, forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms, forming an organic antireflective film or an adhesive film on the resist intermediate film, forming a resist upper layer film on the organic antireflective film or adhesive film using a resist upper layer film material comprising a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the organic antireflective film or adhesive film and the resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the resist intermediate film on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0032] In such a pattern formation method, the organic antireflective coating and adhesive coating can be formed by spin coating using known organic antireflective coating materials, and therefore, except for forming an organic antireflective coating (BARC) or adhesive coating between the silicon-containing resist intermediate film and the resist top layer film, the method can be achieved in a similar manner to the three-layer resist process using the silicon-containing resist intermediate film described above.

[0033] The present invention provides a pattern formation method, comprising the steps of forming an organic film on a workpiece using the organic film-forming composition described above, forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming a resist upper layer film on the inorganic hard mask using a resist upper layer film material consisting of a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the inorganic hard mask by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0034] Such a pattern formation method can be suitably achieved in the same manner as the above-described three-layer resist process using a silicon-containing resist interlayer, except that an inorganic hard mask interlayer is formed on an organic film instead of the silicon-containing resist interlayer.

[0035] The present invention provides a pattern formation method, comprising the steps of forming an organic film on a workpiece using the organic film-forming composition described above, forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming an organic antireflective film or an adhesion film on the inorganic hard mask, forming a resist upper layer film on the organic antireflective film using a resist upper layer film material comprising a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the organic antireflective film and the inorganic hard mask by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0036] Such a pattern formation method can be suitably achieved in the same manner as the above-described 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.

[0037] In the pattern formation method of the present invention, the inorganic hard mask is preferably formed by a CVD method or an ALD method.

[0038] Any pattern formation method that forms an inorganic hard mask by such a CVD method or ALD method can suitably form a pattern.

[0039] 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.

[0040] Such a circuit pattern forming means can more suitably form fine patterns.

[0041] In forming the circuit pattern, it is preferable to develop the circuit pattern using an alkali developer or an organic solvent.

[0042] Such a pattern forming method allows for more suitable production of circuit patterns.

[0043] In the pattern formation method, it is preferable that the workpiece is a semiconductor device substrate, or a semiconductor device substrate on which any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film is formed.

[0044] Such a workpiece can be suitably processed to form a pattern.

[0045] In the pattern formation method, the metal constituting the workpiece is preferably silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof.

[0046] Such a workpiece can be suitably processed to form a pattern.

[0047] The present invention provides a benzenesulfonate compound for forming an organic film, which is represented by the following formula (1), in which the molecular weight of the anion moiety in formula (1) is 200 or more and which does not contain a perfluoroalkyl group. [ka] (wherein R1 represents a linear, cyclic, or branched alkyl group having 1 to 20 carbon atoms, which may have a substituent not including a perfluoroalkyl group, an alkenyl group, an oxoalkyl group, an aryl group, an aralkyl group, or -P(R)2 (wherein R is an alkyl group or an aryl group having 1 to 20 carbon atoms), or a halogen atom or a nitro group; n represents an integer of 1 to 5; A + represents an ammonium cation, a pyridinium cation, a sulfonium cation, a phosphonium cation, an imidazolium cation, a piperidinium cation, or a pyrrolidinium cation.

[0048] Such a benzenesulfonate compound for forming an organic film can be suitably used in the composition for forming an organic film, the method for forming an organic film, and the method for forming a pattern of the present invention.

[0049] The benzenesulfonate compound for forming an organic film is preferably represented by the following general formula (2-1), (2-2) or (2-3). [ka] (A + is A in the above formula (1) + is equivalent to [ka] (wherein R2 represents a chlorine atom or an iodine atom, m represents an integer of 1 to 5, A + is A in the above formula (1) + is equivalent to [ka] (In the formula, R3 is an alkyl group having 1 to 20 carbon atoms which may have a substituent but does not contain a perfluoroalkyl group. A + is A in the above formula (1) + is equivalent to

[0050] Such a benzenesulfonate compound for forming an organic film is more preferably used for forming an organic film.

[0051] The benzenesulfonate compound for forming an organic film preferably has an anion moiety represented by the general formula (2-1), (2-2) or (2-3) having a molecular weight of 245 or more.

[0052] Such a benzenesulfonate compound for forming an organic film can reliably prevent sublimation during heat treatment and is more preferably used for forming an organic film.

[0053] The benzenesulfonate compound for forming an organic film is represented by the general formula (2-3), in which R3 is an alkyl group having 3 to 20 carbon atoms and a branched or cyclic structure, not including a perfluoroalkyl group, and A + is preferably a triethylammonium cation or a tributylammonium cation.

[0054] Such a benzenesulfonate compound for forming an organic film is particularly preferably used for forming an organic film.

[0055] The present invention provides a pattern forming method, which comprises forming an organic film on a workpiece using a resist material containing the above-described organic film-forming composition, exposing the resist film to high-energy rays, and developing the exposed resist film using a developer.

[0056] Such a pattern forming method makes it possible to form a fine pattern using high-energy rays, and to process a fine pattern with excellent in-plane uniformity and few defects. [Effects of the Invention]

[0057] As explained above, the present invention makes it possible to apply a film-forming material that has excellent film-forming properties (in-plane uniformity) and filling properties on a substrate (wafer), and when an organic film-forming material combined with an organic film-forming resin and / or compound is used as an organic underlayer film, it is possible to provide an organic film-forming composition that has excellent film-forming properties on the organic film. Furthermore, when the organic film-forming composition is used as a resist material in combination with a photoacid generator or the like, it is possible to process fine patterns as a resist material for photolithography with excellent in-plane uniformity. The organic film-forming composition of the present invention is extremely useful as an organic film material used in multilayer resist processes such as a two-layer resist process, a three-layer resist process using a silicon-containing resist intermediate film or an inorganic hard mask, or a four-layer resist process using a silicon-containing resist intermediate film or an inorganic hard mask and an organic antireflective film, or as a film-forming material for manufacturing semiconductor devices, such as a photoresist material. An organic film obtained by using the organic film-forming composition of the present invention can have excellent etching resistance when etching an object to be processed. [Brief explanation of the drawings]

[0058] [Figure 1] 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 2] FIG. 1 is an explanatory diagram of a method for evaluating filling characteristics in an example. DETAILED DESCRIPTION OF THE INVENTION

[0059] As described above, there has been a demand for a film-forming material that has excellent film-forming properties, can achieve high in-plane uniformity and filling properties, and can also comply with environmental regulations.

[0060] For example, when forming an organic film, a resin for forming an organic film and a thermal acid generator are dissolved in an organic solvent to form a composition, which is then applied to a substrate on which structures, wiring, etc. have been formed using a coater / developer, the composition is spread as the substrate rotates, the composition at the edges is removed in an EBR process, and the organic film is then formed by baking. If the molecular weight of the thermal acid generator is small during the firing process of the above composition, the acid generator will sublime during firing, resulting in insufficient film effect, mainly at the outer periphery of the wafer, and impairing the uniformity of the entire film.

[0061] The present inventors further conducted extensive research and discovered that the use of a benzenesulfonate compound having a specific molecular weight and substituent group results in a composition for forming an organic film that is excellent in film-forming properties, high-level embedding properties, and flatness, and thus completed the present invention.

[0062] Furthermore, the present inventors have conducted extensive research to obtain a film-forming material that meets recent demands for high flatness after coating, has excellent film-forming properties such as good coating properties at the outermost edge of a substrate (wafer), and generates few defects after coating, development, and etching. As a result, the present inventors have found that a benzenesulfonate compound in which the molecular weight of the anion moiety is 200 or more is a promising material, which led to the completion of the present invention.

[0063] Furthermore, in light of the recent tightening of environmental regulations, there is a demand for the development of materials that do not fall under the category of PFAS. Compounds that do not contain perfluoroalkyl groups do not belong to the OECD classification of PFAS, making them promising as membrane-forming materials.

[0064] That is, the present invention is a film-forming composition containing a benzenesulfonate compound in which the molecular weight of the anion moiety containing no perfluoroalkyl group is 200 or more. The present invention will be described in detail below, but the present invention is not limited thereto.

[0065] [Composition for organic film formation] The present invention relates to a composition for forming an organic film, characterized in that it contains an organic film-forming resin and / or compound (A), a benzenesulfonate compound (B) represented by the following formula (1), in which the molecular weight of the anion moiety in formula (1) is 200 or more and which does not contain a perfluoroalkyl group, and a solvent (C): [ka] (wherein R1 represents a linear, cyclic, or branched alkyl group having 1 to 20 carbon atoms, which may have a substituent not including a perfluoroalkyl group, an alkenyl group, an oxoalkyl group, an aryl group, an aralkyl group, or -P(R)2 (wherein R is an alkyl group or an aryl group having 1 to 20 carbon atoms), or a halogen atom or a nitro group; n represents an integer of 1 to 5; A + represents an ammonium cation, a pyridinium cation, a sulfonium cation, a phosphonium cation, an imidazolium cation, a piperidinium cation, or a pyrrolidinium cation.

[0066] The benzenesulfonate compound (B) is preferably one represented by the following general formula (2-1), (2-2) or (2-3). [ka] (A + is A in the above formula (1) + is equivalent to [ka] (In the formula, R2 represents a chlorine atom or an iodine atom. m represents an integer of 1 to 5. A + is A in the above formula (1) + is equivalent to [ka] (In the formula, R3 is an alkyl group having 1 to 20 carbon atoms which may have a substituent but does not contain a perfluoroalkyl group. A + is A in the above formula (1)+ is equivalent to

[0067] The benzenesulfonate compound (B) is preferably one in which the molecular weight of the anion moiety in the general formula (2-1), (2-2) or (2-3) is 245 or more.

[0068] The benzenesulfonate compound (B) is represented by the general formula (2-3), in which R3 is an alkyl group having 3 to 20 carbon atoms and having a branched or cyclic structure, and does not contain a perfluoroalkyl group; + is preferably a triethylammonium cation or a tributylammonium cation.

[0069] In the above general formula (1), R1 represents a linear, cyclic, or branched alkyl group, alkenyl group, oxoalkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms, which may have a substituent not including a perfluoroalkyl group, or -P(R)2 (wherein R is an alkyl group or aryl group having 1 to 20 carbon atoms), or a halogen atom or a nitro group; and n is an integer of 1 to 5.

[0070] In the above general formula (1), A + represents an ammonium cation (excluding tetramethylbenzylammonium cation), a pyridinium cation, a sulfonium cation, a phosphonium cation, an imidazolium cation, a piperidinium cation, or a pyrrolidinium cation.

[0071] Specific examples of the ammonium cation include trimethylammonium cation, triethylammonium cation, tripropylammonium cation, triisopropylammonium cation, tributylammonium cation, triisobutylammonium cation, tripentylammonium cation, trihexylammonium cation, trioctylammonium cation, tetramethylammonium cation, tetraethylammonium cation, tetrapropylammonium cation, tetraisopropylammonium cation, tetrabutylammonium cation, tetraisobutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, and tetraoctylammonium cation; and specific examples of the pyridinium cation include pyridinium cation, methylpyridinium cation, ethylpyridinium cation, propylpyridinium cation, isopropylpyridinium cation, butylpyridinium cation, fluoropyridinium cation, and chloropyridinium. Examples of the sulfonium cation include triphenylsulfonium cation, diphenyl[4-(phenylthio)phenyl]sulfonium cation, tris(4-methylphenyl)sulfonium cation, tris(4-t-butylphenyl)sulfonium cation, 5-phenyldibenzothiophenium cation, and 10-phenylphenoxathiinium cation. Examples of the phosphonium cation include triethylphosphonium cation, tributylphosphonium cation, triphenylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, and ethyltriphenylphosphonium cation. Examples of the imidazolium cation include 1-allyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-benzyl-3-methylimidazolium cation, 1,3-dimethylimidazolium cation, 2,Examples of the piperidinium cation include 1-butyl-1-methylpiperidinium cation and 1-methyl-1-propylpiperidinium cation, and examples of the pyrrolidinium cation include 1-allyl-1-methylpyrrolidinium cation, 1-butyl-1-methylpyrrolidinium cation, 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, and 1-(2-methoxymethyl)-1-methylpyrrolidinium cation. From the viewpoint of ease of production, tetraethylammonium cation or tetrabutylammonium cation is preferred.

[0072] The benzenesulfonate compound (B) is represented by the general formula (2-3), in which R3 is an alkyl group having 3 to 20 carbon atoms and having a branched or cyclic structure, and does not contain a perfluoroalkyl group; + is preferably a triethylammonium cation or a tributylammonium cation.

[0073] In the general formula (2-2), R2 represents a chlorine atom or an iodine atom. m represents an integer of 1 to 5, preferably 2 or 3 in the case of a chlorine atom, and preferably 1 or 2 in the case of an iodine atom.

[0074] R3 in the general formula (2-3) above represents an alkyl group having 1 to 20 carbon atoms which may have a substituent and does not contain a perfluoroalkyl group. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, etc. Preferred are alkyl groups having 3 to 20 carbon atoms and a branched or cyclic structure, such as an isopropyl group, an isobutyl group, a cyclopentyl group, a cyclohexyl group, etc.

[0075] Examples of the anion component of the benzenesulfonate compound include, but are not limited to, the following structures.

change

[0076] The cation component of the benzenesulfonate compound represents an ammonium cation (excluding tetramethylbenzylammonium cation), a pyridinium cation, a sulfonium cation, a phosphonium cation, an imidazolium cation, a piperidinium cation, or a pyrrolidinium cation. Specific examples of the ammonium cation include a trimethylammonium cation, a triethylammonium cation, a tripropylammonium cation, a triisopropylammonium cation, a tributylammonium cation, a triisobutylammonium cation, a tripentylammonium cation, a trihexylammonium cation, a trioctylammonium cation, a tetramethylammonium cation, a tetraethylammonium cation, a tetrapropylammonium cation, a tetraisopropylammonium cation, a tetrabutylammonium cation, a tetraisobutylammonium cation, a tetrapentylammonium cation, a tetrahexylammonium cation, or a tetraoctylammonium cation. Specific examples of the pyridinium cation include a pyridinium cation, a methylpyridinium cation, an ethylpyridinium cation, a propylpyridinium cation, an isopropylpyridinium cation, or a butylpyridinium cation. Examples of the sulfonium cation include triphenylsulfonium cation, diphenyl[4-(phenylthio)phenyl]sulfonium cation, tris(4-methylphenyl)sulfonium cation, tris(4-t-butylphenyl)sulfonium cation, 5-phenyldibenzothiophenium cation, and 10-phenylphenoxathiinium cation. Examples of the phosphonium cation include triethylphosphonium cation, tributylphosphonium cation, triphenylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, and ethyltriphenylphosphonium cation. Examples of the imidazolium cation include 1-allyl-3-methylimidazolium cation,Examples of the cation include 1-butyl-3-methylimidazolium cation, 1-benzyl-3-methylimidazolium cation, 1,3-dimethylimidazolium cation, and 2,3-dimethyl-1-propylimidazolium cation. Examples of the piperidinium cation include 1-butyl-1-methylpiperidinium cation and 1-methyl-1-propylpiperidinium cation. Examples of the pyrrolidinium cation include 1-allyl-1-methylpyrrolidinium cation, 1-butyl-1-methylpyrrolidinium cation, 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, and 1-(2-methoxymethyl)-1-methylpyrrolidinium cation. From the viewpoint of ease of production, the tetraethylammonium cation or tetrabutylammonium cation is preferred.

[0077] A general method for synthesizing the benzenesulfonate compound represented by formula (1) of the present invention will be described. 1 mol of benzenesulfonic acid is dissolved in water to make a 10% aqueous solution, and 1 mol of amine is added dropwise at room temperature. After aging this solution at room temperature for about 24 hours, the solvent is distilled off under reduced pressure. The benzenesulfonic acid salt can be obtained by drying under reduced pressure at 50°C.

[0078] Materials used in semiconductor photolithography, including the benzenesulfonate compound (B), must have reduced metal impurities because the presence of metal impurities adversely affects the operation of devices manufactured using them. To reduce metals, washing with pure water or ion exchange resins is used. In the case of resist materials, the amount of metal impurities is preferably 100 ppm or less, more preferably 100 ppb or less.

[0079] The film-forming material of the present invention preferably contains the benzenesulfonate compound (B) in an amount of 0.0001 to 10% by mass. The content of the polymer is preferably 0.1 to 7% by mass, more preferably 2 to 5% by mass. In this case, the benzenesulfonate compound (B) serves as an acid generator for imparting film curability. By using the benzenesulfonate compound (B) in combination with an organic compound or the like as an acid generator, it is possible to impart high film-forming properties.

[0080] The organic film-forming material can be used as a component of photosensitive or non-photosensitive resist materials, materials for forming top coats formed on resist films, materials for forming resist intermediate films, etc. As for underlayer film materials, not only organic underlayer films using organic compounds or resins but also film-forming materials containing metal elements such as silicon, titanium, zirconium, tin, and hafnium can be used. For example, resist materials may be either chemically amplified resists or non-chemically amplified resists, hydrocarbon-based resists, or metal-based resists containing silicon, titanium, zirconium, hafnium, selenium, germanium, zinc, iron, cobalt, nickel, copper, tin, antimony, molybdenum, tungsten, indium, etc. Examples of compounds other than organic compounds or resins include silicon-containing resist intermediate layer film materials described in JP 2007-302873 A, JP 2008-19423 A, and the like, coating-type BPSG film-forming compositions described in JP 2016-074774 A, titanium-containing resist intermediate layer film materials described in JP 2014-199429 A, JP 2014-178602 A, and the like, and metal oxide film-forming materials described in JP 2014-134581 A, and the like. In addition to these, the compound is expected to be applicable to various materials as an acid generator during film formation.

[0081] The benzenesulfonate compound (B) and a resin for forming an organic film and / or the compound (A) and a solvent can be combined to form a composition for forming an organic film.

[0082] The present invention provides a composition for forming an organic film, in which the content of the benzenesulfonate compound (B) is 0.01 to 5 parts by mass, based on 100 parts by mass of the resin for organic film-forming materials and / or compound (A).

[0083] Adding the benzenesulfonate compound (B) within the above-mentioned range can improve the film-forming properties of the organic film-forming composition. Therefore, although there are various resins and compounds, such as resins with various repeating units, compounds with rigid structures and high crystallinity, and compounds with highly polar substituents, the benzenesulfonate compound (B) of the present invention can provide an organic film-forming composition with excellent film-forming properties even when using resins or compounds with different properties.

[0084] The composition for forming an organic film may contain the benzenesulfonate compound (B) whose cationic moiety is photodecomposable.

[0085] By preparing such an organic film-forming composition, photosensitivity and the like can be imparted to the organic film-forming composition, and the organic film-forming material can be used as a resist material for photolithography and the like.

[0086] In the organic film-forming composition of the present invention, the benzenesulfonate compound (B), (A) organic film-forming resin and / or compound, and (C) solvent can each be used alone or in combination of two or more. The benzenesulfonate compound (B) of the present invention has excellent heat resistance and functions as an acid generator that imparts excellent film-forming properties and high leveling performance. Its applications are not limited to organic underlayer films, and it can be used in general photolithography coating materials, such as photosensitive resist materials and materials for forming top coats formed on resist films. Furthermore, it can be applied not only to organic underlayer film-forming materials but also to silicon-containing resist intermediate films, and can be used as an acid generator suitable for exhibiting highly versatile film-forming properties that can be applied to various film-forming materials.

[0087] When the benzenesulfonate compound (B) of the present invention is used as an acid generator, one type may be used alone or two or more types may be used in combination. The amount of the benzenesulfonate compound (B) added is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, per 100 parts by mass of the organic film-forming resin and / or compound (A).

[0088] [(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 or compound that satisfies the film-forming properties and curing properties of spin coating. However, when used as an organic underlayer film material, a resin or compound containing an aromatic skeleton is more preferred from the viewpoints of etching resistance, optical properties, heat resistance, etc.

[0089] 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.

[0090] The organic film-forming composition is preferably one in which the organic film-forming resin or compound (A) has any one of a methylol group, an epoxy group, and a phenolic hydroxyl group. Use of such an organic film-forming resin or compound (A) enhances curability, making it possible to provide an even more excellent organic film-forming composition.

[0091] 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 are only applicable within this formula.

[0092] [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.)

[0093] 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.

[0094] [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.)

[0095] [ka] In formula (6), R1 is a hydrogen atom or a methyl group. R2 is a single bond, a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 10 carbon atoms, and may have any of ether, ester, lactone, and amide. R 3 , R 4 are each a hydrogen atom or a glycidyl group. X represents a polymer of any one of hydrocarbons containing an indene skeleton, cycloolefins having 3 to 10 carbon atoms, and maleimide, and may have any one of ethers, esters, lactones, and carboxylic acid anhydrides. R 5 , 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 formulae apply only within this formula.)

[0096] [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.)

[0097] 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 formulas (8) and (9), R 1 ~R 8 are, independently of each other, 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 alkoxycarbonyl 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 are applicable only within this formula.)

[0098]

Chemical formula

[0099]

Chemical formula

[0100] Examples of the formula (11) include the following resins: [ka]

[0101] [ka]

[0102] 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 hydrogen atoms, linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, or alkenyl groups having 2 to 10 carbon atoms, and R 3is a single bond or an alkylene group having a linear, branched or cyclic structure and having 1 to 30 carbon atoms, which may have a bridged cyclic hydrocarbon group, a double bond, a heteroatom or an aromatic group having 6 to 30 carbon atoms; R 4 and R 5 are each independently a hydrogen atom or a glycidyl group, and n is an integer of 1 to 4. The symbols in the formula are applicable only within this formula.

[0103] [ka] (In formula (13), R 1 and R 2 are independently the same or different hydrogen atoms, linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, or alkenyl groups having 2 to 10 carbon atoms, and R 3 is a single bond or an alkylene group having a linear, branched or cyclic structure and having 1 to 30 carbon atoms, which may have a bridged cyclic hydrocarbon group, a double bond, a heteroatom or an aromatic group having 6 to 30 carbon atoms; R 4 and R 5 are each independently a hydrogen atom or a glycidyl group, and R 6 is a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms. The symbols in the formula are applicable only within this formula.

[0104] [ka] (In formula (14), ring Z 1 and ring Z 2 is a fused polycyclic aromatic hydrocarbon ring, R 1a , R 1b , R 2a , and R 2b are the same or different and represent a substituent. k1 and k2 are the same or different and represent an integer of 0 or 1 to 4, m1 and m2 are each an integer of 0 or 1 or more, and n1 and n2 are each an integer of 0 or 1 or more, provided that n1+n2≧1. The symbols in the formulae are only applicable within this formula.

[0105] [Chemical formula] (In formula (15), R 1 , R 2 are the same or different hydrogen atoms, linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, or alkenyl groups having 2 to 10 carbon atoms. 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 or 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.)

[0106] As formula (15), for example, the following resins can be exemplified. [Chemical formula]

[0107] [Chemical formula]

[0108] [Chemical formula]

[0109] [Chemical formula]

[0110] As the resin and / or compound (A) for forming an organic film used in the present invention, resins containing the following structures described in JP-A-2012-214720 can be exemplified. [Chemical formula] (In formula (16), the ring structures Ar1 and Ar2 represent a benzene ring or a naphthalene ring. x and z each independently represent 0 or 1. Note that the symbols in the formula apply only within this formula.)

[0111] Examples of the (A) organic film-forming resin and / or compound 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.)

[0112] 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.

[0113] [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 represents a hydrogen atom, or a halogen atom which may be substituted with 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.

[0114] 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 a combination 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 a combination 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.

[0115] 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.)

[0116] 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; 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.)

[0117] 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 alkyl groups arbitrarily selected from the following may be bonded to form a cyclic substituent. The symbols in the formula are applicable only within this formula.)

[0118] [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.)

[0119] 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.)

[0120] 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.)

[0121] [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.

[0122] [ka] (In the formula, R 10is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom on the benzene ring in the formula may be substituted with a methyl group or a methoxy group. Note that the symbols in the formula apply only within this formula.

[0123] Examples of compounds containing the above structure include the following compounds.

[0124] [ka]

[0125] 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 R4 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.

[0126] Examples of polymers having a repeating unit represented by the above general formula (27-1) include the following polymers.

[0127] [ka]

[0128] [ka]

[0129] (A) The organic film-forming resin and / or compound may be synthesized by a known method, or a commercially available product may be used.

[0130] 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 the in-plane uniformity and filling properties after spin coating. Even with the above-mentioned (A) organic film-forming resin blend ratio, the organic film-forming composition of the present invention can be suitably applied because it can form organic films with excellent in-plane uniformity and filling properties.

[0131] Furthermore, the content of the (B) polymer is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the (A) organic film-forming resin and / or compound. When the organic film-forming composition contains the polymer in such a content, the formed organic film has better in-plane uniformity.

[0132] [Solvent (C)] The solvent (C) that can be used in the organic film-forming composition 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) compound, and is preferably one that can also dissolve the crosslinking agent, surfactant, etc. described below. Specifically, solvents with a boiling point of less than 180°C, such as those described in paragraphs (0091) and (0092) of JP 2007-199653 A, 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.

[0133] The content of the (C) solvent is 200 to 10,000 parts by mass, more preferably 300 to 5,000 parts by mass, per 100 parts by mass of the (A) organic film-forming resin and / or compound. By setting the content within this range, the concentration can be adjusted according to the film thickness to be consumed.

[0134] Furthermore, in the organic film-forming composition 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 as the organic solvent (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.

[0135] The boiling point of the high-boiling solvent may be appropriately selected according to the temperature at which the organic film-forming composition is heat-treated, and the boiling point of the high-boiling 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.

[0136] 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.

[0137] In such an organic film-forming composition, the addition of a high-boiling point solvent to the above-mentioned organic film-forming resin and / or compound provides thermal fluidity, thereby making the organic film-forming material have both high filling and planarizing properties.

[0138] [Other ingredients] Furthermore, a crosslinking agent can be added to the organic film-forming composition of the present invention in order to further promote the crosslinking reaction.

[0139] 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.

[0140] A surfactant may also 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 surfactants described above 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. Such an amount enables the formation of an organic film with excellent in-plane uniformity.

[0141] 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.

[0142] 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.

[0143] [Organic film formation method] The organic film forming method of the present invention is a method for forming an organic film used in the manufacturing process of a semiconductor device, and is a method for forming an organic film by spin-coating the above-mentioned organic film-forming composition of the present invention on a substrate to be processed, and then heat-treating the substrate coated with the organic film-forming composition at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds to harden the composition, thereby forming an organic film.

[0144] 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.

[0145] 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.

[0146] [Pattern formation method] A pattern forming method using the organic film-forming composition of the present invention will be described below.

[0147] Provided is a pattern forming method including the steps of forming a resist film on a substrate using an organic film-forming composition, exposing the resist film to high-energy rays, and developing the exposed resist film using a developer.

[0148] By using the organic film-forming composition of the present invention, a pattern can be formed by carrying out the above-described exposure.

[0149] The high-energy rays are preferably g-rays, i-rays, KrF excimer lasers, ArF excimer lasers, ultraviolet rays, electron beams, or extreme ultraviolet rays having a wavelength of 3 to 15 nm.

[0150] By using the high energy beams described above, it is possible to form fine patterns.

[0151] [Trilayer resist process using silicon-containing resist interlayer] The present invention provides a pattern formation method comprising the steps of forming an organic film on a workpiece using the organic film-forming composition described above, forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms, forming a resist upper layer film on the resist intermediate film using a resist upper layer film material consisting of a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the resist intermediate film on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0152] The workpiece is preferably a semiconductor device substrate, or the semiconductor device substrate on which any 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. Specifically, although not particularly limited, substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, and Al, or the substrate on which the above-mentioned metal film is formed as a workpiece layer, can be used.

[0153] 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.

[0154] 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.

[0155] An organic film is formed on a workpiece using the organic film-forming composition of the present invention, and in this case, the above-described organic film-forming method of the present invention may be applied.

[0156] 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.

[0157] 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.

[0158] 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.

[0159] 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.

[0160] In forming the circuit pattern, it is preferable to develop the circuit pattern using an alkali developer or an organic solvent.

[0161] 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.

[0162] 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.

[0163] 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.

[0164] 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.

[0165] [Four-layer resist process using silicon-containing resist interlayer and organic anti-reflective or adhesive coating] The present invention provides a pattern formation method comprising the steps of forming an organic film on a workpiece using the organic film-forming composition described above, forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms, forming an organic antireflective film or an adhesive film on the resist intermediate film, forming a resist upper layer film on the organic antireflective film or adhesive film using a resist upper layer film material comprising a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the organic antireflective film or adhesive film and the resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the resist intermediate film on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0166] This method can be performed in the same manner as the three-layer resist process using the silicon-containing resist intermediate film described above, except that an organic antireflective coating (BARC) or an adhesive film is formed between the silicon-containing resist intermediate film and the resist top layer film.

[0167] The organic anti-reflection film and the adhesive film can be formed by spin coating using known organic anti-reflection film materials.

[0168] [Trilayer resist process using inorganic hard mask intermediate film] The present invention also provides a pattern formation method, comprising the steps of forming an organic film on a workpiece using the organic film-forming composition described above, forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming a resist upper layer film on the inorganic hard mask using a resist upper layer film material comprising a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the inorganic hard mask by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the inorganic hard mask 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.

[0169] 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.

[0170] 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.

[0171] [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 an 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; a resist upper layer film on which the circuit pattern is formed is used as a mask to transfer the pattern to the organic anti-reflective film or the adhesive film and the inorganic hard mask intermediate film by etching; transferring the pattern 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 organic film onto which the pattern has been transferred is used as a mask to transfer the pattern onto the workpiece by etching.

[0172] 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.

[0173] 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.

[0174] An example of a pattern formation method using the three-layer resist process of the present invention is shown in Figures 1(A) to 1(F). In the three-layer resist process, as shown in Figure 1(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 1(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 1(C), development is performed to form a resist upper layer film pattern 5a. Next, as shown in Figure 1(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 1(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. Furthermore, as shown in Figure 1(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).

[0175] 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.

[0176] 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 originating from the organic film by improving the flatness of the organic film.

[0177] [Organic film-forming composition (resist material)] The organic film-forming composition of the present invention can be used as a resist material. When the benzenesulfonate compound (B) of the present invention is used as an acid generator, the organic film-forming composition of the present invention may contain a surfactant. Examples of the surfactant include those described in paragraphs

[0165] and

[0166] of JP-A-2008-111103. When the organic film-forming composition of the present invention contains a surfactant, the content thereof is not particularly limited.

[0178] [Base polymer] The organic film-forming composition of the present invention may further contain a base polymer. The base polymer is not particularly limited as long as it is used in resist materials.

[0179] (Repeating units a1 and a2) Specifically, in the case of a positive resist material for a chemically amplified resist, the base polymer contains a repeating unit containing an acid labile group. The repeating unit containing an acid labile group is preferably a repeating unit represented by the following formula (a1) (hereinafter also referred to as repeating unit a1) or a repeating unit represented by the following formula (a2) (hereinafter also referred to as repeating unit a2): [ka]

[0180] In formulas (a1) and (a2), R B are each independently a hydrogen atom or a methyl group. 1 Y is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms and containing at least one bond selected from an ester bond, an ether bond, and a lactone ring. 2 is a single bond or an ester bond. 3 is a single bond, an ether bond, or an ester bond. 11 and R 12 are each independently an acid labile group. When the base polymer contains both the repeating unit a1 and the repeating unit a2, R 11 and R 12 R may be the same or different. 13 R is a fluorine atom, a trifluoromethyl group, a cyano group, or a saturated hydrocarbyl group having 1 to 6 carbon atoms. 14 is a single bond or an alkanediyl group having 1 to 6 carbon atoms, and some of the -CH2- in the alkanediyl group may be substituted with ether bonds or ester bonds. a is 1 or 2. b is an integer of 0 to 4, with the proviso that 1≦a+b≦5.

[0181] Specific examples of the monomer that provides the repeating unit a1 include, but are not limited to, the following: B and R 11 is the same as above. [ka]

[0182] Specific examples of the monomer that provides the repeating unit a2 include, but are not limited to, the following: B and R 12 is the same as above. [ka]

[0183] R 11 and R 12 Examples of the acid labile group represented by the formula (I) include those described in JP-A Nos. 2013-80033 and 2013-83821.

[0184] Specific examples of the acid labile group include those represented by any of the following formulae (AL-1) to (AL-3). [ka] (In the formula, the dashed lines represent bonds.)

[0185] In formulas (AL-1) and (AL-2), R L1 and R L2 are each independently a hydrocarbyl group having 1 to 40 carbon atoms, which may contain a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a fluorine atom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. The hydrocarbyl group is preferably a saturated hydrocarbyl group having 1 to 40 carbon atoms, more preferably a saturated hydrocarbyl group having 1 to 20 carbon atoms.

[0186] In formula (AL-1), c is an integer of 0 to 10, and an integer of 1 to 5 is preferred.

[0187] In formula (AL-2), R L3 and R L4 are each independently a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, and may contain heteroatoms such as oxygen, sulfur, nitrogen, and fluorine atoms. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. The hydrocarbyl group is preferably a saturated hydrocarbyl group having 1 to 20 carbon atoms. In addition, R L2 , R L3 and R L4Any two of these may be bonded to each other to form a ring having 3 to 20 carbon atoms together with the carbon atom or the carbon atom and oxygen atom to which they are bonded. As the ring, a ring having 4 to 16 carbon atoms is preferred, and an alicyclic ring is particularly preferred.

[0188] In formula (AL-3), R L5 , R L6 and R L7 are each independently a hydrocarbyl group having 1 to 20 carbon atoms, which may contain a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a fluorine atom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. The hydrocarbyl group is preferably a saturated hydrocarbyl group having 1 to 20 carbon atoms. In addition, R L5 , R L6 and R L7 Any two of these may be bonded to each other to form, together with the carbon atoms to which they are bonded, a ring having 3 to 20 carbon atoms. As the ring, a ring having 4 to 16 carbon atoms is preferred, and an alicyclic ring is particularly preferred.

[0189] (Repeating unit b) The base polymer may contain a repeating unit b containing a phenolic hydroxy group as an adhesive group. Specific examples of the monomer that provides the repeating unit b include, but are not limited to, the following. In the following formula, R B is the same as above. [ka]

[0190] [ka]

[0191] [ka]

[0192] (Repeating unit c) The base polymer may contain a repeating unit c containing, as another adhesive group, a hydroxy group other than a phenolic hydroxy group, a lactone ring, a sultone ring, an ether bond, an ester bond, a sulfonate ester bond, a carbonyl group, a sulfonyl group, a cyano group, a carboxy group, or a hemiacetal structure. Specific examples of monomers that provide the repeating unit c include, but are not limited to, those shown below. In the following formula, R B is the same as above.

[0193] [ka] [ka]

[0194] [ka]

[0195] [ka]

[0196] [ka]

[0197] [ka]

[0198] [ka]

[0199] [ka]

[0200] [ka]

[0201] (Repeating unit d) The base polymer may contain a repeating unit d derived from indene, benzofuran, benzothiophene, acenaphthylene, chromone, coumarin, norbornadiene, or a derivative thereof. Specific examples of monomers that provide the repeating unit d include, but are not limited to, the following:

[0202] [ka]

[0203] (Repeating unit e) The base polymer may include repeat units e derived from styrene, vinylnaphthalene, vinylanthracene, vinylpyrene, methyleneindane, vinylpyridine, or vinylcarbazole.

[0204] (Repeating unit f) The base polymer may contain a repeating unit f derived from an onium salt containing a polymerizable unsaturated bond. Specific examples of preferred repeating units f include a repeating unit represented by the following formula (f1) (hereinafter also referred to as repeating unit f1), a repeating unit represented by the following formula (f2) (hereinafter also referred to as repeating unit f2), and a repeating unit represented by the following formula (f3) (hereinafter also referred to as repeating unit f3). The repeating units f1 to f3 may be used singly or in combination of two or more.

[0205] [ka]

[0206] In formulas (f1) to (f3), R B are each independently a hydrogen atom or a methyl group. 1represents a single bond, an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a naphthylene group, or a group having 7 to 18 carbon atoms obtained by combining these, or -OZ 11 -, -C(=O)-OZ 11 - or -C(=O)-NH-Z 11 -It is. Z 11 Z is an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a naphthylene group, or a group having 7 to 18 carbon atoms obtained by combining these, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxy group. 2 is a single bond or an ester bond. 3 is a single bond, -Z 31 -C(=O)-O-, -Z 31 -O- or -Z 31 -OC(=O)-. Z 31 represents an aliphatic hydrocarbylene group having 1 to 12 carbon atoms, a phenylene group, or a group having 7 to 18 carbon atoms obtained by combining these, and may contain a carbonyl group, an ester bond, an ether bond, an iodine atom, or a bromine atom. Z 4 is a methylene group, a 2,2,2-trifluoro-1,1-ethanediyl group, or a carbonyl group. 5 represents a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, a phenylene group substituted with a trifluoromethyl group, -OZ 51 -, -C(=O)-OZ 51 - or -C(=O)-NH-Z 51 -It is. Z 51 represents an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a fluorinated phenylene group, or a phenylene group substituted with a trifluoromethyl group, and may contain a carbonyl group, an ester bond, an ether bond, a halogen atom, or a hydroxy group.

[0207] In formulas (f1) to (f3), R 21 ~R 28 are each independently a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom.

[0208] R 21 ~R 28 Specific examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0209] R 21 ~R 28 The hydrocarbyl group represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl groups; cyclic saturated hydrocarbyl groups having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl groups; alkenyl groups having 2 to 20 carbon atoms, such as vinyl, propenyl, butenyl, and hexenyl groups; and ethynyl groups. alkynyl groups having 2 to 20 carbon atoms such as a propynyl group or a butynyl group; cyclic unsaturated aliphatic hydrocarbyl groups having 3 to 20 carbon atoms such as a cyclohexenyl group or a norbornenyl group; aryl groups having 6 to 20 carbon atoms such as a phenyl group, a methylphenyl group, an ethylphenyl group, an n-propylphenyl group, an isopropylphenyl group, an n-butylphenyl group, an isobutylphenyl group, a sec-butylphenyl group, a tert-butylphenyl group, a naphthyl group, a methylnaphthyl group, an ethylnaphthyl group, an n-propylnaphthyl group, an isopropylnaphthyl group, an n-butylnaphthyl group, an isobutylnaphthyl group, a sec-butylnaphthyl group or a tert-butylnaphthyl group; aralkyl groups having 7 to 20 carbon atoms such as a benzyl group or a phenethyl group; and groups obtained by combining these.

[0210] The hydrocarbyl group may have some or all of its hydrogen atoms substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom, or some of its -CH- groups substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom, and as a result, the hydrocarbyl group may contain a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-OC(=O)-), a haloalkyl group or the like.

[0211] Also, R 23 and R 24 or R 26 and R 27 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded. In this case, the ring preferably has the following structure:

[0212] [ka] (In the formula, the dashed lines represent bonds.)

[0213] In formula (f1), M -is a non-nucleophilic counter ion. Specific examples of the non-nucleophilic counter ion include halide ions such as chloride ion and bromide ion; fluoroalkylsulfonate ions such as triflate ion, 1,1,1-trifluoroethanesulfonate ion and nonafluorobutanesulfonate ion; arylsulfonate ions such as tosylate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion and 1,2,3,4,5-pentafluorobenzenesulfonate ion; alkylsulfonate ions such as mesylate ion and butanesulfonate ion; imide ions such as bis(trifluoromethylsulfonyl)imide ion, bis(perfluoroethylsulfonyl)imide ion and bis(perfluorobutylsulfonyl)imide ion; and methide ions such as tris(trifluoromethylsulfonyl)methide ion and tris(perfluoroethylsulfonyl)methide ion.

[0214] Further specific examples of the non-nucleophilic counter ion include a sulfonate ion represented by the following formula (f1-1) in which the α-position is substituted with a fluorine atom, and a sulfonate ion represented by the following formula (f1-2) in which the α-position is substituted with a fluorine atom and the β-position is substituted with a trifluoromethyl group. [ka]

[0215] In formula (f1-1), R 31 is a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, and the hydrocarbyl group may contain at least one bond selected from an ether bond, an ester bond, a carbonyl group, a lactone ring, and a fluorine atom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic.

[0216] In formula (f1-2), R 32is a hydrogen atom, a hydrocarbyl group having 1 to 30 carbon atoms, or a hydrocarbyl carbonyl group having 6 to 20 carbon atoms, and the hydrocarbyl group and hydrocarbyl carbonyl group may contain an ether bond, an ester bond, a carbonyl group, or a lactone ring. The hydrocarbyl moiety of the hydrocarbyl group and hydrocarbyl carbonyl group may be saturated or unsaturated, and may be linear, branched, or cyclic.

[0217] Specific examples of the cation of the monomer that gives the repeating unit f1 include, but are not limited to, the following: B is the same as above. [ka]

[0218] Examples of the anion of the monomer that gives the repeating unit f2 include, but are not limited to, those shown below. B is the same as above.

[0219] [ka]

[0220] [ka]

[0221] [ka]

[0222] [ka]

[0223] [ka]

[0224] [ka]

[0225] [ka]

[0226] [ka]

[0227] [ka]

[0228] [ka]

[0229] [ka]

[0230] [ka]

[0231] [ka]

[0232] [ka]

[0233] Examples of the anion of the monomer that gives the repeating unit f3 include, but are not limited to, those shown below. B is the same as above. [ka]

[0234] [ka]

[0235] Specific examples of the cation of the repeating unit f2 or f3 include the same as the sulfonium salts described in paragraphs 0063 to 0080 and the iodonium salt described in paragraph 0082 of JP-A No. 2023-3926.

[0236] The repeating units f1 to f3 function as an acid generator. By bonding the acid generator to the polymer main chain, acid diffusion is reduced, preventing a decrease in resolution due to blurring caused by acid diffusion. Furthermore, the uniform dispersion of the acid generator improves LWR and CDU. When a base polymer containing the repeating unit f is used, the addition of an additive-type acid generator, which will be described later, can be omitted.

[0237] In the case of negative resist materials or non-chemically amplified resist materials, the repeating units a1 and a2 are not necessarily required in the base polymer.

[0238] As the base polymer, in addition to the above-mentioned polymers, resins such as novolak resin, polyimide, polyamide, polyvinylpyrrolidone, polyvinyl alcohol, polythiophene, and polyaniline can also be used.

[0239] [Organic solvents] When the organic film-forming composition of the present invention is used as a resist material, it may contain an organic solvent. The organic solvent is not particularly limited as long as it can dissolve the components described above and the components described below. Specific examples of the organic solvent include ketones such as cyclohexanone, cyclopentanone, methyl-2-n-pentyl ketone, and 2-heptanone, as described in paragraphs

[0144] and

[0145] of JP-A No. 2008-111103; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and diacetone alcohol; propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol monomethyl ether. Examples of suitable solvents include ethers such as glycol dimethyl ether and anisole; 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; lactones such as γ-butyrolactone; lactams such as pyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, and N-hydroxyethyl-2-pyrrolidone; water; and dimethyl sulfoxide.

[0240] In the resist composition of the present invention, the content of the organic solvent is preferably 100 to 10,000 parts by mass, more preferably 200 to 8,000 parts by mass, per 100 parts by mass of the base polymer. The organic solvents may be used singly or in combination of two or more.

[0241] The resist material of the present invention may contain an additive acid generator. Examples of the additive acid generator include sulfonium salts or iodonium salts, sulfonium diazomethane, N-sulfonyloxyimide, and oxime-O-sulfonate, as described in paragraphs

[0122] to

[0142] of JP 2008-111103 A and paragraphs

[0077] to

[0148] of JP 2023-62677 A. When the resist material of the present invention contains the additive acid generator, the content thereof is preferably 0.1 to 50 parts by mass, more preferably 1 to 40 parts by mass, per 100 parts by mass of the base polymer. The additive acid generators may be used alone or in combination of two or more.

[0242] [Quencher] The resist material of the present invention may contain a quencher. The quencher is a compound that can trap the acid generated by the acid generator in the resist material, thereby preventing the acid from diffusing into unexposed areas.

[0243] Examples of the quencher include conventional basic compounds. Examples of conventional basic compounds include primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxy group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amides, imides, and carbamates. Particularly preferred are the primary, secondary, and tertiary amine compounds described in paragraphs

[0146] to

[0164] of JP 2008-111103 A, particularly amine compounds having a hydroxy group, an ether bond, an ester bond, a lactone ring, a cyano group, or a sulfonate ester bond, and compounds having a carbamate group described in Japanese Patent No. 3790649 A. Addition of such basic compounds can, for example, further suppress the diffusion rate of acid in the resist film or correct the shape.

[0244] Further, examples of the quencher include onium salts such as sulfonium salts, iodonium salts, and ammonium salts of sulfonic acids and carboxylic acids not fluorinated at the α-position, as described in JP-A-2008-158339. Sulfonic acids, imide acids, or methide acids fluorinated at the α-position are necessary for deprotecting the acid labile group of a carboxylic acid ester, and the sulfonic acids or carboxylic acids not fluorinated at the α-position are released by salt exchange with onium salts not fluorinated at the α-position. Sulfonic acids and carboxylic acids not fluorinated at the α-position do not undergo deprotection reactions, and therefore function as quenchers.

[0245] Further examples of the quencher include the polymer-type quencher described in JP 2008-239918 A. This quencher enhances the rectangularity of the resist pattern by orienting on the surface of the resist film. The polymer-type quencher also has the effect of preventing pattern film loss and pattern top rounding when a protective film for immersion lithography is applied.

[0246] When the resist composition of the present invention contains the quencher, the content thereof is preferably 0 to 5 parts by mass, more preferably 0 to 4 parts by mass, relative to 100 parts by mass of the base polymer. The quencher may be used alone or in combination of two or more types.

[0247] [Crosslinking agent] The resist material of the present invention may contain a crosslinking agent when it is a negative resist. The incorporation of a crosslinking agent can further increase the difference in dissolution rate between the exposed and unexposed areas. Specific examples of crosslinking agents include those described in paragraphs

[0170] to

[0177] of JP 2020-027297 A. When the resist material of the present invention contains the crosslinking agent, the content thereof is preferably 0 to 30 parts by mass, more preferably 0 to 20 parts by mass, per 100 parts by mass of the base polymer. A content within this range is preferable because there is no risk of increased swelling in the developer.

[0248] A resist material using the organic film-forming composition of the present invention may contain a water-repellency improver to improve the water repellency of the resist film surface. The water-repellency improver can be used in immersion lithography without a topcoat. Examples of the water-repellency improver include polymers containing fluorinated alkyl groups and polymers containing a specific 1,1,1,3,3,3-hexafluoro-2-propanol residue structure, and more preferably those exemplified in JP-A Nos. 2007-297590 and 2008-111103. The water-repellency improver must be soluble in an alkaline developer or an organic solvent developer. The water-repellency improver containing the specific 1,1,1,3,3,3-hexafluoro-2-propanol residue described above has good solubility in the developer. As a water-repellency improver, polymers containing repeating units containing amino groups or amine salts are highly effective in preventing acid evaporation during post-exposure baking (PEB) and preventing poor hole pattern opening after development. When the coating material or resist material for photolithography of the present invention contains the water repellency improver, the content thereof is preferably 0 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the base polymer. The water repellency improvers may be used alone or in combination of two or more.

[0249] The surfactant contained in the resist composition for forming an organic film of the present invention can also be used as the water repellency improver. In this case, a surfactant having a high water repellency improving function can be combined with a surfactant having a high surface activity.

[0250] The resist material of the present invention may contain an acetylene alcohol. Specific examples of the acetylene alcohol include those described in paragraphs

[0179] to

[0182] of JP 2008-122932 A. When the resist material of the present invention contains the acetylene alcohol, the content thereof is preferably 0 to 5 parts by mass per 100 parts by mass of the base polymer. The acetylene alcohols may be used alone or in combination of two or more types.

[0251] [Pattern formation method] When the resist material of the present invention is used in the manufacture of various integrated circuits, known lithography techniques can be applied. For example, a pattern formation method can include a method comprising the steps of forming a resist film on a substrate using the resist material, exposing the resist film to high-energy radiation, and developing the exposed resist film using a developer.

[0252] First, the resist material of the present invention is applied to a substrate for integrated circuit manufacturing (Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflective coating, etc.) or a substrate for mask circuit manufacturing (Cr, CrO, CrON, CrN, MoSi2, SiO 2、 The resist is applied onto a surface of a resist such as a Ta, MoSi laminated film, Ru, Ni, Co, W, Mo, V, or an alloy thereof, by a suitable coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc. The resulting solution is pre-baked on a hot plate preferably at 60 to 150°C for 10 seconds to 30 minutes, more preferably at 80 to 150°C for 30 seconds to 20 minutes, to form a resist film.

[0253] Before applying the resist material of the present invention, the substrate may be treated by irradiation with light, EB, plasma, or the like, or may be treated with CVD, ozone, hexamethyldisilazane (HMDS), or the like.

[0254] The thickness of the resist film is preferably 1 nm to 200 μm, and more preferably 2 nm to 100 μm.

[0255] A protective film may be formed on the resist film, and the protective film preferably has functions such as environmental protection, light absorption, antistatic properties, reduction of resist pattern defects, and resist pattern shape correction.

[0256] Next, the resist film is exposed to high-energy radiation. Specific examples of the high-energy radiation include ultraviolet radiation, far ultraviolet radiation, EB, EUV radiation with a wavelength of 3 to 15 nm, X-rays, soft X-rays, excimer laser light, gamma rays, and synchrotron radiation. When ultraviolet radiation, far ultraviolet radiation, EUV radiation, X-rays, soft X-rays, excimer laser light, gamma rays, and synchrotron radiation are used as the high-energy radiation, the exposure dose is preferably 1 to 200 mJ / cm, either directly or using a mask for forming a desired pattern. 2 approximately, more preferably 10 to 100 mJ / cm 2 When EB is used as the high energy beam, the exposure dose is preferably 0.1 to 1000 μC / cm 2 approximately, more preferably 0.5 to 900 μC / cm 2 The resist composition of the present invention is particularly suitable for fine patterning using high-energy rays such as g-rays, i-rays, KrF excimer laser light, ArF excimer laser light, EB, EUV, X-rays, soft X-rays, γ-rays, and synchrotron radiation.

[0257] After the exposure, PEB may be performed on a hot plate, preferably at 40 to 150° C. for 10 seconds to 30 minutes, more preferably at 50 to 120° C. for 30 seconds to 20 minutes.

[0258] After exposure or PEB, the desired pattern is formed on the substrate by developing using a developer for 3 seconds to 3 minutes, preferably 5 seconds to 2 minutes, by a conventional method such as dipping, puddling, or spraying.

[0259] The developer may be an organic solvent developer or an alkaline aqueous developer. Examples of the organic solvent developer include 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, 3-ethoxypropyl ... Examples of suitable alkaline developers include ethyl lactate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, 2-phenylethyl acetate, diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, xylene, toluene, anisole, methanol, ethanol, isopropanol, n-butyl alcohol, isobutyl alcohol, acetic anhydride, and acetic acid. Specific examples of the alkaline aqueous developer include aqueous solutions of potassium hydroxide, sodium hydroxide, and the like, and aqueous alkaline solutions of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline hydroxide. The developers may be used alone or in combination of two or more.

[0260] After the development is completed, the resist film is rinsed. A solvent that is miscible with the developer but does not dissolve the resist film is preferred as the rinse solution. Preferred examples of such solvents include alcohols having 3 to 10 carbon atoms, ether compounds having 8 to 12 carbon atoms, alkanes, alkenes, alkynes having 6 to 12 carbon atoms, aromatic solvents, and pure water.

[0261] Specific examples of the alcohol having 3 to 10 carbon atoms include n-propyl alcohol, isopropyl alcohol, 1-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, tert-pentyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, and 3-hexanol. Examples of the alcohol include 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, and 1-octanol.

[0262] Specific examples of the ether compound having 8 to 12 carbon atoms include di-n-butyl ether, diisobutyl ether, di-sec-butyl ether, di-n-pentyl ether, diisopentyl ether, di-sec-pentyl ether, di-tert-pentyl ether, and di-n-hexyl ether.

[0263] Specific examples of the alkanes having 6 to 12 carbon atoms include hexane, heptane, octane, nonane, decane, undecane, dodecane, methylcyclopentane, dimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cycloheptane, cyclooctane, cyclononane, etc. Specific examples of the alkes having 6 to 12 carbon atoms include hexene, heptene, octene, cyclohexene, methylcyclohexene, dimethylcyclohexene, cycloheptene, cyclooctene, etc. Specific examples of the alkynes having 6 to 12 carbon atoms include hexyne, heptine, octyne, etc.

[0264] Examples of aromatic solvents include toluene, xylene, ethylbenzene, isopropylbenzene, tert-butylbenzene, and mesitylene.

[0265] Rinsing can reduce the occurrence of resist pattern collapse and defects. Rinsing is not always necessary, and not performing rinsing can reduce the amount of solvent used.

[0266] The developed hole or trench pattern can also be shrunk using thermal flow, RELACS, or DSA. A shrink agent is applied to the hole pattern, and the diffusion of an acid catalyst from the resist film during baking causes crosslinking of the shrink agent on the surface of the resist film, resulting in adhesion of the shrink agent to the sidewalls of the hole pattern. The baking temperature is preferably 70 to 180°C, more preferably 80 to 170°C, and the baking time is preferably 10 to 300 seconds. Excess shrink agent is removed, and the hole pattern is shrunk. [Example]

[0267] The present invention will be explained in more detail below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to these. 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.

[0268] [Synthesis of benzenesulfonate (BSA-1)] 20 g of compound (A-1) was dissolved in a mixed solvent of 50 mL of water and 50 mL of dioxane. This solution was aged at 100°C for 24 hours, and then the solvent was distilled off under reduced pressure. 21 g of compound (A'-1) was obtained as a colorless, transparent liquid by drying under reduced pressure at 50°C. 21 g of compound (A'-1) was dissolved in 40 mL of water, and 8 g of triethylamine was added dropwise at room temperature. This solution was aged at room temperature for 24 hours, and then the solvent was distilled off under reduced pressure. 25 g of benzenesulfonate (BSA-1) was obtained as a white solid by drying under reduced pressure at 50°C. Molecular formula:C 12 H 16 NO3SF5 Molecular weight: 349.32

[0269] [ka]

[0270] [Synthesis of benzenesulfonate (BSA-2)] 20 g of compound (A-2) was dissolved in a mixed solvent of 50 mL of water and 50 mL of dioxane. This solution was aged at 100°C for 24 hours, and then the solvent was distilled off under reduced pressure. 19 g of compound (A'-2) was obtained as a white solid by drying under reduced pressure at 50°C. 19 g of compound (A'-2) was dissolved in 180 mL of water, and 7 g of triethylamine was added dropwise at room temperature. This solution was aged at room temperature for 24 hours, and then the solvent was distilled off under reduced pressure. 23 g of benzenesulfonate (BSA-2) was obtained as a white solid by drying under reduced pressure at 50°C. Molecular formula:C 21 H 39 NO3S Molecular weight: 385.61

[0271] [ka]

[0272] [Synthesis of benzenesulfonate (BSA-3)] 20 g of compound (A-3) was dissolved in a mixed solvent of 140 mL of water and 1000 mL of ethanol. 21 g of potassium hydroxide was added to this solution, and the mixture was aged at 90°C for 24 hours. After that, hydrochloric acid was added and the solvent was removed by distillation under reduced pressure. 150 mL of dichloromethane and 150 mL of water were added, and the organic layer was separated. The solvent was removed by distillation under reduced pressure, and the resulting solid was dried under reduced pressure at 50°C to obtain 20 g of compound (A'-3) as a white solid. 19 g of compound (A'-3) was dissolved in 150 mL of water, and 7 g of tripropylamine was added dropwise at room temperature. This solution was aged at room temperature for 24 hours, and the solvent was removed by distillation under reduced pressure. 22 g of benzenesulfonate (BSA-3) was obtained as a white solid by drying under reduced pressure at 50°C. Molecular formula:C 33 H 57 NO3S Molecular weight: 547.88

[0273] [ka]

[0274] [Synthesis of benzenesulfonate (BSA-4)] 20 g of compound (A-4) was dissolved in 200 mL of water, and 6 g of pyridine was added dropwise at room temperature. After aging the solution at room temperature for 24 hours, the solvent was distilled off under reduced pressure. After drying under reduced pressure at 50°C, 24 g of benzenesulfonate (BSA-4) was obtained as a white solid. Molecular formula:C 11 H9NO3SCl2 Molecular weight: 306.16

[0275] [ka]

[0276] [Synthesis of benzenesulfonate (BSA-5)] 20 g of compound (A-5) was dissolved in 200 mL of water, and 8 g of triethylamine was added dropwise at room temperature. After aging the solution at room temperature for 24 hours, the solvent was distilled off under reduced pressure. After drying under reduced pressure at 50°C, 25 g of benzenesulfonate (BSA-5) was obtained as a white solid. Molecular formula:C12 H 18 NO3SCl3 Molecular weight: 362.69

[0277] [ka]

[0278] [Synthesis of benzenesulfonate (BSA-6)] 20 g of compound (A-6) was dissolved in 200 mL of water, and 8 g of tripropylamine was added dropwise at room temperature. After aging the solution at room temperature for 24 hours, the reaction solution was filtered to obtain a white solid. After drying under reduced pressure at 50°C, 17 g of benzenesulfonate (BSA-6) was obtained as a white solid. Molecular formula:C 27 H 36 NO3SP Molecular weight: 485.62

[0279] [ka]

[0280] [Synthesis of benzenesulfonate (R-1)] 20 g of compound (S-1) was dissolved in 200 mL of water, and 8 g of pyridine was added dropwise at room temperature. After aging the solution at room temperature for 24 hours, the solvent was distilled off under reduced pressure. After drying under reduced pressure at 50°C, 26 g of benzenesulfonate (R-1) was obtained as a white solid. Molecular formula:C 12 H 13 NO3S Molecular weight: 251.30

[0281] [ka]

[0282] [Synthesis of benzenesulfonate (R-2)] 20 g of compound (S-1) was dissolved in 200 mL of water, and 11 g of triethylamine was added dropwise at room temperature. After aging the solution at room temperature for 24 hours, the solvent was distilled off under reduced pressure. After drying under reduced pressure at 50°C, 29 g of benzenesulfonate (R-2) was obtained as a white solid. Molecular formula:C 13 H 23 NO3S Molecular weight: 273.39

[0283] [ka]

[0284] [Resin and / or compound for forming organic film] C1: Resin represented by the following formula (C1): C2: Resin represented by the following formula (C2) C3: Resin represented by the following formula (C3): C4: Resin represented by the following formula (C4): C5: Resin represented by the following formula (C5): C6: Resin represented by the following formula (C6): C7: Resin represented by the following formula (C7): C8: Resin represented by the following formula (C8): C9: Resin represented by the following formula (C9): C10: A resin represented by the following formula (C10): C11: A resin represented by the following formula (C11):

[0285] [ka]

[0286] [ka]

[0287] [solvent] (D1): Propylene glycol monomethyl ether acetate (D2): Propylene glycol monoethyl ether (D3): Cyclohexanone

[0288] [Preparation of Organic Film-Forming Compositions (Sols. 1 to 24, Comparative Sols. 1 to 5)] The above compounds (B) (acid generators): (BSA-1) to (BSA-6), (R1) to (R2), organic film-forming resins (C1) to (C11), and solvents (D1) to (D3) were dissolved in the proportions shown in Tables 1 and 2, and the resulting mixture was filtered through a 0.1 μm fluorine resin filter to prepare organic film materials (resist intermediate film materials: Sol. 1 to 24, comparative Sol. 1 to 5).

[0289] [Table 1] [Table 2]

[0290] [Preparation of Silicon Wafers with Organic Cured Films Formed Using Organic Film-Forming Compositions (Sols. 1 to 24, Comparative Sols. 1 to 5)] Using a Tokyo Electron Limited coater / developer "CLEAN TRACK LITHIUS Pro AP," 2 mL of the organic film-forming compositions (Sols. 1-24, comparative Sols. 1-5) was dispensed onto the center of a 300 mm silicon wafer and spread to form a film. The wafer was rotated at 1000 rpm, and a remover solution (a mixture of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether (30:70, mass ratio)) was dispensed at a rate of 2 mL / s. The nozzle was then moved at a rate of 5 mm / s from the outer periphery of the wafer to a position 3 mm toward the center. At this position, the remover solution was dispensed at a rate of 2 mL / s for 5 seconds. Dispensing of the 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.

[0291] [Solvent Resistance Evaluation: Examples 1-1 to 1-24, Comparative Examples 1-1 to 1-5] Using the method described above, organic film-forming compositions (Sols. 1 to 24, Comparative Sols. 1 to 5) were deposited on silicon wafers to obtain Films 1 to 29. The film thickness at the periphery was measured, and PGMEA (propylene glycol monomethyl ether acetate) solvent was dispensed onto the wafer. The wafer was left for 30 seconds, spin-dried, and baked at 100°C for 60 seconds to evaporate the PGMEA. The film thickness at the periphery was then measured. The film thickness before dispensing the PGMEA solvent was designated X, and the film thickness after dispensing the PGMEA solvent was designated X1. The absolute value of the value calculated by (X1 - 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 greater was considered poor.

[0292] [In-plane uniformity evaluation: Examples 1-1 to 1-24, Comparative Examples 1-1 to 1-5] For Films 1 to 29 formed on silicon wafers using the above method, the film thickness was measured within a radius of 145 mm from the center of the organic cured film, and the maximum film thickness Xmax, minimum film thickness Xmin, and average film thickness 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.

[0293] [Evaluation of Coatability of Silicon-Containing Resist Interlayer: Examples 1-1 to 1-24, Comparative Examples 1-1 to 1-5] Using the method described above, organic film-forming compositions (Sol. 1 to 24, Comparative Sol. 1 to 5) were deposited on silicon wafers to obtain Films 1 to 29. The silicon-containing resist interlayer material (SOG1) described below was then coated on top of the films and baked at 200°C for 60 seconds to form silicon-containing resist interlayer films. 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.

[0294] 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 3, and filtering the resultant mixture through a 0.1 μm fluororesin filter. [Table 3]

[0295] The polymer (SP1) is shown below. [ka]

[0296] TMPANO3: Trimethylphenylammonium nitrate PGEE: Propylene glycol ethyl ether

[0297] [Table 4]

[0298] As shown in Table 4, the organic film-forming compositions (Sol. 1-1 to 24) of the present invention, which use thermal acid generators with large molecular weights (BSA-1 to BSA-6), were confirmed to be excellent in solvent resistance, in-plane uniformity, and coatability of silicon-containing resist intermediate films. At the same time, good in-plane uniformity was obtained. The acid generator used in the comparative example had a small molecular weight and was therefore prone to sublimation, resulting in poor solvent resistance, lack of film thickness uniformity, and poor coating of the silicon-containing resist intermediate film, particularly in the outer periphery of the film.

[0299] [Pattern formation test: Examples 2-1 to 2-24] Using the method described above, an organic cured film was formed on a SiO2 wafer substrate using an organic film-forming composition (Sol. 1-24). The following silicon-containing resist intermediate film material (SOG2) was then applied on top of the 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 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.

[0300] 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 5, and filtering the resultant mixture through a 0.1 μm fluororesin filter. [Table 5]

[0301] 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 PGMEA (propylene glycol monomethyl ether acetate) solvent containing 0.1 mass% FC-430 (manufactured by Sumitomo 3M Limited) in the proportions shown in Table 6, and filtering the solution through a 0.1 μm fluororesin filter. [Table 6]

[0302] The polymer (RP1), acid generator (PAG1), and basic compound (Amine1) are shown below. [ka]

[0303] The immersion protective film material (TC-1) was prepared by dissolving the polymer (PP1) in an organic solvent in the ratio shown in Table 7 and filtering the solution through a 0.1 μm fluorine resin filter. [Table 7]

[0304] The polymer (PP1) is shown below. [ka]

[0305] 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).

[0306] 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 follows:

[0307] (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

[0308] (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

[0309] (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

[0310] The cross section of the obtained pattern was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd. The results are shown in Table 8. [Table 8]

[0311] As shown in Table 8, in Examples 2-1 to 2-24 in which the organic film-forming composition of the present invention (Sol. 1 to 24) was used, the resist upper layer film pattern was ultimately transferred successfully to the SiO2 wafer substrate, confirming that the organic film-forming composition of the present invention is suitable for use in microfabrication using the multilayer resist method.

[0312] From the above, the organic film-forming composition of the present invention has excellent film-forming properties and in-plane uniformity, and is excellent in coatability for forming silicon-containing resist intermediate films, making it extremely useful as an organic film material for use in multilayer resist processes. It is also capable of forming fine patterns with high precision and of forming organic films with suppressed humps, making it possible to efficiently manufacture semiconductor elements and the like.

[0313] This specification includes the following inventions. [1]: A composition for forming an organic film, characterized in that it contains an organic film-forming resin and / or compound (A), a benzenesulfonate compound (B) represented by the following formula (1), in which the molecular weight of the anion moiety in formula (1) is 200 or more and which does not contain a perfluoroalkyl group, and a solvent (C). [ka] (wherein R1 represents a linear, cyclic, or branched alkyl group having 1 to 20 carbon atoms, which may have a substituent not including a perfluoroalkyl group, an alkenyl group, an oxoalkyl group, an aryl group, or an aralkyl group, or -P(R)2 (wherein R is an alkyl group or an aryl group having 1 to 20 carbon atoms), or a halogen atom or a nitro group; n represents an integer of 1 to 5; A + represents an ammonium cation, a pyridinium cation, a sulfonium cation, a phosphonium cation, an imidazolium cation, a piperidinium cation, or a pyrrolidinium cation. [2]: The composition for forming an organic film according to [1], wherein the benzenesulfonate compound (B) is represented by the following general formula (2-1), (2-2) or (2-3): [ka] (A + is A in the above formula (1) + is equivalent to [ka] (In the formula, R2 represents a chlorine atom or an iodine atom. m represents an integer of 1 to 5. A + is A in the above formula (1) + is equivalent to [ka] (In the formula, R3 is an alkyl group having 1 to 20 carbon atoms which may have a substituent but does not contain a perfluoroalkyl group. A + is A in the above formula (1) +is equivalent to [3]: The organic film-forming composition according to [2], characterized in that the benzenesulfonate compound (B) is one in which the molecular weight of the anion moiety in the general formula (2-1), (2-2) or (2-3) is 245 or more. [4]: The benzenesulfonate compound (B) is represented by the general formula (2-3), in which R3 does not contain a perfluoroalkyl group and is an alkyl group having 3 to 20 carbon atoms and a branched or cyclic structure, and A + The composition for forming an organic base film according to [2] or [3], wherein is a triethylammonium cation or a tributylammonium cation. [5]: The composition for forming an organic film according to any one of [1] to [4], wherein the resin for forming an organic film or the compound (A) has any one of a methylol group, an epoxy group, or a phenolic hydroxyl group. [6]: A method for forming an organic film used in the manufacturing process of a semiconductor device, comprising spin-coating the composition for forming an organic film according to any one of [1] to [5] onto a substrate to be processed, and heat-treating the substrate coated with the composition for forming an organic film at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds to form a cured film. [7]: A pattern forming method comprising the steps of forming an organic film on a workpiece using the organic film-forming composition according to any one of [1] to [5], forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms, forming a resist upper layer film on the resist intermediate film using a resist upper layer film material consisting of a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the resist intermediate film on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask. [8]: A pattern formation method comprising the steps of forming an organic film on a workpiece using the organic film-forming composition according to any one of [1] to [5], forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms, forming an organic antireflective film or an adhesive film on the resist intermediate film, forming a resist upper layer film on the organic antireflective film or adhesive film using a resist upper layer film material consisting of a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the organic antireflective film or adhesive film and the resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the resist intermediate film on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask. [9]: A pattern formation method comprising the steps of forming an organic film on a workpiece using the organic film-forming composition according to any one of [1] to [5], forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming a resist upper layer film on the inorganic hard mask using a resist upper layer film material comprising a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the inorganic hard mask by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[10] : A pattern formation method comprising the steps of forming an organic film on a workpiece using the organic film-forming composition according to any one of [1] to [5], forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming an organic antireflective film or an adhesion film on the inorganic hard mask, forming a resist upper layer film on the organic antireflective film using a resist upper layer film material comprising a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the organic antireflective film and the inorganic hard mask by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

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

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

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

[11] , 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

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

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

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

[15] : The pattern forming method according to [7], 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 benzenesulfonate compound (B) for forming an organic film, which is represented by the following formula (1), in which the molecular weight of the anion moiety in the formula (1) is 200 or more, and which does not contain a perfluoroalkyl group. [ka] (wherein R1 represents a linear, cyclic, or branched alkyl group having 1 to 20 carbon atoms, which may have a substituent not including a perfluoroalkyl group, an alkenyl group, an oxoalkyl group, an aryl group, or an aralkyl group, or -P(R)2 (wherein R is an alkyl group or an aryl group having 1 to 20 carbon atoms), or a halogen atom or a nitro group; n represents an integer of 1 to 5; A + represents an ammonium cation, a pyridinium cation, a sulfonium cation, a phosphonium cation, an imidazolium cation, a piperidinium cation, or a pyrrolidinium cation.

[17] : The benzenesulfonate compound according to

[16] , which is represented by the following general formula (2-1), (2-2) or (2-3): [ka] (A + is A in the above formula (1) + is equivalent to [ka] (wherein R2 represents a chlorine atom or an iodine atom, m represents an integer of 1 to 5, A + is A in the above formula (1) + is equivalent to [ka] (In the formula, R3 is an alkyl group having 1 to 20 carbon atoms which may have a substituent but does not contain a perfluoroalkyl group. A + is A in the above formula (1) + is equivalent to

[18] : The benzenesulfonate compound according to

[17] , wherein the molecular weight of the anion moiety represented by the general formula (2-1), (2-2) or (2-3) is 245 or more.

[19] : A compound represented by the general formula (2-3), wherein R3 does not contain a perfluoroalkyl group and is an alkyl group having 3 to 20 carbon atoms and a branched or cyclic structure; + is a triethylammonium cation or a tributylammonium cation.

[20] : A pattern forming method comprising forming an organic film on a workpiece using a resist material prepared using the composition for forming an organic film according to any one of [1] to [5], exposing the resist film to high-energy rays, and developing the exposed resist film using a developer.

[0314] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention. [Explanation of symbols]

[0315] 1...substrate, 2...processed layer, 2a...pattern formed on the processed layer, 3...organic film, 3'...organic film-forming composition, 3a...organic film pattern, 4...silicon-containing resist underlayer film, 4a...silicon-containing resist underlayer film pattern, 5...resist upper layer film, 5a...resist upper layer film pattern, 6...exposed portion

Claims

1. A composition for forming an organic film, characterized in that it contains an organic film-forming resin and / or compound (A), a benzenesulfonate compound (B) represented by the following formula (1), in which the molecular weight of the anion moiety in formula (1) is 200 or more and which does not contain a perfluoroalkyl group, and a solvent (C): 【Chemistry 1】 (In the formula, R １ is a linear, cyclic or branched alkyl group having 1 to 20 carbon atoms, which may have a substituent not including a perfluoroalkyl group, an alkenyl group, an oxoalkyl group, an aryl group, an aralkyl group, or -P(R) ２ (R is an alkyl group or an aryl group having 1 to 20 carbon atoms), or a halogen atom or a nitro group; n is an integer of 1 to 5; A ＋ represents an ammonium cation, a pyridinium cation, a sulfonium cation, a phosphonium cation, an imidazolium cation, a piperidinium cation, or a pyrrolidinium cation.

2. The organic film-forming composition according to claim 1, wherein the benzenesulfonate compound (B) is represented by the following general formula (2-1), (2-2) or (2-3): 【Chemistry 2】 (A ＋ is A in the above formula (1). ＋ is synonymous with 【Transformation 3】 (In the formula, R ２ represents a chlorine atom or an iodine atom. m represents an integer of 1 to 5. ＋ is A in the above formula (1). ＋ is synonymous with 【Chemistry 4】 (In the formula, R ３ A is an alkyl group having 1 to 20 carbon atoms which may have a substituent but does not contain a perfluoroalkyl group. ＋ is A in the above formula (1). ＋ is synonymous with

3. The organic film-forming composition according to claim 2, wherein the benzenesulfonate compound (B) is a compound represented by the general formula (2-1), (2-2), or (2-3) in which the molecular weight of the anion moiety is 245 or more.

4. The benzenesulfonate compound (B) is represented by the general formula (2-3), wherein R ３ is an alkyl group having 3 to 20 carbon atoms and having a branched or cyclic structure, and does not contain a perfluoroalkyl group, and A ＋ 3. The composition for forming an organic base film according to claim 2, wherein is a triethylammonium cation or a tributylammonium cation.

5. 2. The composition for forming an organic film according to claim 1, wherein the resin for forming an organic film or the compound (A) has any one of a methylol group, an epoxy group, and a phenolic hydroxyl group.

6. A method for forming an organic film used in a manufacturing process of a semiconductor device, comprising spin-coating the organic film-forming composition according to any one of claims 1 to 5 onto a substrate to be processed, and heat-treating the substrate coated with the organic film-forming composition at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds, thereby forming a cured film.

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

8. a resist intermediate film material containing silicon atoms formed on the organic film; an organic antireflective film or an adhesive film formed on the resist intermediate film; a resist upper layer film formed on the organic antireflective film or the adhesive film using a resist upper layer film material comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern by etching onto the organic antireflective film or the adhesive film and the resist intermediate film using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern by etching onto the organic film using the resist intermediate film on which the pattern has been transferred as a mask; and further transferring the pattern onto the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

9. 6. A pattern formation method comprising: forming an organic film on a workpiece using the organic film-forming composition according to claim 1; forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film; forming a resist upper layer film on the inorganic hard mask using a resist upper layer film material comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the inorganic hard mask by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

10. a resist upper layer film formed on the organic antireflective coating using a resist upper layer film material comprising a photoresist composition; a circuit pattern formed on the resist upper layer film; a pattern transfer step using the resist upper layer film having the circuit pattern formed thereon as a mask to transfer the pattern to the organic antireflective coating and the inorganic hard mask by etching; a pattern transfer step using the inorganic hard mask having the pattern transferred thereon as a mask to transfer the pattern to the organic film by etching; and a pattern transfer step using the organic film having the pattern transferred thereon as a mask to transfer the pattern to the workpiece by etching.

11. 10. The pattern formation method according to claim 9, wherein the inorganic hard mask 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 on which any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film is formed.

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 benzenesulfonate compound for forming an organic film, which is represented by the following formula (1), in which the molecular weight of the anion moiety in formula (1) is 200 or more, and which does not contain a perfluoroalkyl group: 【Transformation 5】 (In the formula, R １ is a linear, cyclic or branched alkyl group having 1 to 20 carbon atoms, which may have a substituent not including a perfluoroalkyl group, an alkenyl group, an oxoalkyl group, an aryl group, an aralkyl group, or -P(R) ２ (R is an alkyl group or an aryl group having 1 to 20 carbon atoms), or a halogen atom or a nitro group; n is an integer of 1 to 5; A ＋ represents an ammonium cation, a pyridinium cation, a sulfonium cation, a phosphonium cation, an imidazolium cation, a piperidinium cation, or a pyrrolidinium cation.

17. The benzenesulfonate compound according to claim 16, which is represented by the following general formula (2-1), (2-2) or (2-3): 【Transformation 6】 (A ＋ is A in the above formula (1). ＋ is synonymous with 【Transformation 7】 (In the formula, R ２ represents a chlorine atom or an iodine atom, m is an integer of 1 to 5, A ＋ is A in the above formula (1). ＋ is synonymous with 【Transformation 8】 (In the formula, R ３ A is an alkyl group having 1 to 20 carbon atoms which may have a substituent but does not contain a perfluoroalkyl group. ＋ is A in the above formula (1). ＋ is synonymous with

18. The benzenesulfonate compound according to claim 17, wherein the molecular weight of the anion moiety represented by the general formula (2-1), (2-2) or (2-3) is 245 or more.

19. Represented by the general formula (2-3), wherein R ３ is an alkyl group having 3 to 20 carbon atoms and having a branched or cyclic structure, and does not contain a perfluoroalkyl group, and A ＋ 19. The benzenesulfonate compound of claim 18, wherein is a triethylammonium cation or a tributylammonium cation.

20. 6. A pattern forming method comprising: forming an organic film on a workpiece using a resist material that uses the composition for forming an organic film according to claim 1; exposing the resist film to high-energy rays; and developing the exposed resist film using a developer.

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