Film-forming composition, method for forming organic film, patterning process, monomer, and polymer

Abstract

To provide a film-forming composition exhibiting reduced environmental impact and superior coating performance on a substrate.SOLUTION: A film-forming composition comprising a polymer having an aromatic group with a pentafluorosulfanyl group as a substituent.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a film-forming composition, an organic film-forming method, a pattern-forming method, a monomer, and a polymer. [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 underlayer film, a silicon-containing film is formed on top of that as a resist underlayer film, and a conventional organic photoresist film is formed on top of that as a resist upper layer film. For dry etching using fluorine-based gas plasma, the organic resist upper layer film has a good etching selectivity relative to the silicon-containing resist intermediate film, so the resist pattern is transferred to the silicon-containing resist underlayer film by dry etching using fluorine-based gas plasma. This method can transfer a pattern to the silicon-containing film even 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 with oxygen-based gas plasma can result in 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 underlayer films (silicon-containing intermediate films, organic underlayer films).

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

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

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

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

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

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

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

[0014] [Patent Document 1] Patent No. 4355943 etc. [Patent Document 2] Japanese Patent Application Laid-Open No. 2004-205685 [Patent Document 3] Japanese Patent Application Publication No. 6-186735 [Patent Document 4] Japanese Patent Application Publication No. 6-214380 [Patent Document 5] Japanese Patent Application Laid-Open No. 2010-139822 [Patent Document 6] Special Publication No. 2008-526792 [Patent Document 7] International Publication No. 2023-223624 Summary of the Invention [Problem to be solved by the invention]

[0015] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a film-forming composition that has a low environmental impact and excellent applicability to a substrate. [Means for solving the problem]

[0016] In order to solve the above problems, the present invention provides: A film-forming composition, The film-forming composition contains a polymer having an aromatic group having a pentafluorosulfanyl group as a substituent.

[0017] In this case, the polymer is preferably a polymer (a) having a repeating unit a having an aromatic group having a pentafluorosulfanyl group as a substituent.

[0018] If the film-forming composition contains the polymer having such a structure, the aromatic group having the pentafluorosulfanyl group as a repeating group makes it easier to form an aggregate structure by the interaction between the pentafluorosulfanyl group and the benzene ring, and the behavior of the hydrophobic group is coordinated, and it is thought that it can utilize the same effect as the "fluorophilic" effect that is discussed in perfluoroalkyl groups, and the synergistic effect of the interaction between aromatic rings.Therefore, the film-forming composition of the present invention can provide a film-forming material that can be applied not only to the film-forming ability of using various polymers alone, but also to the film-forming material that uses organic polymers, compounds, or inorganic materials such as silicon, titanium, zirconium, etc.

[0019] The repeating unit a is preferably represented by any one of the following formulas (a1) to (a4). [ka] (In the above formula, p is an integer of 1 to 3, n is an integer of 0 to 5, and m is an integer of 0 to 4. R1 is a hydrogen atom or a methyl group, R2 is a hydrocarbyl group having 1 to 6 carbon atoms, a hydrocarbyloxy group having 1 to 12 carbon atoms, a hydrocarbyloxycarbonyl group having 2 to 6 carbon atoms, a hydrocarbylcarbonyloxy group having 2 to 12 carbon atoms, a hydroxy group, a carboxy group, a halogen atom, a trifluoromethoxy group, a cyano group, or a nitro group. X1 is a single bond, an ester bond, an ether bond, a sulfonate ester group, a sulfonamide group, an amide bond, or is a phenylene group, X2 is a single bond or a hydrocarbylene group having 1 to 20 carbon atoms when p is 1, and is a (p+1)-valent hydrocarbon group having 1 to 20 carbon atoms when p is 2 or 3, and these hydrocarbylene groups and (p+1)-valent hydrocarbon groups may contain at least one atom selected from oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. X3 is a single bond or an ether bond. Ar1 is each independently a (m+n+1)-valent group derived from benzene or naphthalene, provided that at least one of the n's in the formula is 1 or greater.) [ka] (In the above formula, n and m are the same as defined above, l is an integer of 0 to 3, and at least one of the two n's and two l's in the formula is 1 or greater. R2 and X3 are the same as defined above, and R3 is the following general formula (a2-1). Ar2's are each independently an (n+m+l+2)-valent aromatic hydrocarbon group having 6 to 30 carbon atoms. Ar3 is an (n+m+l+1)-valent group derived from benzene or naphthalene.) [ka] (In the above formula, X3 and n are the same as defined above, X4 is a single bond or a hydrocarbylene group having 1 to 12 carbon atoms, and the hydrocarbylene group may have at least one of a hydroxy group, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, an ether bond, an ester bond, and an amide bond. Ar4 is an (n+1)-valent group derived from benzene or naphthalene.) [ka] (In the above formula, n, m, l, Ar2, R2, R3, and X3 are the same as defined above, and R4 is a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms, and the hydrocarbyl group may contain an oxygen atom. However, it does not contain a substituent containing SF5. Also, at least one of n and l in the formula is 1 or greater.) [ka] (wherein R3 and R4 are the same as above.)

[0020] A polymer having the repeating units shown above can effectively utilize the intermolecular interactions described above, making it possible to provide an excellent film-forming material.

[0021] In this case, the repeating unit a is preferably represented by the formula (a1).

[0022] The repeating unit represented by (a1) is advantageous in terms of ease of production of the material and the range of combinations with polymers and compounds for forming organic films.

[0023] It is preferable that the polymer (a) further contains a repeating unit (b1) having a hydrophilic group selected from an ether bond, an ester bond, a hydroxy group, a carboxy group, a sulfonamide bond, a sulfonimide bond, a sulfo group, a lactone ring, a sultone ring, a carbonate bond, a urethane bond, and an amide bond.

[0024] As described above, the film-forming material has excellent film-forming properties, and by combining the above-described hydrophilic groups with repeating units, they can serve as units for relaxing the aggregation structure described above, thereby broadening the versatility of the film-forming material. For example, it is possible to provide a film-forming material that can accommodate various film thicknesses (independent of solution concentration) by adjusting the surfactant activity.

[0025] The film-forming composition is preferably an organic film-forming composition containing (A) an organic film-forming resin or compound, (B) the polymer (a), and (C) a solvent.

[0026] The above-described polymer (a), a resin or compound for forming an organic film, and a solvent can be combined to form a composition for forming an organic film.

[0027] Furthermore, the content of the component (B) is preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the component (A).

[0028] By adding the polymer (a) in such a range, the film-forming properties of the organic film-forming composition can be improved. Therefore, although there are various resins and compounds, such as resins having various repeating units, compounds having a rigid structure and high crystallinity, and compounds having highly polar substituents, the polymer (a) of the present invention can provide an organic film-forming composition having excellent film-forming properties even when using resins or compounds with different properties.

[0029] It is preferable that the composition further contains (D) a photoacid generator or (E) a thermal acid generator.

[0030] By preparing such a composition for forming an organic film, photosensitivity and the like can be imparted to the composition for forming an organic film, and the composition for forming an organic film of the present invention can be used as a resist material for photolithography and the like.

[0031] In addition, in the present invention, The present invention provides a method for forming an organic film used in the manufacturing process of a semiconductor device, which comprises spin-coating the above-described film-forming composition on a substrate to be processed, and then heat-treating the substrate coated with the film-forming composition at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds to form a cured film.

[0032] The organic film-forming composition of the present invention is particularly useful when it is used to fill complex patterns on a substrate to be processed by spin coating, to form an organic film with excellent in-plane uniformity, and to remove the organic film from the edges while suppressing humps in the EBR process.

[0033] In addition, in the present invention, The present invention provides a pattern formation method that includes forming an organic film on a workpiece using the above-described film-forming composition, forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms, forming a resist upper layer film on the resist intermediate film using a resist upper layer film material consisting of a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the resist intermediate film on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0034] In addition, in the present invention, The present invention provides a pattern formation method including the steps of forming an organic film on a workpiece using the above-described film-forming composition, forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms, forming an organic antireflective film or 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 by etching onto the organic antireflective film or adhesive film and the resist intermediate film using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern by etching onto the organic film using the resist intermediate film on which the pattern has been transferred as a mask, and further transferring the pattern onto the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0035] In addition, in the present invention, The present invention provides a pattern formation method, which includes forming an organic film on a workpiece using the above-described film-forming composition, forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming a resist upper layer film on the inorganic hard mask using a resist upper layer film material 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.

[0036] In addition, in the present invention, The present invention provides a pattern formation method, which includes forming an organic film on a workpiece using the above-described film-forming composition, forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming an organic antireflective film or an adhesive film on the inorganic hard mask, forming a resist upper layer film on the organic antireflective film or adhesive film using a resist upper layer film material comprising a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern by etching onto the organic antireflective film or adhesive film and the inorganic hard mask using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern by etching onto the organic film using the inorganic hard mask on which the pattern has been transferred as a mask, and further transferring the pattern onto the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0037] As described above, the organic film-forming composition of the present invention can be suitably used in various pattern formation methods, such as a three-layer resist process using a silicon-containing resist intermediate film or an inorganic hard mask, 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.

[0038] Furthermore, it is preferable that the inorganic hard mask be formed by a CVD method or an ALD method.

[0039] In the pattern formation method of the present invention, for example, an inorganic hard mask can be formed by such a method.

[0040] 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.

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

[0042] In the pattern forming method of the present invention, such circuit pattern forming means and developing means can be suitably used.

[0043] Furthermore, 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] In this case, the metal constituting the workpiece is preferably silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof.

[0045] The pattern forming method of the present invention makes it possible to form a pattern by processing the above-mentioned workpiece.

[0046] In addition, in the present invention, The present invention provides a pattern forming method including the steps of forming a resist film on a substrate using the above-described film-forming composition, exposing the resist film to high-energy rays, and developing the exposed resist film using a developer.

[0047] By using the film-forming composition of the present invention, a pattern can be formed by carrying out the above-mentioned exposure.

[0048] In this case, the high energy ray is preferably g-ray, i-ray, KrF excimer laser, ArF excimer laser, ultraviolet ray, electron beam, or extreme ultraviolet ray having a wavelength of 3 to 15 nm.

[0049] By using the high energy beams described above, it is possible to form fine patterns.

[0050] The present invention also provides a monomer represented by the following general formula (a5): [ka] (In the formula, R x is a hydrogen atom or a methyl group, and X a is a linking group having 1 to 12 carbon atoms which is a single bond, a phenylene group, a naphthylene group, or an ester bond, an ether bond, or a lactone ring, and may have an oxygen atom, a nitrogen atom, a sulfur atom, and / or a halogen atom; La is an acid labile group which has an aromatic group having at least one pentafluorosulfanyl group as a substituent.

[0051] The monomer of the present invention is preferably represented by the following general formula (a6). [ka] (In the formula, X a , R x As mentioned above. R 11 , R 12 are each independently a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkenyl group having 2 to 12 carbon atoms, a linear, branched, or cyclic alkynyl group having 2 to 12 carbon atoms, or an aryl group having 5 to 10 carbon atoms, which may have an oxygen atom and / or a sulfur atom; R 11 and R 12 may be bonded to form a ring. 13 are each independently a hydrogen atom, a halogen atom, or an alkyl or alkoxy group having 1 to 4 carbon atoms. m is an integer of 0 to 4, and n is an integer of 1 to 3.

[0052] Monomers such as those described above are not subject to PFAS regulations and are therefore promising candidates to replace conventional monomers that incorporate fluorine substituents.

[0053] The present invention also provides a polymer that contains a repeating unit represented by the following general formula (a7) and has a weight-average molecular weight in the range of 100 to 500,000. [ka] (In the formula, Rx is a hydrogen atom or a methyl group, and X a is a linking group having 1 to 12 carbon atoms which is a single bond, a phenylene group, a naphthylene group, or an ester bond, an ether bond, or a lactone ring, and may have an oxygen atom, a nitrogen atom, a sulfur atom, and / or a halogen atom; La is an acid labile group which has an aromatic group having at least one pentafluorosulfanyl group as a substituent.

[0054] The polymer of the present invention preferably contains a repeating unit represented by the following general formula (a8) and has a weight average molecular weight in the range of 100 to 500,000. [ka] (In the formula, X a , R x As mentioned above. R 11 , R 12 are each independently a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkenyl group having 2 to 12 carbon atoms, a linear, branched, or cyclic alkynyl group having 2 to 12 carbon atoms, or an aryl group having 5 to 10 carbon atoms, which may have an oxygen atom and / or a sulfur atom; R 11 and R 12 may be bonded to form a ring. 13 are each independently a hydrogen atom, a halogen atom, or an alkyl or alkoxy group having 1 to 4 carbon atoms. m is an integer of 0 to 4, and n is an integer of 1 to 3.

[0055] Polymers such as those described above are not subject to PFAS regulations and are promising candidates to replace conventional polymers that incorporate fluorine substituents. [Effects of the Invention]

[0056] As described above, the present invention allows for the application of film-forming materials with excellent film-forming properties (in-plane uniformity) and filling properties on substrates (wafers). When an organic film-forming material combined with an organic film-forming resin and compound is used as an organic underlayer film, it provides an organic film-forming composition that exhibits excellent film-forming properties on the organic film and suppresses humps during the EBR process. Furthermore, even when the organic film-forming composition is used as a resist material by combining a photoacid generator or the like, it can be used as a photolithography resist material with excellent in-plane uniformity to fabricate fine patterns. Furthermore, by incorporating hydrophilic units into the copolymer, the composition can be applied not only to various organic film-forming materials but also to film-forming materials containing metal atoms such as silicon, making it useful as a film-forming material that achieves high versatility and high film-forming properties. 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 underlayer film or an inorganic hard mask, or a four-layer resist process using a silicon-containing resist underlayer film or an inorganic hard mask and an organic antireflective film, or as a film-forming material for semiconductor device production, such as a photoresist material. Furthermore, the film-forming composition of the present invention is environmentally friendly. [Brief explanation of the drawings]

[0057] [Figure 1] 1 is an example of a graph showing the height of humps measured using a contact profiler in a composition for forming an organic film in which humps are suppressed. [Figure 2] 1 is an example of a graph showing the height of humps measured using a contact profiler in an organic film-forming composition in which humps are not suppressed. [Figure 3] 1A to 1C are explanatory diagrams illustrating an example of a pattern formation method using a three-layer resist process according to the present invention. [Figure 4] FIG. 1 is an explanatory diagram of a method for evaluating filling characteristics in an example. DETAILED DESCRIPTION OF THE INVENTION

[0058] As described above, there has been a demand for a film-forming material that has excellent hump characteristics and film-forming properties, can achieve high in-plane uniformity and filling characteristics, and can also comply with environmental regulations.

[0059] For example, when forming an organic film, a resin for forming the organic film and additives are dissolved in an organic solvent to form a composition, which is then applied 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.

[0060] If the surfactant effect of the above composition is insufficient, uneven distribution of the surfactant in the film occurs, resulting in the formation of voids when filling holes or trenches with very high aspect ratios. In addition, if the resin or additives used to form the organic film have poor solubility in the remover used in the EBR process, humps may form on the periphery of the organic film.

[0061] The present inventors have conducted further intensive research to obtain a film-forming material that meets the recent demand for high flatness after coating, excellent film-forming properties such as good coating properties at the outermost edge of the substrate (wafer), and minimal defects after coating, development, and etching. They have discovered that the use of a polymer having a specific substituent results in an organic film-forming composition that is excellent in film-forming properties, advanced embedding properties, and hump suppression during the EBR process, thereby completing the present invention. The film-forming composition of the present invention, which uses a polymer having a pentafluorosulfanyl group as a substituent on the aromatic group, has a structure that does not fall under PFAS regulations, and is therefore expected to be an industrially useful material that is also environmentally friendly.

[0062] That is, the present invention is a film-forming composition, which contains a polymer having an aromatic group having a pentafluorosulfanyl group as a substituent.

[0063] The present invention will be described in detail below, but the present invention is not limited thereto.

[0064] [Film-forming composition] The present invention provides a film-forming composition using a polymer containing an aromatic group having a pentafluorosulfanyl group as a substituent, which is not a perfluoroalkyl compound (PFAS).

[0065] By using an organic film-forming composition containing this polymer, it is possible to form a film with excellent coating properties, such as reduced pinholes and other coating defects on the substrate (wafer), film-forming properties (in-plane uniformity), and embedding properties. Furthermore, by using this organic film-forming composition as an organic underlayer film material, it is possible to provide an organic film with excellent process tolerance when used as an organic underlayer film for a multilayer resist, and organic film formation methods and pattern formation methods using this organic film-forming composition can be provided. Furthermore, this organic film-forming composition is also useful as a photoresist material, providing excellent film flatness after application and fewer defects not only after application but also after development, and further providing a pattern formation method using this. The above makes it possible to provide a film-forming material that is free of PFASs, making it useful as a film-forming material with low environmental impact.

[0066] The polymer is preferably a polymer (a) having a repeating unit a having an aromatic group having a pentafluorosulfanyl group as a substituent, and the substituent is preferably —SF5 or —OSF5 directly substituted on the aromatic ring.

[0067] The repeating unit a of the polymer is preferably represented by any one of the following formulas (a1) to (a4).

[0068] The repeating unit (a1) represented by general formula (a1) is shown below. [ka] (In the above formula, p is an integer of 1 to 3, n is an integer of 0 to 5, and m is an integer of 0 to 4. R1 is a hydrogen atom or a methyl group, R2 is a hydrocarbyl group having 1 to 6 carbon atoms, a hydrocarbyloxy group having 1 to 12 carbon atoms, a hydrocarbyloxycarbonyl group having 2 to 6 carbon atoms, a hydrocarbylcarbonyloxy group having 2 to 12 carbon atoms, a hydroxy group, a carboxy group, a halogen atom, a trifluoromethoxy group, a cyano group, or a nitro group. X1 is a single bond, an ester bond, an ether bond, a sulfonate ester group, a sulfonamide group, an amide bond, or is a phenylene group, X2 is a single bond or a hydrocarbylene group having 1 to 20 carbon atoms when p is 1, and is a (p+1)-valent hydrocarbon group having 1 to 20 carbon atoms when p is 2 or 3, and these hydrocarbylene groups and (p+1)-valent hydrocarbon groups may contain at least one atom selected from oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. X3 is a single bond or an ether bond. Ar1 is each independently a (m+n+1)-valent group derived from benzene or naphthalene, provided that at least one of the n's in the formula is 1 or greater.)

[0069] In the general formula (a1), n ​​is an integer of 0 to 5, preferably 1 or 2 from the viewpoint of film-forming properties, and preferably 1 from the viewpoint of easy availability of raw materials. Furthermore, p is an integer of 1 to 3, preferably 1 or 2 from the viewpoint of ease of production. m is an integer of 0 to 4, preferably 0 from the viewpoint of versatility of raw materials, that is, m is 0, i.e., the substituent on the aromatic ring is hydrogen.

[0070] In the general formula (a1), R1 is a hydrogen atom or a methyl group, and R2 is a hydrocarbyl group having 1 to 6 carbon atoms, a hydrocarbyloxy group having 1 to 12 carbon atoms, a hydrocarbyloxycarbonyl group having 2 to 6 carbon atoms, a hydrocarbylcarbonyloxy group having 2 to 12 carbon atoms, a hydroxy group, a carboxy group, a halogen atom, a trifluoromethoxy group, a cyano group, or a nitro group.

[0071] In the above general formula (a1), X1 is a single bond, an ester bond, an ether bond, an amide bond, or a phenylene group; when p is 1, X2 is a single bond or a hydrocarbylene group having 1 to 20 carbon atoms; when p is 2 or 3, X2 is a (p+1)-valent hydrocarbon group having 1 to 20 carbon atoms; these hydrocarbylene groups and (p+1)-valent hydrocarbon groups may contain at least one atom selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a halogen atom; and X3 is a single bond or an ether bond.

[0072] The hydrocarbylene group represented by X2 may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include a methanediyl group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, a nonane-1,9-diyl group, a decane-1,10-diyl group, an undecane-1,11-diyl group, and a dodecane-1,12-diyl group. Examples of such a hydrocarbon group include alkanediyl groups having 1 to 20 carbon atoms; cyclic saturated hydrocarbylene groups having 3 to 20 carbon atoms, such as cyclopentanediyl, cyclohexanediyl, norbornanediyl, and adamantanediyl; unsaturated aliphatic hydrocarbylene groups having 2 to 20 carbon atoms, such as vinylene and propene-1,3-diyl; arylene groups having 6 to 20 carbon atoms, such as phenylene and naphthylene; and groups obtained by combining these. The (p+1)-valent hydrocarbon group having 1 to 20 carbon atoms, represented by X2, may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include groups obtained by further removing one or two hydrogen atoms from the aforementioned hydrocarbylene group, and groups obtained by substituting one or two hydrogen atoms of the aforementioned hydrocarbylene group with a hydrocarbylene group.

[0073] At least one of X1 and X2 is preferably not a single bond.

[0074] The repeating unit (a2) represented by general formula (a2) is shown below. [ka] (In the above formula, n and m are the same as defined above, l is an integer of 0 to 3, and at least one of the two n's and two l's in the formula is 1 or greater. R2 and X3 are the same as defined above, and R3 is the following general formula (a2-1). Ar2's are each independently an (n+m+l+2)-valent aromatic hydrocarbon group having 6 to 30 carbon atoms. Ar3 is an (n+m+l+1)-valent group derived from benzene or naphthalene.)

[0075] In the above general formula (a2), n is an integer of 0 to 5, m is an integer of 0 to 4, and l is an integer of 0 to 3, and at least one of the two n's and two l's in the formula is 1 or greater. R2 and X3 are the same as above, and R3 is represented by the following general formula (a2-1). Ar2 each independently represents an (n+m+l+2)-valent aromatic hydrocarbon group having 6 to 30 carbon atoms, and the (n+m+l+2)-valent aromatic hydrocarbon group having 6 to 30 carbon atoms is preferably derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, fluorene, biphenyl, diphenylmethane, trisphenyl, fluorenebisphenol, fluorenebisnaphthol, etc., and may have a substituted or unsubstituted hydroxy group or a saturated hydrocarbyl group having 1 to 12 carbon atoms, to which a benzene or naphthalene having a substituted or unsubstituted hydroxy group may be bonded. Ar3 is an (n+m+l+1)-valent group derived from benzene or naphthalene.

[0076] R3 is the following general formula (a2-1). [ka] (In the above formula, X3 and n are the same as defined above, X4 is a single bond or a hydrocarbylene group having 1 to 12 carbon atoms, and the hydrocarbylene group may have at least one of a hydroxy group, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, an ether bond, an ester bond, and an amide bond. Ar4 is an (n+1)-valent group derived from benzene or naphthalene.)

[0077] The repeating unit (a3) ​​represented by general formula (a3) ​​is shown below. [ka] (In the above formula, n, m, l, Ar2, R2, R3, and X3 are the same as defined above, and R4 is a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms, and the hydrocarbyl group may contain an oxygen atom. However, it does not contain a substituent containing SF5. Also, at least one of n and l in the formula is 1 or greater.)

[0078] The repeating unit (a4) represented by general formula (a4) is shown below. [ka] (wherein R3 and R4 are the same as above.)

[0079] It is more preferable that the number of substituents on the aromatic ring containing SF5 in the repeating units (a1) to (a4) is n=1 from the viewpoint of controlling film-forming properties and ease of obtaining raw materials.

[0080] The polymer is preferably a polymer containing at least one repeating unit selected from the repeating units (a1) (hereinafter also referred to as polymer (a1)).

[0081] Examples of monomers that give polymers having an aromatic group with a pentafluorosulfanyl group as a substituent, which give the repeating unit (a1), include, but are not limited to, the following: In the following formula, R1 is the same as defined above.

[0082] [ka]

[0083] [ka]

[0084] [ka]

[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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[0095] [ka]

[0096] [ka]

[0097] [ka]

[0098] The polymer (a1) preferably further contains a repeating unit (b1) having a hydrophilic group. By containing the highly water-repellent repeating unit (a1) having a fluorine atom and the repeating unit (b1) having a hydrophilic group, the polymer (a1) can sufficiently improve film-forming properties.

[0099] The repeating unit (b1) has a hydrophilic group selected from an ether bond, an ester bond, a hydroxy group, a carboxy group, a sulfonamide bond, a sulfonimide bond, a sulfo group, a lactone ring, a sultone ring, a carbonate bond, a urethane bond, and an amide bond.

[0100] Specific examples of the monomer that provides the repeating unit (b1) include, but are not limited to, the following.

[0101] [ka]

[0102] [ka]

[0103] [ka]

[0104] [ka]

[0105] [ka]

[0106] [ka]

[0107] [ka]

[0108] [ka]

[0109] [ka]

[0110] [ka]

[0111] [ka]

[0112] [ka] (wherein R1 is a hydrogen atom or a methyl group).

[0113] The polymer (a1) preferably further contains a repeating unit (c1) having a fluorinated aromatic group, or a repeating unit (c2) having a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethylthio group, or a difluoromethylthio group. By containing the highly water-repellent repeating unit (a1) having a fluorine atom and the highly water-repellent repeating units (c1) and / or (c2), the water repellency and alkali solubility can be further improved.

[0114] Specific examples of the monomer that provides the repeating unit (c1) include, but are not limited to, the following.

[0115] [ka]

[0116] [ka]

[0117] [ka]

[0118] [ka]

[0119] [ka]

[0120] [ka]

[0121] [ka]

[0122] [ka]

[0123] [ka]

[0124] [ka]

[0125] [ka]

[0126] [ka]

[0127] [ka]

[0128] [ka]

[0129] [ka]

[0130] [ka]

[0131] [ka]

[0132] [ka] (wherein R1 is a hydrogen atom or a methyl group).

[0133] Examples of monomers having a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethylthio group, or a difluoromethylthio group that provide the repeating unit c2 include, but are not limited to, those shown below.

[0134] [ka]

[0135] [ka]

[0136] [ka]

[0137] [ka]

[0138] [ka]

[0139] [ka]

[0140] [ka]

[0141] [ka]

[0142] [ka]

[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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[0148]

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[0149]

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[0150]

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[0151]

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[0152]

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[0153]

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[0154]

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[0155]

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[0156]

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[0157]

change

[0158]

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[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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[0166]

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[0167]

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[0168]

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[0169]

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[0170]

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[0171]

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[0172]

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[0173]

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[0174]

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[0175] [Chemical formula]

[0176] [Chemical formula]

[0177] [Chemical formula]

[0178] [Chemical formula]

[0179] [Chemical formula] (In the formula, R1 is a hydrogen atom or a methyl group.)

[0180] The polymer (a1) can further copolymerize with the repeating unit X (repeating units x1 and x2) used in the polymer for resist shown below. Details of the repeating unit X are shown in the description of the resist.

[0181] In the polymer (a1), the content ratios of the repeating units (a1), (b1), (c1), and (c2) are preferably 0 < a1 ≤ 1.0 and 0 ≤ b1 < 1.0, 0 ≤ c1 < 1.0, 0 ≤ c2 < 1.0, more preferably 0.1 ≤ a1 ≤ 0.9 and 0.1 ≤ b1 ≤ 0.9, 0.1 ≤ c1 ≤ 0.9, 0.1 ≤ c2 ≤ 0.9, and even more preferably 0.2 ≤ a1 ≤ 0.8 and 0.2 ≤ b1 ≤ 0.8, 0.2 ≤ c1 ≤ 0.8, 0.2 ≤ c2 ≤ 0.8. However, a1 + b1 + c1 + c2 = 1.0.

[0182] The polymer (a1) preferably has a weight-average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) using THF as a solvent of 1,000 to 500,000, more preferably 2,000 to 30,000. Furthermore, if the molecular weight distribution (Mw / Mn) of the polymer (a1) is broad, the presence of low-molecular-weight and high-molecular-weight polymers may result in the appearance of foreign matter on the pattern after exposure or deterioration of the pattern shape. As the pattern rule becomes finer, the effects of Mw and Mw / Mn tend to become greater. Therefore, to obtain a resist material suitable for fine pattern dimensions, the Mw / Mn of the polymer (a1) is preferably narrowly distributed, i.e., 1.0 to 4.0, particularly 1.0 to 3.0. Because of concerns about reduced surfactant effect due to low-molecular-weight components and reduced solubility due to the inclusion of ultrahigh-molecular-weight components, which may result in deterioration of hump characteristics, it is preferable to narrow the dispersity within a range that does not include large amounts of these components.

[0183] The polymer (a1) may contain two or more polymers having different composition ratios, Mw, or Mw / Mn, or may be a blend of polymers containing different repeating units (a1) and (b1), (c1), or (c2).

[0184] The polymer (a1) can be obtained by polymerizing a monomer that provides the repeating unit (a1) and a repeating unit selected from (b1), (c1), and (c2) by a method such as radical polymerization, anionic polymerization, or cationic polymerization.

[0185] When polymer (a1) contains two or more types of repeating units, it may be a random copolymer or a block copolymer, but block copolymers are characterized by their stronger surfactant effects. Block copolymers containing repeating units (a1) and (b1), (c1), and (c2) are particularly preferred. The block copolymer may be a diblock copolymer consisting of two units, a triblock copolymer consisting of three units, or a tetrablock copolymer consisting of four units.

[0186] Random copolymerization by radical polymerization typically involves mixing copolymerizing monomers and a radical initiator and then heating the mixture. If the first monomer is polymerized in the presence of a radical initiator and then a second monomer is added, the resulting polymer molecule will have a block of the first monomer polymerized on one side and a block of the second monomer polymerized on the other. However, in this case, the repeating units derived from both the first and second monomers are mixed in the middle, resulting in a different structure from a block copolymer. Living radical polymerization is preferred for forming block copolymers by radical polymerization. In a living radical polymerization method called reversible addition fragmentation chain transfer (RAFT) polymerization, radicals at the polymer end are always alive. By initiating polymerization with the first monomer and then adding the second monomer once the first monomer is consumed, block copolymers consisting of the first and second repeating units can be formed. Initiating polymerization with the first monomer, then adding the second monomer once the first monomer is consumed, followed by the addition of a third monomer, can form triblock copolymers. RAFT polymerization is also characterized by the formation of narrow-dispersity polymers.

[0187] Examples of organic solvents used during polymerization include toluene, benzene, tetrahydrofuran (THF), diethyl ether, and dioxane. Examples of polymerization initiators include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2-azobis(2-methylpropionate), benzoyl peroxide, and lauroyl peroxide. The polymerization temperature is preferably 50 to 80°C. The reaction time is preferably 2 to 100 hours, and more preferably 5 to 20 hours.

[0188] RAFT polymerization requires a chain transfer agent, examples of which include 2-cyano-2-propyl benzothioate, 4-cyano-4-phenylcarbonothioylthiopentanoic acid, 2-cyano-2-propyl dodecyl trithiocarbonate, 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid, 2-(dodecylthiocarbonothioylthio)-2-methylpropanoic acid, cyanomethyl dodecyl thiocarbonate, cyanomethyl N-methyl-N-phenylcarbamothioate, bis(thiobenzoyl)disulfide, and bis(dodecylsulfanylthiocarbonyl)disulfide. Of these, 2-cyano-2-propyl benzothioate is most preferred.

[0189] When RAFT polymerization is performed by adding the monomers all at once, narrowly dispersed polymers can be synthesized.

[0190] When the polymer contains at least one repeating unit selected from the repeating units (a2) and (a3), the polymer is a so-called novolak resin (hereinafter also referred to as polymer (a2-a3)). The polymer (a2-a3) can be obtained by a polycondensation reaction between a phenol compound and an aldehyde compound. At least one of the phenol compound and the aldehyde compound has a pentafluorosulfanyl group as a substituent on the aromatic ring.

[0191] The phenol compound is a compound having a hydroxy group bonded to an aromatic ring, and examples thereof include phenol, cresol, naphthol, dihydroxynaphthalene, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(6-hydroxynaphthyl)fluorene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxyphenyl)adamantane, 4,4',4''-trihydroxytriphenylmethane, and 9-hydroxy-9-phenylfluorene.

[0192] Examples of the aldehyde compound include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural, etc. Among these, formaldehyde is particularly preferred. These aldehyde compounds can be used singly or in combination of two or more.

[0193] At least one of the phenol compound and the aldehyde compound has a pentafluorosulfanyl group as a substituent on the aromatic ring. Examples of compounds having these groups include the following.

[0194] Examples of the aldehyde compound having a pentafluorosulfanyl group include the following.

[0195] [ka]

[0196] [ka]

[0197] Examples of phenol compounds having a pentafluorosulfanyl group include the following.

[0198] [ka]

[0199] The phenol compounds can be used alone or in combination of two or more, and the aldehyde compounds can be used alone or in combination of two or more. The amount of the aldehyde compound used is preferably 0.2 to 5 mol, more preferably 0.5 to 2 mol, per 1 mol of the phenol compound.

[0200] A catalyst can also be used in the polycondensation reaction of a phenol compound with an aldehyde. Examples of the catalyst include acid catalysts such as hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, methanesulfonic acid, camphorsulfonic acid, tosylic acid, and trifluoromethanesulfonic acid. The amount of these acid catalysts used is 1 × 10 per mole of the phenol compound. -5 ~5×10 -1 Molar is preferred.

[0201] The reaction solvent for polycondensation may be water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, or a mixture thereof. These solvents are preferably used in an amount of 0 to 2000 parts by mass per 100 parts by mass of the raw materials. The reaction temperature may be appropriately selected depending on the reactivity of the raw materials, but is usually in the range of 10 to 200°C.

[0202] The polycondensation reaction can be carried out by charging the phenol compound, aldehyde compound, and catalyst all at once, or by adding the phenol compound and aldehyde compound dropwise in the presence of a catalyst. After the polycondensation reaction is complete, the temperature of the reaction vessel is raised to 130 to 230°C, and volatile matter can be removed at a pressure of about 1 to 50 mmHg to remove unreacted raw materials, catalyst, etc., remaining in the system.

[0203] Examples of the substituent represented by R3 in the polymer include the following.

[0204] [ka]

[0205] [ka]

[0206] Another method for introducing the above-mentioned substituent R3 is to obtain an intermediate polymer from a phenolic compound and an aldehyde compound using the method described above, and then introduce (modify) R3. For example, in the case of repeating unit (a2), it can be synthesized by condensing a compound (phenolic compound) represented by a circle Ar2 having a phenolic hydroxyl group on the aromatic ring with a compound (aldehyde compound) represented by Ar3 having a phenolic hydroxyl group on the aromatic ring, followed by esterification or etherification of the phenolic hydroxyl group. Similarly, in the case of repeating unit (a3), the above-mentioned phenolic compound can be condensed with an aldehyde compound corresponding to R4, followed by modification of the phenolic hydroxyl group to obtain polymer (a2-a3).

[0207] 1. Case (a2) [ka]

[0208] 2.In the case of (a3) [ka]

[0209] Examples of the aldehyde component having a phenolic hydroxyl group used in the above reaction include the following. Examples of the aldehyde having a substituent represented by R4 include those exemplified as the aldehyde compounds used to obtain the polymer (a2-a3).

[0210] [ka]

[0211] Examples of the compound having a phenolic hydroxyl group used in the above reaction include the compounds listed as the phenol compounds used to obtain the polymer (a2-a3), but more specific examples include the following.

[0212] [ka]

[0213] When etherifying in the above reaction, it can be synthesized by reacting with a halide, mesylate, or tosylate corresponding to R3.

[0214] Etherification can be easily achieved by known methods. Specifically, it can be obtained by reaction with a halide, mesylate, or tosylate corresponding to the partial structure of R3. Preferably, ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; aromatic solvents such as benzene, toluene, and xylene; acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, and water are used alone or in combination to react the polymer obtained in STEP 1 with a halide, mesylate, or tosylate corresponding to the partial structure of R3. A base catalyst such as sodium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, potassium phosphate, triethylamine, pyridine, or N-methylmorpholine is added sequentially or simultaneously, and the mixture is cooled or heated as necessary. The resulting reaction product can be purified, for example, by washing with water, and recovered as a powder or solution.

[0215] When esterifying by the above reaction, synthesis can be carried out by reacting with an acid chloride or acid anhydride corresponding to R3.

[0216] Esterification can be easily carried out by known methods. Specifically, it is preferable to use an acid chloride or acid anhydride corresponding to the partial structure of R3. When an acid chloride is used, it is preferable to carry out the reaction without a solvent or in a solvent such as methylene chloride, acetonitrile, toluene, or hexane by sequentially or simultaneously adding the polymer obtained in STEP 1, the acid chloride, and a base such as triethylamine, pyridine, or 4-dimethylaminopyridine, and cooling or heating as necessary. When an acid anhydride is used, it is preferable to carry out the reaction by sequentially or simultaneously adding the polymer obtained in STEP 1 and a base such as triethylamine, pyridine, or 4-dimethylaminopyridine, and cooling or heating as necessary. The resulting reaction product can be purified, such as by washing with water, and recovered as a powder or solution.

[0217] When the above production method is used, the modification rate of the substituent R3 in the repeating units of the polymer can be controlled to any ratio, and where c1 is the ratio of modified hydroxyl groups R3 in all repeating units and c2 is the ratio of unmodified hydroxyl groups, 0≦c1≦1.0 and 0≦c2≦1.0 are preferred, 0.1≦c1≦0.9 and 0.1≦c2≦0.9 are more preferred, and 0.2≦c1≦0.8 and 0.2≦c2≦0.8 are even more preferred, provided that c1+c2=1.0.

[0218] The polymer (a2-a3) preferably has a weight-average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) using THF as a solvent of 1,000 to 500,000, more preferably 1,500 to 30,000. Furthermore, if the polymer (a2-a3) has a broad molecular weight distribution (Mw / Mn), the presence of low-molecular-weight and high-molecular-weight polymers may lead to the occurrence of sublimates due to low molecular weights or foreign matter due to high molecular weights during film formation, such as foreign matter appearing on the pattern after exposure, or deterioration of the pattern shape. To ensure highly accurate control of in-plane film uniformity and film formability on substrates with complex shapes, the Mw / Mn of the polymer (a2-a3) is preferably a narrow distribution of 1.0 to 5.0, particularly 1.5 to 3.5.

[0219] The polymer (a2-a3) may contain two or more polymers having different composition ratios, Mw, or Mw / Mn.

[0220] When the polymer has the repeating unit (a4), the polymer is a ring-opening polymer of an oxetane compound (hereinafter also referred to as polymer (a4)). The polymer (a4) can be obtained by ring-opening polymerization of an oxetane compound, and the substituent represented by R3 of the oxetane compound has at least one pentasulfenyl group as a substituent on the aromatic ring.

[0221] Examples of the oxetane compound include the following: R3 is the same as above.

[0222] [ka]

[0223] The polymer having the repeating unit (a4) can be synthesized by using an oxetane compound as a monomer and subjecting the oxetane compound to ring-opening polymerization using a hydroxyl group-containing compound as an initiator in the presence or absence of a catalyst and a solvent.

[0224] Examples of initiators include 3-ethyl-3-(2-hydroxyethyl)oxymethyloxetane, 3-ethyl-3-(3-hydroxypropyl)oxymethyloxetane, 3-ethyl-3-(4-hydroxybutyl)oxymethyloxetane, 3-ethyl-3-(5-hydroxypentyl)oxymethyloxetane, 3-ethyl-3-(2-hydroxyethyloxyethyl)oxymethyloxetane, 3-ethyl-3-(2,3-dihydroxypropyl)oxymethyloxetane, and 3-ethyl-3-hydroxy-poly(ethyleneoxy). Examples of suitable initiators include alcohol group-containing oxetane compounds such as methyloxetane and 3-ethyl-3-hydroxy-poly(propyleneoxy)methyloxetane; alcohol compounds such as methanol, ethanol, propanol, and butanol; and diol compounds such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, diethylene glycol, triethylene glycol, and tetraethylene glycol. Diol compounds are preferred from the viewpoint of molecular weight control. The amount of these initiators used is, for example, 0.1 to 100 mol, preferably 0.5 to 100 mol, and particularly preferably 1 to 100 mol, per 100 mol of the oxetane compound. The molecular weight of the resulting polymer can be controlled by controlling the molar ratio of the oxetane compound to the initiator.

[0225] Examples of catalysts include Lewis acid catalysts, such as boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, zinc chloride, aluminum bromide, and other complexes. Among these, the preferred catalyst is BF3·THF complex, which is preferable from the viewpoint of raw material handling. The catalyst and initiator are preferably mixed in a solvent for 5 to 10 minutes before the addition of the monomer, with the catalyst / initiator ratio ranging from 1:1 to 1:5 mol / mol, preferably 1:1 to 1:2 mol / mol.

[0226] The ring-opening reaction can be carried out without a solvent, but when a solvent is used, there are no particular limitations as long as the solvent is inert to the catalyst used in the reaction and the oxetane compound as a monomer, and examples of the solvent include methylene chloride, carbon tetrachloride, chloroform, trichloroethylene, chlorobenzene, ethyl bromide, dichloroethane, sulfur dioxide, hexane, petroleum ether, toluene, dioxane, xylene, etc. These solvents can be used alone or in combination, and are preferably used in an amount of 0 to 2000 parts by mass per 100 parts by mass of the monomer.

[0227] Ring-opening polymerization can be easily carried out by known methods. However, it is preferable to mix the catalyst and initiator in a solvent before adding one or more oxetane compounds as monomers, and then slowly add the monomers over time while controlling the heat generation to carry out the reaction. After the reaction is complete, the reaction is quenched using water or the like, and the catalyst is removed by separation and washing, and the polymer can be recovered by crystallization in a poor solvent or by vacuum distillation of unreacted monomers. The reaction temperature is preferably -20°C to 60°C, more preferably 0°C to 40°C. The monomer to catalyst charging ratio is preferably 10:1 to 300:1, more preferably 50:1 to 100:1 monomer / catalyst.

[0228] The polymer (a4) preferably has a weight-average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) using THF as a solvent of 1,000 to 500,000, more preferably 1,500 to 30,000. Furthermore, if the polymer (a4) has a broad molecular weight distribution (Mw / Mn), coating performance may be impaired due to sublimates resulting from low molecular weight components or foreign matter resulting from high molecular weight components during film formation. Therefore, the influence of Mw and Mw / Mn tends to be significant. Therefore, when used as a high-precision film-forming material, the polymer (a4) preferably has a narrow Mw / Mn distribution of 1.0 to 5.0, particularly 1.5 to 3.5.

[0229] The polymer (a4) may contain two or more polymers having different composition ratios, Mw, and Mw / Mn.

[0230] Materials used in semiconductor photolithography, including the polymers (a1), (a2-a3), and (a4), must have reduced metal impurities, since the presence of metal impurities adversely affects the operation of devices fabricated 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.

[0231] The film-forming composition of the present invention preferably contains 0.0001 to 3 mass% of the polymer (a). The content of the polymer is preferably 0.0001 to 2 mass%, more preferably 0.0002 to 1 mass%. In this case, the polymer (a) serves as a surfactant for imparting film-forming properties. By using the polymer (a) in combination with an organic compound or the like as a surfactant, it is possible to impart high film-forming properties due to the effects of the interaction between fluorine atoms resulting from SF5 introduced into the repeating unit and the interaction with the aromatic ring.

[0232] The film-forming composition can be used as a component of a photosensitive or non-photosensitive resist material, a material for forming a top coat formed on a resist film, a material for forming a resist underlayer film, etc. Underlayer film materials can be used not only for organic underlayer films using organic compounds or resins, but also for film-forming materials containing metal elements such as silicon, titanium, zirconium, tin, and hafnium. For example, resist materials can 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 underlayer 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 underlayer 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 a surfactant during film formation.

[0233] [Monomer] The present invention also provides a monomer represented by the following general formula (a5): [ka] (In the formula, R x is a hydrogen atom or a methyl group, and X a is a linking group having 1 to 12 carbon atoms which is a single bond, a phenylene group, a naphthylene group, or an ester bond, an ether bond, or a lactone ring, and may have an oxygen atom, a nitrogen atom, a sulfur atom, and / or a halogen atom; La is an acid labile group which has an aromatic group having at least one pentafluorosulfanyl group as a substituent.

[0234] The monomer of the present invention is preferably represented by the following general formula (a6). [ka] (In the formula, X a , R x As mentioned above. R 11 , R 12 are each independently a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkenyl group having 2 to 12 carbon atoms, a linear, branched, or cyclic alkynyl group having 2 to 12 carbon atoms, or an aryl group having 5 to 10 carbon atoms, which may have an oxygen atom and / or a sulfur atom; R 11 and R 12 may be bonded to form a ring. 13 are each independently a hydrogen atom, a halogen atom, or an alkyl or alkoxy group having 1 to 4 carbon atoms. m is an integer of 0 to 4, and n is an integer of 1 to 3.

[0235] Specific examples of the monomer represented by general formula (a6) include the following.

[0236] [ka]

[0237] Monomers such as those described above are expected to be used in a variety of industries as raw materials for next-generation environmentally friendly materials that comply with PFAS regulations.

[0238] [Polymer] The present invention also provides a polymer that contains a repeating unit represented by the following general formula (a7) and has a weight-average molecular weight in the range of 100 to 500,000. [ka] (In the formula, R x is a hydrogen atom or a methyl group, and X ais a linking group having 1 to 12 carbon atoms which is a single bond, a phenylene group, a naphthylene group, or an ester bond, an ether bond, or a lactone ring, and may have an oxygen atom, a nitrogen atom, a sulfur atom, and / or a halogen atom; La is an acid labile group which has an aromatic group having at least one pentafluorosulfanyl group as a substituent.

[0239] The polymer of the present invention preferably contains a repeating unit represented by the following general formula (a8) and has a weight average molecular weight in the range of 100 to 500,000. [ka] (In the formula, X a , R x As mentioned above. R 11 , R 12 are each independently a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkenyl group having 2 to 12 carbon atoms, a linear, branched, or cyclic alkynyl group having 2 to 12 carbon atoms, or an aryl group having 5 to 10 carbon atoms, which may have an oxygen atom and / or a sulfur atom; R 11 and R 12 may be bonded to form a ring. 13 are each independently a hydrogen atom, a halogen atom, or an alkyl or alkoxy group having 1 to 4 carbon atoms. m is an integer of 0 to 4, and n is an integer of 1 to 3.

[0240] Polymers such as those described above are not subject to PFAS regulations and are promising candidates to replace conventional polymers that incorporate fluorine substituents.

[0241] [Composition for organic film formation] The organic film-forming composition contains (A) an organic film-forming resin or compound, (B) a polymer (a), and (C) a solvent.

[0242] In the organic film-forming composition of the present invention, the (B) polymer (a), the (A) organic film-forming resin or compound, and the (C) solvent can each be used alone or in combination of two or more. The polymer (a) in the present invention functions as a surfactant that imparts excellent film-forming properties and high leveling performance. Its applications are not limited to organic underlayer films, but can be used in general photolithography coating materials, such as photosensitive resist materials and materials for forming top coats formed on resist films. Furthermore, it can be applied not only to organic film-forming materials but also to silicon-containing resist underlayer films, and can be used as a surfactant suitable for achieving highly versatile film-forming properties that can be applied to various film-forming materials.

[0243] In the present invention, when the polymer (a) is used as a surfactant, one type may be used alone or two or more types may be used in combination. The amount of the polymer (a) added is 0.01 to 5 parts by mass per 100 parts by mass of the (A) organic film-forming resin or compound.

[0244] [(A) Organic film-forming resin or compound (organic underlayer film)] The (A) organic film-forming resin or compound 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.

[0245] 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.

[0246] Examples of the organic film-forming resin or compound (A) used in the present invention include resins containing the following structures described in JP-A Nos. 2012-001687 and 2012-077295.

[0247] [ka] (In formula (1), the ring structures Ar1 and Ar2 represent a benzene ring or a naphthalene ring. X represents a single bond or an alkylene group having 1 to 20 carbon atoms. m represents 0 or 1. n represents any natural number such that the molecular weight is 100,000 or less. Note that the symbols in the formula apply only within this formula.)

[0248] [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.)

[0249] Further examples of the (A) organic film-forming resin or compound used in the present invention include resins containing the following structures described in JP-A Nos. 2004-264710, 2005-043471, 2005-250434, 2007-293294, and 2008-065303.

[0250] [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.

[0251] [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.)

[0252] [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 formula apply only within this formula.

[0253] [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.)

[0254] Specific examples of the organic film-forming resin or compound (A) used in the present invention include resins containing the following structures described in JP-A Nos. 2004-205685, 2007-171895, and 2009-014816.

[0255] [ka] (In formula (8) and formula (9), R 1 ~R 8 are each independently a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group having 1 to 6 carbon atoms, an optionally substituted alkoxy group having 1 to 6 carbon atoms, an optionally substituted alkoxycarboxyl group having 2 to 6 carbon atoms, an optionally substituted aryl group having 6 to 10 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, an isocyanate group, or a glycidyl group. m and n are positive integers. Note that the symbols in the formula apply only within this formula.

[0256] [ka] (In formula (10), R 1 , R 6 is a hydrogen atom or a methyl group. 2 , R 3 , R 4 is a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, an acetoxy group, or an alkoxycarbonyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and R 5 is a condensed polycyclic hydrocarbon group having 13 to 30 carbon atoms, -OR 7 , -C(=O)-OR 7 , -OC(=O)-R 7 or -C(=O)-NR 8 -R 7 where m is 1 or 2, n is an integer of 0 to 4, and p is an integer of 0 to 6. 7 is an organic group with 7 to 30 carbon atoms, R 8is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Z is any one of a methylene group, -O-, -S-, and -NH-. a, b, c, d, and e are within the ranges of 0 < a < 1.0, 0 ≦ b ≦ 0.8, 0 ≦ c ≦ 0.8, 0 ≦ d ≦ 0.8, 0 ≦ e ≦ 0.8, and 0 < b + c + d + e < 1.0. In addition, the symbols in the formula are applicable only within this formula.)

[0257]

Chemical formula

[0258] Examples of formula (11) include the following resins.

[0259]

Chemical formula

[0260]

Chemical formula

[0261] Examples of the organic film-forming resin or compound (A) used in the present invention include resins containing the following structures described in JP-A Nos. 2007-199653, 2008-274250, and 2010-122656.

[0262] [ka] (In formula (12), R 1 and R 2 are independently the same or different hydrogen atoms, linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, or alkenyl groups having 2 to 10 carbon atoms, and R 3 is a single bond or an alkylene group having a linear, branched or cyclic structure and having 1 to 30 carbon atoms, which may have a bridged cyclic hydrocarbon group, a double bond, a heteroatom or an aromatic group having 6 to 30 carbon atoms; R 4 and R 5 are each independently a hydrogen atom or a glycidyl group, and n is an integer of 1 to 4. The symbols in the formula are applicable only within this formula.

[0263] [ka] (In formula (13), R 1 and R 2 are independently the same or different hydrogen atoms, linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, or alkenyl groups having 2 to 10 carbon atoms, and R 3 is a single bond or an alkylene group having a linear, branched or cyclic structure and having 1 to 30 carbon atoms, which may have a bridged cyclic hydrocarbon group, a double bond, a heteroatom or an aromatic group having 6 to 30 carbon atoms; R 4 and R 5 are each independently a hydrogen atom or a glycidyl group, and R 6 is a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms. The symbols in the formula are only applicable within this formula.

[0264] [Chemical formula] (In formula (14), ring Z 1 and ring Z 2 are fused polycyclic aromatic hydrocarbon rings, R 1a , R 1b , R 2a , and R 2b represent the same or different substituents. k1 and k2 represent the same or different integers of 0 or 1 to 4, m1 and m2 each represent an integer of 0 or 1 or more, and n1 and n2 each represent an integer of 0 or 1 or more. However, n1 + n2 ≥ 1. Note that the symbols in the formula are applicable only within this formula.)

[0265] [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, R 5 is a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms, R 6 , R 7 are benzene rings or naphthalene rings. p and q are each 1 or 2. 0 < n ≤ 1. Note that the symbols in the formula are applicable only within this formula.)

[0266] As formula (15), for example, the following resins are exemplified.

[0267] [Chemical formula] <00(01639>

[0268] [Chemical formula]

[0269] [Chemical formula]

[0270] [ka]

[0271] Examples of the organic film-forming resin or compound (A) used in the present invention include resins containing the following structure described in JP-A No. 2012-214720.

[0272] [ka] (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.)

[0273] Examples of the (A) organic film-forming resin or compound used in the present invention include resins described in JP-A-2014-29435.

[0274] [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.)

[0275] Furthermore, examples of the organic film-forming resin or compound (A) used in the present invention include polymers containing a unit structure represented by the following formula (18) and a unit structure represented by the following formula (19) described in WO 2012 / 077640, in which the molar ratio of the unit structure represented by formula (18) to the unit structure represented by formula (19) is 3 to 97:97 to 3.

[0276] [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.

[0277] [ka] In formula (19), Ar represents an aromatic ring group having 6 to 20 carbon atoms, R6 represents a hydroxy group, R7 represents a hydrogen atom, a halogen atom, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination of these groups which may contain an ether bond, a ketone bond, or an ester bond, and R8 may be substituted with a hydrogen atom, a halogen atom, a nitro group, an amino group, or a hydroxy group. R8 represents an aryl group or heterocyclic group having 6 to 40 carbon atoms, R9 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, a nitro group, an amino group, or a hydroxy group, or an aryl group or heterocyclic group having 6 to 40 carbon atoms, and R8 and R9 may together form a ring. n6 represents an integer of 1 to p, and n7 represents an integer of p-n6, where p represents the maximum number of substituents that can be substituted on the aromatic ring group Ar. The symbols in the formula are only applicable within this formula.

[0278] Examples of the organic film-forming resin or compound (A) used in the present invention include polymers containing a unit structure represented by the following formula (20) described in WO 2010 / 147155.

[0279] [ka] (In formula (20), R1 and R2 are each selected from the group consisting of a hydrogen atom, a halogen group, a nitro group, an amino group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group, or the aryl group represents a group which may contain an ether bond, a ketone bond, or an ester bond; R3 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and combinations thereof, and the alkyl group, the alkenyl group Alternatively, the aryl group represents a group which may contain an ether bond, a ketone bond, or an ester bond; R4 represents an aryl group or heterocyclic group having 6 to 40 carbon atoms which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxy group; R5 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an aryl group or a heterocyclic group having 6 to 40 carbon atoms which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxy group; R4 and R5 may form a ring together with the carbon atoms to which they are bonded; and n1 and n2 are each an integer of 1 to 3. Note that the symbols in the formula apply only within this formula.

[0280] Examples of the (A) organic film-forming resin or compound used in the present invention include novolak resins obtained by reacting one or more phenols, such as phenol, cresol, xylenol, catechol, resorcinol, hydroquinone, pyrogallol, hydroxyquinol, and phloroglucinol, with one or more aldehyde sources, such as formaldehyde, paraformaldehyde, and trioxane, using an acidic catalyst; and resins containing a repeating unit structure represented by the following formula (21), which are described in WO 2012 / 176767.

[0281] [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.)

[0282] Examples of the organic film-forming resin or compound (A) used in the present invention include novolak resins having a fluorene or tetrahydrospirobiindene structure described in JP-A Nos. 2005-128509, 2006-259249, 2006-259482, 2006-293298, and 2007-316282, and resins containing a repeating unit structure represented by the following formula (22-1) or (22-2):

[0283] [ka] (In formula (22-1) and formula (22-2), R 1 , R 2 , R 6 , R 7 are independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an allyl group, or a halogen atom; R 3 , R 4 , R 8 , R 9 are independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms or a glycidyl group, and R 5 , R 14 are independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. n, m, p and q are integers of 1 to 3. R 10 ~R 13 are independently a hydrogen atom, a halogen atom, a hydroxy group, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms. Note that the symbols in the formula apply only within this formula.)

[0284] The organic film-forming resin or compound (A) used in the present invention can be, for example, a reaction product obtained by the method described in JP 2012-145897 A. More specifically, a polymer obtained by condensing one or more compounds represented by the following general formula (23-1) and / or (23-2) with one or more compounds represented by the following general formula (24-1) and / or (24-2) and / or their equivalents can be exemplified.

[0285] [ka] (In the general formula (23-1) and the general formula (23-2), R 1 ~R 8 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an isocyanato group, a glycidyloxy group, a carboxyl group, an amino group, an alkoxy group having 1 to 30 carbon atoms, an alkoxycarbonyl group having 1 to 30 carbon atoms, an alkanoyloxy group having 1 to 30 carbon atoms, or an optionally substituted saturated or unsaturated organic group having 1 to 30 carbon atoms. 1 ~R 4 or R 5 ~R 8 Two substituents arbitrarily selected from the following may be bonded to form a cyclic substituent. The symbols in the formula are applicable only within this formula.)

[0286] [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.)

[0287] 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.

[0288] [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.)

[0289] Examples of the organic film-forming resin or compound (A) used in the present invention include compounds containing the following structure described in JP-A-2017-119671.

[0290] [ka] (In formula (26-1), R is a single bond or an organic group having 1 to 50 carbon atoms, X is a group represented by the following general formula (26-2), and m1 is an integer satisfying 2≦m1≦10. Note that the symbols in the formula apply only within this formula.) [ka] (In the formula, X 2 is a divalent organic group having 1 to 10 carbon atoms, n1 is 0 or 1, n2 is 1 or 2, and X 3 is a group represented by the following general formula (26-3), and n5 is 0, 1, or 2. The symbols in the formula apply only within this formula. [ka] (In the formula, R 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.

[0291] Examples of compounds containing the above structure include the following compounds.

[0292] [ka]

[0293] Examples of the organic film-forming resin or compound (A) used in the present invention include polymers having a repeating unit represented by the following general formula (27-1) described in JP-A-2019-044022.

[0294] [ka] In formula (27-1), AR1 and AR2 are benzene rings or naphthalene rings which may have a substituent, and R 1 , R 2 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R 1 and R 2 If is an organic group, R 1 and R 2 may form a cyclic organic group by bonding intramolecularly. n is 0 or 1, and when n=0, AR1 and AR2 do not form a bridged structure between the aromatic rings of AR1 and AR2 via Z, and when n=1, AR1 and AR2 form a bridged structure between the aromatic rings of AR1 and AR2 via Z, and Z is either a single bond or the following formula (27-2). Y is a group represented by the following formula (27-3). Note that the symbols in the formula apply only within this formula. [ka] [ka] (In the formula, R 3is a single bond or a divalent organic group having 1 to 20 carbon atoms, and R 4 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and the dashed line represents a bond. Note that the symbols in the formula are only applicable within this formula.

[0295] Examples of polymers having a repeating unit represented by the above general formula (27-1) include the following polymers.

[0296] [ka]

[0297] [ka]

[0298] (A) The organic film-forming resin or compound may be synthesized by a known method, or a commercially available product may be used.

[0299] The amount of the (A) organic film-forming resin or compound is not particularly limited as long as the organic film-forming composition satisfies the film-forming properties of spin coating. Preferably, the amount of the (A) organic film-forming resin or compound is 10 to 40 parts by weight, more preferably 10 to 30 parts by weight, and even more preferably 10 to 25 parts by weight, per 100 parts by weight of the organic film-forming composition. For example, when filling holes or trenches with extremely high aspect ratios in 3D NAND memory architecture with an organic film-forming composition, a large amount of the organic film-forming resin is required. However, such organic film-forming compositions have high viscosity, which can degrade the in-plane uniformity and filling properties after spin coating. Even with the above-mentioned (A) organic film-forming resin blend ratio, the organic film-forming composition of the present invention can be suitably applied because it can form organic films with excellent in-plane uniformity and filling properties.

[0300] Furthermore, the content of the (B) polymer (a) is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the (A) organic film-forming resin or compound. When the organic film-forming composition contains the polymer in such a content, the formed organic film has better in-plane uniformity.

[0301] 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 or compound and the (B) polymer (a), and is preferably one that can also dissolve the acid generator, crosslinking agent, surfactant, etc., which will be described later. Specifically, solvents with a boiling point of less than 180°C, such as those described in paragraphs (0091) and (0092) of JP-A No. 2007-199653, can be used. Among these, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclopentanone, cyclohexanone, and mixtures of two or more of these are preferably used.

[0302] The content of the (C) solvent is 200 to 10,000 parts by mass, more preferably 300 to 5,000 parts by mass, per 100 parts by mass of the (A) organic film-forming resin or compound. By setting the content within this range, the concentration can be adjusted according to the film thickness to be consumed.

[0303] Furthermore, in the organic film-forming material of the present invention, a high-boiling solvent having a boiling point of 180° C. or higher can be added to the above-mentioned solvent having a boiling point of less than 180° C. (a mixture of a solvent having a boiling point of less than 180° C. and a solvent having a boiling point of 180° C. or higher). The high-boiling organic solvent is not particularly limited as long as it can dissolve the organic film-forming compound, and may be any of hydrocarbons, alcohols, ketones, esters, ethers, chlorinated solvents, etc., but specific examples include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-Hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, n-nonyl acetate, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol-n-butyl ether, triethylene glycol butyl methyl ether, triethylene Glycol diacetate, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, propylene glycol diacetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,Examples of the diester include 6-hexanediol diacetate, triethylene glycol diacetate, γ-butyrolactone, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, and dibutyl adipate, and these may be used alone or in combination.

[0304] The boiling point of the high-boiling solvent may be appropriately selected according to the temperature at which the organic film-forming material is heat-treated, and the boiling point of the high-boiling solvent to be added is preferably 180°C to 300°C, and more preferably 200°C to 300°C. Such a boiling point prevents the solvent from volatilizing too quickly during baking (heat treatment) due to a boiling point that is too low, thereby ensuring sufficient thermal fluidity. Furthermore, such a boiling point is so high that the solvent does not remain in the film after baking without volatilizing, and therefore does not adversely affect film properties such as etching resistance.

[0305] 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.

[0306] In such an organic film-forming composition, the addition of a high-boiling point solvent to the (A) organic film-forming resin or compound provides thermal fluidity, thereby making the organic film-forming material have both high filling and planarizing properties.

[0307] [Other ingredients] In addition, an acid generator or crosslinking agent can be added to the organic film-forming composition of the present invention to further promote the crosslinking reaction. Acid generators include those that generate acid upon thermal decomposition ((E) thermal acid generator) and those that generate acid upon light irradiation ((D) photoacid generator), and either can be added. Specific examples of acid generators include those described in paragraphs

[0061] to

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

[0308] Specific examples of crosslinking agents include those described in paragraphs

[0055] to

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

[0309] To further improve the in-plane uniformity during spin coating, a surfactant other than the compound (B) of the present invention may be added to the organic film-forming composition of the present invention. Specific examples of surfactants include those described in paragraphs

[0142] to

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

[0310] 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 a basic compound is added, the amount added is preferably 0.05 to 50 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the (A) organic film-forming resin or compound. This amount can improve the storage stability of the organic film-forming composition.

[0311] 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.

[0312] [Organic film formation method] The present invention provides a method for forming an organic film used in the manufacturing process of a semiconductor device, which comprises spin-coating the above-mentioned film-forming composition of the present invention onto a substrate to be processed, and heat-treating the substrate coated with the 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.

[0313] 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.

[0314] 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.

[0315] [Pattern formation method] A pattern forming method using the organic film-forming composition of the present invention will be described below.

[0316] [Trilayer resist process using silicon-containing resist interlayer] The present invention provides a pattern formation method, which includes forming an organic film on a workpiece using the above-described film-forming composition, forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms, forming a resist upper layer film on the resist intermediate film using a resist upper layer film material consisting of a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the resist intermediate film on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0317] The workpiece is preferably a semiconductor device substrate, or the semiconductor device substrate on which any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal carbide oxide film, and a metal oxynitride film is formed. More specifically, although not particularly limited, substrates such as Si, α-Si, p-Si, SiO, SiN, SiON, W, TiN, and Al, and the substrate on which the above-mentioned metal film or the like is formed as a workpiece layer, can be used.

[0318] 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.

[0319] 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.

[0320] When forming an organic film on a workpiece using the organic film-forming composition of the present invention, the above-described organic film-forming method of the present invention may be applied.

[0321] 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.

[0322] 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.

[0323] 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.

[0324] 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.

[0325] In forming the circuit pattern, it is preferable to develop the circuit pattern using an alkali developer or an organic solvent.

[0326] 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.

[0327] 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.

[0328] 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 by 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 etching with fluorocarbon-based gases, the silicon-containing resist underlayer film pattern is stripped simultaneously with the substrate processing. On the other hand, if the substrate is processed using etching with chlorine- or bromine-based gases, a separate dry etching stripping process using fluorocarbon-based gases is required after substrate processing to strip the silicon-containing resist underlayer film pattern.

[0329] 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.

[0330] [Four-layer resist process using silicon-containing resist interlayer and organic anti-reflective or adhesive coating] The present invention also provides a pattern formation method, which includes forming an organic film on a workpiece using the above-described film-forming composition, forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms, forming an organic antireflective film or an adhesive film on the resist intermediate film, forming a resist upper layer film on the organic antireflective film or adhesive film using a resist upper layer film material comprising a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern 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.

[0331] This method can be performed in the same manner as the three-layer resist process using the silicon-containing resist intermediate film described above, except that an organic antireflective coating (BARC) or an adhesion film is formed between the silicon-containing resist intermediate film and the resist top layer film.

[0332] The organic anti-reflection film and the adhesive film can be formed by spin coating using known organic anti-reflection film materials.

[0333] [Trilayer resist process using inorganic hard mask intermediate film] The present invention also provides a pattern formation method, which includes forming an organic film on a workpiece using the above-mentioned film-forming composition, forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming a resist upper layer film on the inorganic hard mask using a resist upper layer film material 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.

[0334] 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.

[0335] 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.

[0336] [Four-layer resist process using inorganic hard mask intermediate film and organic anti-reflective or adhesive film] The present invention also provides a pattern formation method, which includes forming an organic film on a workpiece using the above-described film-forming composition, forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming an organic antireflective film or an adhesive film on the inorganic hard mask, forming a resist upper layer film on the organic antireflective film or adhesive film using a resist upper layer film material comprising a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the organic antireflective film or adhesive film and the inorganic hard mask by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0337] 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.

[0338] 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.

[0339] An example of a pattern formation method using the three-layer resist process of the present invention is shown in Figures 3(A) to 3(F). In the three-layer resist process, as shown in Figure 3(A), an organic film 3 is formed on a processable layer 2 formed on a substrate 1 using the organic film-forming composition of the present invention, followed by the formation of a silicon-containing resist intermediate film 4, and then a resist upper layer film 5 is formed thereon. Next, as shown in Figure 3(B), the exposed portion 6 of the resist upper layer film 5 is exposed and subjected to PEB (post-exposure bake). Next, as shown in Figure 3(C), development is performed to form a resist upper layer film pattern 5a. Next, as shown in Figure 3(D), using the resist upper layer film pattern 5a as a mask, the silicon-containing resist intermediate film 4 is dry-etched using a fluorocarbon-based gas to form a silicon-containing resist intermediate film pattern 4a. Next, as shown in Figure 3(E), after removing the resist upper layer film pattern 5a, the organic film 3 is oxygen-plasma etched using the silicon-containing resist intermediate film pattern 4a as a mask to form an organic film pattern 3a. 3(F), after removing the silicon-containing resist intermediate film pattern 4a, the workpiece layer 2 is etched using the organic film pattern 3a as a mask to form a pattern 2a. By suppressing the formation of humps during the formation of the organic film, it is possible to reduce defects caused by humps in the organic film during the dry etching process shown in Figures (D), (E), and (F).

[0340] 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.

[0341] As described above, the pattern formation method of the present invention makes it possible to form a fine pattern on a workpiece with high precision by a multilayer resist process, and also to reduce defects resulting from humps in the organic film by suppressing hump formation in the organic film.

[0342] [Organic film-forming composition (resist material)] The organic film-forming composition of the present invention can be used as a resist material.

[0343] When the polymer (a) of the present invention is used as a surfactant, the organic film-forming composition of the present invention may further contain a conventional surfactant. Examples of conventional surfactants include those described in paragraphs

[0165] to

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

[0344] 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.

[0345] 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 (x1) (hereinafter also referred to as repeating unit x1) or a repeating unit represented by the following formula (x2) (hereinafter also referred to as repeating unit x2):

[0346] [ka]

[0347] In formulas (x1) and (x2), 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- groups 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.

[0348] Specific examples of the monomer that provides the repeating unit x1 include, but are not limited to, the following: B and R 11 is the same as above.

[0349] [ka]

[0350] Specific examples of the monomer that provides the repeating unit x2 include, but are not limited to, the following: Band R 12 is the same as above.

[0351] [ka]

[0352] 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.

[0353] Specific examples of the acid labile group include those represented by any of the following formulae (AL-1) to (AL-3).

[0354] [ka] (In the formula, the dashed lines represent bonds.)

[0355] 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.

[0356] In formula (AL-1), c is an integer of 0 to 10, and an integer of 1 to 5 is preferred.

[0357] In formula (AL-2), R L3 and R L4are 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 L4 Any 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.

[0358] 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.

[0359] The base polymer may contain a repeating unit y containing a phenolic hydroxy group as an adhesive group. Specific examples of the monomer that provides the repeating unit y include, but are not limited to, the following. In the following formula, R B is the same as above.

[0360] [ka]

[0361] [ka]

[0362] [ka]

[0363] 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, or a carboxy group. 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.

[0364] [ka]

[0365] [ka]

[0366] [ka]

[0367] [ka]

[0368] [ka]

[0369] [ka]

[0370] [ka]

[0371] [ka]

[0372] [ka]

[0373] 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:

[0374] [ka]

[0375] The base polymer may include repeat units e derived from styrene, vinylnaphthalene, vinylanthracene, vinylpyrene, methyleneindane, vinylpyridine, or vinylcarbazole.

[0376] 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.

[0377] [ka]

[0378] In formulas (f1) to (f3), R B are each independently a hydrogen atom or a methyl group. 1 represents 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.

[0379] In formulas (f1) to (f3), R 21 ~R 28are each independently a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom.

[0380] 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.

[0381] 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.

[0382] 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.

[0383] 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:

[0384] [ka] (In the formula, the dashed lines represent bonds.)

[0385] 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.

[0386] 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.

[0387] [ka]

[0388] 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.

[0389] 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.

[0390] 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.

[0391] [ka]

[0392] 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.

[0393] [ka]

[0394] [ka]

[0395] [ka]

[0396] [ka]

[0397] [ka]

[0398] [ka]

[0399] [ka]

[0400] [ka]

[0401] [ka]

[0402] [ka]

[0403] [ka]

[0404] [ka]

[0405] [ka]

[0406] [ka]

[0407] 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.

[0408] [ka]

[0409] [ka]

[0410] 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.

[0411] 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 repeating units f1 to f3 is used, the addition of an additive-type acid generator, which will be described later, can be omitted.

[0412] In the case of negative resist materials or non-chemically amplified resist materials, the repeating units x1 and x2 are not necessarily required in the base polymer.

[0413] 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.

[0414] [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.

[0415] 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.

[0416] The resist material of the present invention may contain an additive acid generator. Examples of additive acid generators 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 types.

[0417] The resist material of the present invention may contain a quencher. The quencher refers to 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.

[0418] 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.

[0419] 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.

[0420] 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.

[0421] 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.

[0422] The resist material of the present invention may contain a crosslinking agent when it is a negative resist. Adding a crosslinking agent can further increase the difference in dissolution rate between the exposed and unexposed areas, but it also increases the risk of swelling in the developer. 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.

[0423] The resist material using the organic film-forming composition of the present invention may contain a water repellency improver for improving the water repellency of the resist film surface. The water repellency improver can be used in immersion lithography that does not use a top coat.

[0424] The water repellency improver is preferably a polymer containing a fluorinated alkyl group or a polymer containing a 1,1,1,3,3,3-hexafluoro-2-propanol residue of a specific structure, and more preferably those exemplified in JP-A Nos. 2007-297590 and 2008-111103. The water repellency improver needs to be soluble in an alkaline developer or an organic solvent developer. The water repellency improver having 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, a polymer containing a repeating unit containing an amino group or an amine salt is highly effective in preventing acid evaporation during post-exposure baking (PEB) and preventing poor opening of the hole pattern after development.

[0425] 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.

[0426] By adding the resin material containing pentafluorosulfate groups of the present invention to a resist composition, the pentafluorosulfate groups orient on the resist film surface during spin coating, thereby enhancing the water repellency of the resist surface. This prevents the acid generated from the acid generator during immersion lithography using water from dissolving in water, resulting in a T-top shape in positive resists or a rounded top shape in negative resists. This also prevents water droplets from remaining on the resist film even during high-speed stage scanning during immersion lithography, resulting in a highly water-repellent surface. The incorporation of an acid-eliminating unit that improves alkali solubility with acid or a hydrolyzable unit that improves hydrophilicity with alkali into the resin of the present invention further enhances the resolution of the resist and prevents the occurrence of blob defects. When used as a water repellency improver for immersion lithography, the amount of the resin of the present invention added is 0.1 to 20 parts by weight, preferably 0.2 to 15 parts by weight, per 100 parts by weight of the resin for the resist. A resin of the present invention functioning as a surfactant can also be used in combination with a resin of the present invention serving as a water repellency improver for immersion lithography.

[0427] 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.

[0428] 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.

[0429] [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 be a pattern formation method comprising the steps of forming a resist film on a substrate using the film-forming composition of the present invention, exposing the resist film to high-energy rays, and developing the exposed resist film using a developer.

[0430] 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.

[0431] 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.

[0432] The thickness of the resist film is preferably 1 nm to 200 μm, and more preferably 2 nm to 100 μm.

[0433] 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.

[0434] The resist film is then exposed to high-energy radiation, such as ultraviolet radiation, far ultraviolet radiation, electron beam (EB), EUV radiation with a wavelength of 3 to 15 nm, X-rays, soft X-rays, excimer laser light, gamma rays, and synchrotron radiation.

[0435] When ultraviolet rays, far ultraviolet rays, EUV, X-rays, soft X-rays, excimer laser light, gamma rays, synchrotron radiation, or the like is used as the high-energy rays, the exposure dose is preferably 1 to 200 mJ / cm 2 , 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 pattern is written directly or using a mask to form the desired pattern.

[0436] The resist material 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, gamma rays, and synchrotron radiation.

[0437] 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.

[0438] 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.

[0439] The developer may be an organic solvent developer or an alkaline aqueous developer.

[0440] 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 the lactate 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.

[0441] Specific examples of the alkaline aqueous developer include aqueous solutions of potassium hydroxide, sodium hydroxide, etc., and aqueous alkaline solutions of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline hydroxide, etc.

[0442] The developers may be used alone or in combination of two or more.

[0443] 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.

[0444] 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.

[0445] 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.

[0446] 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.

[0447] Examples of aromatic solvents include toluene, xylene, ethylbenzene, isopropylbenzene, tert-butylbenzene, and mesitylene.

[0448] 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.

[0449] 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]

[0450] The present invention will be explained in more detail below with reference to Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited thereto. The molecular weight was measured specifically as follows: The weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene were determined by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent (solvent), and the polydispersity (Mw / Mn) was also determined.

[0451] [Synthesis of polymers (B1) to (B18)] The monomers used in the synthesis of the example polymers (B1) to (B18) are shown below.

[0452] [ka]

[0453] [Synthesis Example 1] Synthesis of polymer (B1) [ka] 10.0 g of propylene glycol monomethyl ether acetate (PGMEA) was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 5.04 g (15.0 mmol) of monomer a-(1), 0.173 g (0.75 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (B1). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B1) was 12,900 and the polydispersity (Mw / Mn) was 1.45.

[0454] [Synthesis Example 2] Synthesis of polymer (B2) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 4.83 g (15.0 mmol) of monomer a-(2), 0.173 g (0.75 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (B2). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B2) was 14,200 and the polydispersity (Mw / Mn) was 1.38.

[0455] [Synthesis Example 3] Synthesis of polymer (B3) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 3.87 g (12.0 mmol) of monomer a-(2), 0.36 g (3.0 mmol) of monomer a-(3), 0.173 g (0.75 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (B3). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B3) was 12,800 and the polydispersity (Mw / Mn) was 1.58.

[0456] [Synthesis Example 4] Synthesis of polymer (B4) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 4.32 g (15.0 mmol) of monomer a-(4), 0.173 g (0.75 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (B4). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B4) was 10,800 and the polydispersity (Mw / Mn) was 1.44.

[0457] [Synthesis Example 5] Synthesis of polymer (B5) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 4.31 g (15.0 mmol) of monomer a-(5), 0.173 g (0.75 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (B5). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B5) was 12,300 and the polydispersity (Mw / Mn) was 1.34.

[0458] [Synthesis Example 6] Synthesis of polymer (B6) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 4.55 g (15.0 mmol) of monomer a-(6), 0.173 g (0.75 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (B6). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B6) was 11,200 and the polydispersity (Mw / Mn) was 1.41.

[0459] [Synthesis Example 7] Synthesis of polymer (B7) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 5.40 g (15.0 mmol) of monomer a-(7), 0.173 g (0.75 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (B7). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B7) was 16,300 and the polydispersity (Mw / Mn) was 1.56.

[0460] [Synthesis Example 8] Synthesis of polymer (B8) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 5.40 g (15.0 mmol) of monomer a-(8), 0.173 g (0.75 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (B8). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B8) was 14,900 and the polydispersity (Mw / Mn) was 1.54.

[0461] [Synthesis Example 9] Synthesis of polymer (B9) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 5.44 g (15.0 mmol) of monomer a-(9), 0.173 g (0.75 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (B9). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B9) was 17,100 and the polydispersity (Mw / Mn) was 1.42.

[0462] [Synthesis Example 10] Synthesis of polymer (B10) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 5.85 g (15.0 mmol) of monomer a-(10), 0.173 g (0.75 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (B10). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B10) was 16,100 and the polydispersity (Mw / Mn) was 1.55.

[0463] [Synthesis Example 11] Synthesis of polymer (B11) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 5.85 g (15.0 mmol) of monomer a-(11), 0.173 g (0.75 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (B11). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B11) was 18,100 and the polydispersity (Mw / Mn) was 1.65.

[0464] [Synthesis Example 12] Synthesis of polymer (B12) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 5.18 g (15.0 mmol) of monomer a-(12), 0.173 g (0.75 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the desired polymer (B12). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B12) was 16,100 and the polydispersity (Mw / Mn) was 1.55.

[0465] [Synthesis Example 13] Synthesis of polymer (B13) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 4.35 g (12.0 mmol) of monomer a-(9), 1.45 g (3.0 mmol) of monomer a-(13), 0.173 g (0.75 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the desired polymer (B13). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B13) was 18,800 and the polydispersity (Mw / Mn) was 1.65.

[0466] [Synthesis Example 14] Synthesis of polymer (B14) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 2.72 g (7.5 mmol) of monomer a-(9), 3.62 g (7.5 mmol) of monomer a-(13), 0.173 g (0.75 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the desired polymer (B14). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B14) was 21,200 and the polydispersity (Mw / Mn) was 1.75.

[0467] [Synthesis Example 15] Synthesis of polymer (B15) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 2.92 g (7.5 mmol) of monomer a-(10), 0.87 g (7.5 mmol) of monomer a-(14), 0.173 g (0.75 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the desired polymer (B15). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B15) was 11,200 and the polydispersity (Mw / Mn) was 1.38.

[0468] [Synthesis Example 16] Synthesis of polymer (B16) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 4.68 g (12.0 mmol) of monomer a-(10), 0.52 g (3.0 mmol) of monomer a-(15), 0.173 g (0.75 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the desired polymer (B16). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B16) was 21,200 and the polydispersity (Mw / Mn) was 1.75.

[0469] [Synthesis Example 17] Synthesis of polymer (B17) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 5.85 g (15.0 mmol) of monomer a-(10), 0.103 g (0.45 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (B17). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B17) was 28,100 and the polydispersity (Mw / Mn) was 1.89.

[0470] [Synthesis Example 18] Synthesis of polymer (B18) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 5.85 g (15.0 mmol) of monomer a-(10), 0.069 g (0.30 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the desired polymer (B18). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B18) was 32,100 and the polydispersity (Mw / Mn) was 2.03.

[0471] [Synthesis of polymers (B19) to (B29)] The raw materials used in the synthesis of the example polymers (B19) to (B29) are shown below: For b-(9), a 37% aqueous solution of formalin was used.

[0472] [ka]

[0473] [ka]

[0474] [Synthesis Example 19] Synthesis of polymer (intermediate 1) [ka] Under a nitrogen atmosphere, 216.8 g (2.00 mol) of raw material b-(1), 146.0 g (equivalent to 1.80 mol of formaldehyde) of raw material b-(9), 9.0 g of oxalic acid, and 100 g of dioxane were added and reacted at an internal temperature of 100 °C for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, 1000 ml of methyl isobutyl ketone (MIBK) was added, and the mixture was washed six times with 500 ml of pure water. The organic layer was recovered, and the pressure was reduced to 2 mmHg at an internal temperature of 150 °C to remove water, solvent, and residual monomers under reduced pressure, yielding a polymer (intermediate 1). Analysis revealed that the weight-average molecular weight (Mw) of the polymer (intermediate 1) was 8100 and the polydispersity (Mw / Mn) was 3.51.

[0475] [Synthesis Example 20] Synthesis of polymer (B19) [ka] Under a nitrogen atmosphere, 10.0 g (equivalent to 83.2 mmol, calculated as repeating units) of polymer (intermediate 1), 13.80 g (99.9 mmol) of potassium carbonate, and 100 g of DMF were added to form a uniform dispersion at an internal temperature of 50 °C. 25.23 g (99.9 mmol) of raw material b-(7) was slowly added, and the reaction was carried out at an internal temperature of 50 °C for 24 hours. 300 ml of MIBK and 300 g of pure water were added to the reaction solution to dissolve the precipitated salt, and the separated aqueous layer was removed. 1500 g of hexane was added to the resulting organic layer, and the upper layer was removed. The lower layer, which precipitated in a mochi-like form, was collected and redissolved in 300 ml of MIBK. After washing six times with 100 g of 3% aqueous nitric acid solution and 100 g of pure water, the organic layer was evaporated to dryness under reduced pressure to obtain polymer (B19). As a result of analysis, the weight average molecular weight (Mw) of the polymer (B19) was 17,400, and the dispersity (Mw / Mn) was 3.21.

[0476] [Synthesis Example 21] Synthesis of polymer (B20) [ka] Under a nitrogen atmosphere, 10.0 g (equivalent to 83.2 mmol, calculated as repeating units) of polymer (intermediate 1), 13.80 g (99.9 mmol) of potassium carbonate, and 100 g of DMF were added to form a homogeneous dispersion at an internal temperature of 50 °C. 29.53 g (99.9 mmol) of raw material b-(8) was slowly added, and the reaction was carried out at an internal temperature of 50 °C for 24 hours. 300 ml of MIBK and 300 g of pure water were added to the reaction solution to dissolve the precipitated salt, and the separated aqueous layer was removed. 1500 g of hexane was added to the resulting organic layer, and the upper layer was removed. The lower layer, which precipitated as a mochi-like substance, was collected and redissolved in 300 ml of MIBK. After washing six times with 100 g of 3% aqueous nitric acid solution and 100 g of pure water, the organic layer was evaporated to dryness under reduced pressure to obtain polymer (B20). As a result of analysis, the weight average molecular weight (Mw) of the polymer (B20) was 20,400, and the dispersity (Mw / Mn) was 3.11.

[0477] [Synthesis Example 22] Synthesis of polymer (B21) [ka] Under a nitrogen atmosphere, 10.0 g (equivalent to 83.2 mmol, calculated as repeating units) of polymer (intermediate 1), 11.50 g (83.2 mmol) of potassium carbonate, and 100 g of DMF were added to form a homogeneous dispersion at an internal temperature of 50 °C. 14.72 g (58.3 mmol) of raw material b-(7) was slowly added, and the reaction was carried out at an internal temperature of 50 °C for 24 hours. 300 ml of MIBK and 300 g of pure water were added to the reaction solution to dissolve the precipitated salt, and the separated aqueous layer was removed. 1500 g of hexane was added to the resulting organic layer, and the upper layer was removed. The lower layer, which precipitated in a mochi-like form, was collected and redissolved in 300 ml of MIBK. After washing six times with 100 g of 3% aqueous nitric acid solution and 100 g of pure water, the organic layer was evaporated to dryness under reduced pressure to obtain polymer (B21). As a result of analysis, the weight average molecular weight (Mw) of the polymer (B21) was 15,400 and the dispersity (Mw / Mn) was 2.98.

[0478] [Synthesis Example 23] Synthesis of polymer (B22) [ka] Under a nitrogen atmosphere, 10.0 g (equivalent to 83.2 mmol, calculated as repeating units) of polymer (intermediate 1), 11.50 g (83.2 mmol) of potassium carbonate, and 100 g of DMF were added to form a homogeneous dispersion at an internal temperature of 50 °C. 12.30 g (41.6 mmol) of raw material b-(8) was slowly added, and the reaction was carried out at an internal temperature of 50 °C for 24 hours. 300 ml of MIBK and 300 g of pure water were added to the reaction solution to dissolve the precipitated salt, and the separated aqueous layer was removed. 1500 g of hexane was added to the resulting organic layer, and the upper layer was removed. The lower layer, which precipitated as a mochi-like substance, was collected and redissolved in 300 ml of MIBK. After washing six times with 100 g of 3% aqueous nitric acid solution and 100 g of pure water, the organic layer was evaporated to dryness under reduced pressure to obtain polymer (B22). As a result of analysis, the weight average molecular weight (Mw) of the polymer (B22) was 17,900 and the dispersity (Mw / Mn) was 3.08.

[0479] [Synthesis Example 24] Synthesis of polymer (B23) [ka] Under a nitrogen atmosphere, 5.00 g (16.0 mmol) of raw material b-(5), 1.17 g of raw material b-(9) (corresponding to 14.4 mmol as formaldehyde), 0.5 g of oxalic acid, and 20 g of dioxane were added and reacted at an internal temperature of 100°C for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, 60 g of hexane was added, and the upper layer was removed. The lower layer, which precipitated in a mochi-like form, was collected, 100 ml of MIBK was added, and the mixture was washed six times with 50 ml of pure water. The organic layer was collected, and the pressure was reduced to 2 mmHg at an internal temperature of 150°C to remove water, solvent, and residual monomers under reduced pressure, yielding polymer (B23). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B23) was 10100 and the polydispersity (Mw / Mn) was 2.91.

[0480] [Synthesis Example 25] Synthesis of polymer (B24) [ka] Under a nitrogen atmosphere, 5.00 g (22.7 mmol) of raw material b-(6), 1.17 g (20.4 mmol) of raw material b-(10), 0.5 g of paratoluenesulfonic acid monohydrate, and 20 g of dioxane were added and reacted at an internal temperature of 100°C for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, 60 g of hexane was added, and the upper layer was removed. The lower layer, which precipitated in a mochi-like form, was collected, 100 ml of MIBK was added, and the mixture was washed six times with 50 ml of pure water. The organic layer was collected, and the pressure was reduced to 2 mmHg at an internal temperature of 150°C to remove water, solvent, and residual monomers under reduced pressure, yielding polymer (B24). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B24) was 6800 and the polydispersity (Mw / Mn) was 2.12.

[0481] [Synthesis Example 26] Synthesis of polymer (intermediate 2) [ka] Under a nitrogen atmosphere, 5.00 g (14.3 mmol) of raw material b-(2), 2.98 g (12.8 mmol) of raw material b-(10), 0.5 g of paratoluenesulfonic acid monohydrate, and 20 g of dioxane were added and reacted at an internal temperature of 100 °C for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, 60 g of hexane was added, and the upper layer was removed. The lower layer, which precipitated in a mochi-like form, was collected, 100 ml of MIBK was added, and the mixture was washed six times with 50 ml of pure water. The organic layer was collected, and the pressure was reduced to 2 mmHg at an internal temperature of 150 °C to remove water, solvent, and residual monomers under reduced pressure, yielding a polymer (intermediate 2). Analysis revealed that the weight-average molecular weight (Mw) of the polymer (intermediate 2) was 3800 and the polydispersity (Mw / Mn) was 2.52.

[0482] [Synthesis Example 27] Synthesis of polymer (B25) [ka] Under a nitrogen atmosphere, 5.0 g (equivalent to 8.86 mmol, calculated as repeating units) of polymer (intermediate 2), 2.45 g (17.7 mmol) of potassium carbonate, and 30 g of DMF were added to form a homogeneous dispersion at an internal temperature of 50 °C. 2.24 g (8.86 mmol) of raw material b-(7) was slowly added, and the reaction was carried out at an internal temperature of 50 °C for 24 hours. 100 ml of MIBK and 100 g of pure water were added to the reaction solution to dissolve the precipitated salt, and the separated aqueous layer was removed. 200 g of hexane was added to the resulting organic layer, and the upper layer was removed. The lower layer, which precipitated in a mochi-like form, was collected and redissolved in 100 ml of MIBK. After washing six times with 50 g of 3% aqueous nitric acid solution and 50 g of pure water, the organic layer was evaporated to dryness under reduced pressure to obtain polymer (B25). As a result of analysis, the weight average molecular weight (Mw) of the polymer (B25) was 5,900 and the dispersity (Mw / Mn) was 2.58.

[0483] [Synthesis Example 28] Synthesis of polymer (intermediate 3) [ka] Under a nitrogen atmosphere, 5.00 g (11.1 mmol) of raw material b-(3), 1.90 g (10.0 mmol) of raw material b-(11), 0.5 g of paratoluenesulfonic acid monohydrate, and 20 g of dioxane were added and reacted at an internal temperature of 100 °C for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, 60 g of diisopropyl ether was added, and the upper layer was removed. The lower layer, which precipitated in a mochi-like form, was collected, 100 ml of MIBK was added, and the mixture was washed six times with 50 ml of pure water. The organic layer was collected, and the pressure was reduced to 2 mmHg at an internal temperature of 150 °C to remove water, solvent, and residual monomers under reduced pressure, yielding a polymer (intermediate 3). Analysis revealed that the weight-average molecular weight (Mw) of the polymer (intermediate 3) was 4400 and the polydispersity (Mw / Mn) was 2.34.

[0484] [Synthesis Example 29] Synthesis of polymer (B26) [ka] Under a nitrogen atmosphere, 5.0 g (equivalent to 8.03 mmol, calculated as repeating units) of polymer (intermediate 3), 2.22 g (16.1 mmol) of potassium carbonate, and 30 g of DMF were added to form a homogeneous dispersion at an internal temperature of 50 °C. 2.03 g (8.03 mmol) of raw material b-(7) was slowly added, and the reaction was carried out at an internal temperature of 50 °C for 24 hours. 100 ml of MIBK and 100 g of pure water were added to the reaction solution to dissolve the precipitated salt, and the separated aqueous layer was removed. 200 g of diisopropyl ether was added to the resulting organic layer, and the upper layer was removed. The lower layer, which precipitated as a mochi-like substance, was collected and redissolved in 100 ml of MIBK. After washing six times with 50 g of 3% aqueous nitric acid solution and 50 g of pure water, the organic layer was evaporated to dryness under reduced pressure to obtain polymer (B26). As a result of analysis, the weight average molecular weight (Mw) of the polymer (B26) was 7,300, and the dispersity (Mw / Mn) was 2.28.

[0485] [Synthesis Example 30] Synthesis of polymer (intermediate 4) [ka] Under a nitrogen atmosphere, 5.00 g (16.3 mmol) of raw material b-(4), 3.98 g (17.1 mmol) of raw material b-(10), 4.70 g of methanesulfonic acid, and 20 g of 1,2-dichloroethane were added and reacted at an internal temperature of 80 °C for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, 120 g of diisopropyl ether was added, and the upper layer was removed. The lower layer, which precipitated in a mochi-like form, was collected, 100 ml of MIBK was added, and the mixture was washed six times with 50 ml of pure water. The organic layer was collected, and the pressure was reduced to 2 mmHg at an internal temperature of 150 °C to remove water, solvent, and residual monomers under reduced pressure, yielding a polymer (intermediate 4). Analysis revealed that the weight-average molecular weight (Mw) of the polymer (intermediate 4) was 7700 and the polydispersity (Mw / Mn) was 3.64.

[0486] [Synthesis Example 31] Synthesis of polymer (B27) [ka] Under a nitrogen atmosphere, 5.0 g (9.60 mmol, calculated as repeating units) of polymer (intermediate 4), 3.98 g (28.8 mmol) of potassium carbonate, and 30 g of DMF were added to form a homogeneous dispersion at an internal temperature of 50 °C. 2.18 g (8.65 mmol) of raw material b-(7) was slowly added, and the reaction was carried out at an internal temperature of 50 °C for 24 hours. 100 ml of MIBK and 100 g of pure water were added to the reaction solution to dissolve the precipitated salt, and the separated aqueous layer was removed. 200 g of hexane was added to the resulting organic layer, and the upper layer was removed. The lower layer, which precipitated as a mochi-like substance, was collected and redissolved in 100 ml of MIBK. After washing six times with 50 g of 3% aqueous nitric acid solution and 50 g of pure water, the organic layer was evaporated to dryness under reduced pressure to obtain polymer (B27). As a result of analysis, the weight average molecular weight (Mw) of the polymer (B27) was 9600 and the dispersity (Mw / Mn) was 3.48.

[0487] [Synthesis Example 32] Synthesis of polymer (intermediate 5) [ka] Under a nitrogen atmosphere, 5.00 g (31.2 mmol) of raw material b-(12), 3.43 g (28.1 mmol) of raw material b-(13), 0.50 g of paratoluenesulfonic acid monohydrate, and 30 g of propylene glycol monomethyl ether were added and reacted at an internal temperature of 120 °C for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, 80 g of diisopropyl ether was added, and the upper layer was removed. The lower layer, which precipitated in a mochi-like form, was collected, 100 ml of MIBK was added, and the mixture was washed six times with 50 ml of pure water. The organic layer was collected, and the pressure was reduced to 2 mmHg at an internal temperature of 150 °C to remove water, solvent, and residual monomers under reduced pressure, yielding a polymer (Intermediate 5). Analysis revealed that the weight-average molecular weight (Mw) of the polymer (Intermediate 5) was 3700 and the polydispersity (Mw / Mn) was 2.84.

[0488] [Synthesis Example 33] Synthesis of polymer (B28) [ka] Under a nitrogen atmosphere, 5.0 g (18.92 mmol, calculated as repeating units) of polymer (intermediate 5), 7.84 g (56.8 mmol) of potassium carbonate, and 30 g of DMF were added to form a homogeneous dispersion at an internal temperature of 50 °C. 7.17 g (28.4 mmol) of raw material b-(7) was slowly added, and the reaction was carried out at an internal temperature of 50 °C for 24 hours. 100 ml of MIBK and 100 g of pure water were added to the reaction solution to dissolve the precipitated salt, and the separated aqueous layer was removed. 200 g of hexane was added to the resulting organic layer, and the upper layer was removed. The lower layer, which precipitated as a mochi-like substance, was collected and redissolved in 100 ml of MIBK. After washing six times with 50 g of 3% aqueous nitric acid solution and 50 g of pure water, the organic layer was evaporated to dryness under reduced pressure to obtain polymer (B28). As a result of analysis, the weight average molecular weight (Mw) of the polymer (B28) was 7,300, and the dispersity (Mw / Mn) was 2.98.

[0489] [Synthesis Example 34] Synthesis of polymer (B29) [ka] Under a nitrogen atmosphere, 0.142 g (13.69 mmol) of 2,2-dimethyl-1,3-propanediol as an initiator, 0.192 g (13.69 mmol) of boron trifluoride tetrahydrofuran complex, and 30 g of methylene chloride were added and made into a homogeneous solution in a water bath. 10.0 g (32.8 mmol) of raw material b-(14) was slowly added dropwise. After the dropwise addition, the mixture was allowed to react at room temperature for 24 hours, and then 30 g of 5% sodium bicarbonate solution was added in an ice bath to quench the reaction. After removing the separated aqueous layer, the mixture was washed five times with 30 g of pure water. The organic layer was evaporated to dryness under reduced pressure to obtain polymer (B29). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B29) was 4300 and the polydispersity (Mw / Mn) was 2.11.

[0490] [Synthesis of polymers (B30) to (B42)] The monomers used in the synthesis of the example polymers (B30) to (B42) are shown below.

[0491] [ka]

[0492] [ka]

[0493] [Synthesis Example 35] Synthesis of polymer (B30) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 3.02 g (10.5 mmol) of monomer a-(4), 1.38 g (4.5 mmol) of monomer a-(16), 0.069 g (0.30 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the desired polymer (B30). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B30) was 10,600 and the polydispersity (Mw / Mn) was 1.83.

[0494] [Synthesis Example 36] Synthesis of polymer (B31) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 3.02 g (10.5 mmol) of monomer a-(4), 1.07 g (4.5 mmol) of monomer a-(17), 0.069 g (0.30 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the desired polymer (B31). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B31) was 9800 and the polydispersity (Mw / Mn) was 1.77.

[0495] [Synthesis Example 37] Synthesis of polymer (B32) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 3.02 g (10.5 mmol) of monomer a-(4), 1.00 g (4.5 mmol) of monomer a-(18), 0.069 g (0.30 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the desired polymer (B32). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B32) was 10,800 and the polydispersity (Mw / Mn) was 1.87.

[0496] [Synthesis Example 38] Synthesis of polymer (B33) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 5.78 g (15.0 mmol) of monomer a-(19), 0.069 g (0.30 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the desired polymer (B33). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B33) was 10,800 and the polydispersity (Mw / Mn) was 1.87.

[0497] [Synthesis Example 39] Synthesis of polymer (B34) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 7.70 g (15.0 mmol) of monomer a-(20), 0.069 g (0.30 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (B34). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B34) was 9200 and the polydispersity (Mw / Mn) was 1.81.

[0498] [Synthesis Example 40] Synthesis of polymer (B35) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 2.16 g (7.5 mmol) of monomer a-(4), 3.51 g (7.5 mmol) of monomer a-(21), 0.069 g (0.30 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the desired polymer (B35). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B35) was 9300 and the polydispersity (Mw / Mn) was 1.85.

[0499] [Synthesis Example 41] Synthesis of polymer (B36) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 3.37 g (7.5 mmol) of monomer a-(22), 3.51 g (7.5 mmol) of monomer a-(21), 0.069 g (0.30 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the desired polymer (B36). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B36) was 7800 and the polydispersity (Mw / Mn) was 1.65.

[0500] [Synthesis Example 42] Synthesis of polymer (B37) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 2.48 g (7.5 mmol) of monomer a-(23), 3.51 g (7.5 mmol) of monomer a-(21), 0.069 g (0.30 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the desired polymer (B37). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B37) was 7600 and the polydispersity (Mw / Mn) was 1.69.

[0501] [Synthesis Example 43] Synthesis of polymer (B38) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 2.52 g (7.5 mmol) of monomer a-(24), 4.45 g (7.5 mmol) of monomer a-(26), 0.069 g (0.30 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the desired polymer (B38). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B38) was 7400 and the polydispersity (Mw / Mn) was 1.61.

[0502] [Synthesis Example 44] Synthesis of polymer (B39) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 2.66 g (7.5 mmol) of monomer a-(25), 4.45 g (7.5 mmol) of monomer a-(26), 0.069 g (0.30 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the desired polymer (B39). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B39) was 7800 and the polydispersity (Mw / Mn) was 1.60.

[0503] [Synthesis Example 45] Synthesis of polymer (B40) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 3.87 g (7.5 mmol) of monomer a-(27), 2.21 g (7.5 mmol) of monomer a-(30), 0.069 g (0.30 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the desired polymer (B40). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B40) was 6900 and the polydispersity (Mw / Mn) was 1.50.

[0504] [Synthesis Example 46] Synthesis of polymer (B41) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 2.90 g (7.5 mmol) of monomer a-(28), 2.36 g (7.5 mmol) of monomer a-(31), 0.069 g (0.30 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the desired polymer (B41). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B41) was 8600 and the polydispersity (Mw / Mn) was 1.78.

[0505] [Synthesis Example 47] Synthesis of polymer (B42) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 3.60 g (7.5 mmol) of monomer a-(29), 2.75 g (7.5 mmol) of monomer a-(32), 0.069 g (0.30 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the desired polymer (B42). Analysis revealed that the weight-average molecular weight (Mw) of polymer (B42) was 8800 and the polydispersity (Mw / Mn) was 1.82.

[0506] [Synthesis of Comparative Polymers (R1) to (R7) and Comparative Compound (R8)] The raw materials used in the synthesis of comparative polymers or compounds (R1) to (R8) are shown below. Polymers (R1) to (R7) were obtained using monomers (c1) to (c9). Compound (R8) was synthesized using (c10).

[0507] [ka]

[0508] [Comparative Synthesis Example 1] Synthesis of Comparative Polymer (R1) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 3.44 g (10.8 mmol) of monomer (c1), 7.46 g (34.2 mmol) of monomer (c3), 0.473 g (2.05 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the desired polymer (R1). Analysis revealed that the weight-average molecular weight (Mw) of polymer (R1) was 9300 and the polydispersity (Mw / Mn) was 1.23.

[0509] [Comparative Synthesis Example 2] Synthesis of Comparative Polymer (R2) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 1.43 g (4.5 mmol) of monomer (c1), 5.76 g (34.2 mmol) of monomer (c4), 0.473 g (2.05 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the desired polymer (R2). Analysis revealed that the weight-average molecular weight (Mw) of polymer (R2) was 6300 and the polydispersity (Mw / Mn) was 1.50.

[0510] [Comparative Synthesis Example 3] Synthesis of Comparative Polymer (R3) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 7.00 g (31.5 mmol) of monomer (c2), 2.95 g (13.5 mmol) of monomer (c4), 0.473 g (2.05 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 20.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the desired polymer (R3). Analysis revealed that the weight-average molecular weight (Mw) of polymer (R3) was 6300 and the polydispersity (Mw / Mn) was 1.38.

[0511] [Comparative Synthesis Example 4] Synthesis of Comparative Polymer (R4) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 5.0 g (22.5 mmol) of monomer (c2), 4.46 g (22.5 mmol) of monomer (c5), 0.473 g (2.05 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the desired polymer (R4). Analysis revealed that the weight-average molecular weight (Mw) of polymer (R4) was 8300 and the polydispersity (Mw / Mn) was 1.33.

[0512] [Comparative Synthesis Example 5] Synthesis of Comparative Polymer (R5) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 2.0 g (9.0 mmol) of monomer (c2), 4.83 g (36.0 mmol) of monomer (c6), 0.473 g (2.05 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the desired polymer (R5). Analysis revealed that the weight-average molecular weight (Mw) of polymer (R5) was 4300 and the polydispersity (Mw / Mn) was 1.43.

[0513] [Comparative Synthesis Example 6] Synthesis of Comparative Polymer (R6) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 4.0 g (13.7 mmol) of monomer (c7), 1.66 g (3.5 mmol) of monomer (c8), 0.198 g (0.86 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the desired polymer (R6). Analysis revealed that the weight-average molecular weight (Mw) of polymer (R6) was 12,300 and the polydispersity (Mw / Mn) was 1.57.

[0514] [Comparative Synthesis Example 7] Synthesis of Comparative Polymer (R7) [ka] 10.0 g of PGMEA was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise a mixture of 4.73 g (9.8 mmol) of monomer (c8), 4.00 g (9.8 mmol) of monomer (c9), 0.225 g (0.98 mmol) of dimethyl 2,2-azobis(2-methylpropionate), and 15.0 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the desired polymer (R7). Analysis revealed that the weight-average molecular weight (Mw) of polymer (R7) was 16,300 and the polydispersity (Mw / Mn) was 1.62.

[0515] [Comparative Synthesis Example 8] Synthesis of Comparative Compound (R8) [ka] Under a nitrogen atmosphere, 10.0 g (29.35 mmol) of raw material (c10) was uniformly dispersed in 400 mL of THF, and then 23.48 g (293.5 mmol as sodium hydroxide) of 50 wt% aqueous sodium hydroxide solution was added dropwise and the mixture was allowed to react under reflux for 10 hours. After the reaction, 65 g of 20% aqueous sodium hydroxide solution was added while cooling in an ice bath to make the liquid acidic, and then extracted with 200 mL of diisopropyl ether. The organic layer was then washed five times with pure water. The organic layer was collected and evaporated to dryness under reduced pressure. 100 mL of ethanol was then added, and the residue was dispersed again. 28.2 g of 50% aqueous sodium hydroxide solution (equivalent to 352.2 mmol as sodium hydroxide) was added, and the mixture was heated and stirred at 100 °C for 1 hour, after which crystals were precipitated while stirring in an ice bath. The precipitated crystals were filtered off, washed twice with 100 mL of ethanol, collected, and dried at 40 °C to obtain comparative compound (R8).

[0516] [Resin or compound for forming organic film] A1: a resin represented by the following formula (A1): A2: a resin represented by the following formula (A2): A3: A compound represented by the following formula (A3): A4: A compound represented by the following formula (A4): A5: Resin represented by the following formula (A5): A6: Resin represented by the following formula (A6):

[0517] [ka]

[0518] [ka]

[0519] [ka]

[0520] [ka]

[0521] [ka]

[0522] [ka]

[0523] [solvent] (C1): Propylene glycol monomethyl ether acetate (C2): Propylene glycol monoethyl ether

[0524] [Preparation of Organic Film-Forming Compositions (UDL-1 to 138, Comparative UDL-1 to 26)] The polymers (A1) to (A29), (R1) to (R7), comparative compound (R8), organic film-forming resins (C1) to (C6), and solvents were dissolved in the proportions shown in Tables 1-1 to 1-6, and the resulting solution was filtered through a 0.1 μm fluororesin filter to prepare organic film materials (resist underlayer film materials: UDL-1 to 138, comparative examples UDL-1 to 26).

[0525] [Table 1-1]

[0526] [Table 1-2]

[0527] [Table 1-3]

[0528] [Table 1-4]

[0529] [Table 1-5]

[0530] [Table 1-6]

[0531] [Preparation of Silicon Wafers with Organic Cured Films Formed Using Organic Film-Forming Compositions (UDL-1 to 109, Comparative UDL-1 to 19)] Using a Tokyo Electron Limited coater / developer "CLEAN TRACK LITHIUS Pro AP," 2 mL of each of the organic film-forming compositions (UDL-1 to 109, Comparative UDL-1 to 19) was dispensed onto the center of a 300 mm silicon wafer. After baking, the wafer was rotated at a rotation speed sufficient to achieve the average film thickness listed in Tables 2-1 to 2-5. While the silicon wafer was rotated at 1000 rpm, the remover nozzle was moved at a speed of 5 mm / s from the outer periphery of the silicon wafer to a position 3 mm toward the center, discharging the remover (a mixture of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether (30:70, mass ratio)) at a rate of 2 mL / s. At this position, the remover was further dispensed at a rate of 2 mL / s for 5 seconds. Dispensing of the dispensed solution was then stopped, and the wafer was rotated at 1000 rpm for an additional 30 seconds. Next, the silicon wafer on which the organic film-forming composition was formed was heated at 350° C. for 60 seconds to obtain a silicon wafer on which a cured organic film was formed.

[0532] [Solvent Resistance Evaluation: Examples 1-1 to 1-109, Comparative Examples 1-1 to 1-19] Using the method described above, organic film-forming compositions (UDL-1 to 109, Comparative UDL-1 to 19) were deposited on silicon wafers, the film thickness was measured, PGMEA solvent was dispensed onto the film, the film was left for 30 seconds, spin-dried, and baked at 100°C for 60 seconds to evaporate the PGMEA, and the film thickness was measured. The film thickness before dispensing the PGMEA solvent was defined as X, and the film thickness after dispensing the PGMEA solvent was defined as X1. The absolute value of the value calculated by (X1 - X) / X x 100 was used as the film thickness change rate (%). A film thickness change rate of less than 0.5% was considered good, and a film thickness change rate of 0.5% or more was considered poor.

[0533] [In-plane uniformity evaluation: Examples 1-1 to 1-109, Comparative Examples 1-1 to 1-19] The organic film-forming compositions (UDL-1 to 109, comparative UDL-1 to 19) were formed on silicon wafers using the above method, and the thickness of the organic cured film was measured at 225 concentric points within a radius of 145 mm from the center of the wafer using an optical film thickness meter. max, minimum X min , average value X average As, (X max -X min ) / X average The value obtained by the above was taken as the in-plane uniformity (%). When the in-plane uniformity was less than 2%, it was rated as A (good), when it was 2% or more but less than 3%, it was rated as B, and when it was 3% or more, it was rated as C (poor).

[0534] [Table 2-1]

[0535] [Table 2-2]

[0536] [Table 2-3]

[0537] [Table 2-4]

[0538] [Table 2-5]

[0539] [Hump suppression evaluation: Examples 2-1 to 2-109, Comparative Examples 2-1 to 2-12] Using the method described above, organic film-forming compositions (UDL-1 to 109, comparative UDL-1 to 12) were deposited on silicon wafers, and the height change from the outer periphery of the organic film to 1000 μm toward the center of the silicon wafer was measured using an Alpha-Step D-600 (contact profiler) manufactured by KLA-Tencor. Assuming the height of the silicon wafer was 0, the maximum height was rated A (good) if it was less than 110% of the film thickness, as shown in Figure 1; B if it was 110% or more but less than 150%; and C (poor) if there was a region where the height was 150% or more, as shown in Figure 2.

[0540] [Embedding Evaluation-1: Examples 2-1 to 2-109, Comparative Examples 2-1 to 2-12] As shown in Figure 4, organic film-forming compositions (UDL-1 to 109, Comparative UDL-1 to 12) were deposited by the above method on SiO2 wafer substrates with a dense hole pattern (hole diameter 0.2 μm, hole depth 1.0 μm, center-to-center distance between adjacent holes 0.4 μm) to form resist underlayer films 8. The substrates used were base substrates (SiO2 wafer substrates) 7 with a dense hole pattern as shown in Figure 4(G) (overhead view) and (H) (cross-sectional view). The cross-sectional shape of each wafer substrate was observed using a scanning electron microscope (SEM) to confirm whether the holes were filled with the resist underlayer film without any voids. When a resist underlayer film material with poor filling properties was used, voids were generated within the holes. When a resist underlayer film material with good filling properties was used, the holes were filled with the resist underlayer film without any voids, as shown in Figure 4(I). A sample was rated as good if no voids were generated, and as poor if voids were generated.

[0541] [Embedding Evaluation-2: Examples 2-81 to 2-109] As shown in Figure 4, organic film-forming compositions (UDL-81 to 109) were deposited by the above method on a SiO2 wafer substrate with a dense hole pattern (hole diameter 0.2 μm, hole depth 2.0 μm, center-to-center distance between adjacent holes 0.4 μm), forming a resist underlayer film 8. The substrate used was a base substrate (SiO2 wafer substrate) 7 with a dense hole pattern as shown in Figure 4(G) (overhead view) and (H) (cross-sectional view). The cross-sectional shape of each wafer substrate was observed using a scanning electron microscope (SEM) to confirm whether the holes were filled with the resist underlayer film without any voids. When a resist underlayer film material with poor filling properties was used, voids were generated within the holes. When a resist underlayer film material with good filling properties was used, the holes were filled with the resist underlayer film without any voids, as shown in Figure 4(I). A sample was rated as good if no voids were generated, and as poor if voids were generated. In addition, in order to evaluate the quality of filling performance, the evaluation conditions are strict, making it easier for voids to be filled, even with a rating of -1.

[0542] [Evaluation of Coatability of Silicon-Containing Resist Interlayer: Examples 2-1 to 2-109, Comparative Examples 2-1 to 2-12] Using the above method, an organic cured film was formed on a silicon wafer substrate using an organic film-forming composition (UDL-1 to 109, Comparative UDL-1 to 12). The following silicon-containing resist interlayer material (SOG1) was then applied thereon and baked at 200°C for 60 seconds to form a silicon-containing resist interlayer. The condition of the silicon-containing resist interlayer was then visually observed and evaluated. A good coating was rated as good, and a poor coating was rated as poor if pinholes were present. In this evaluation, the thickness of the silicon-containing resist interlayer was set to 5 nm, a special and strict evaluation condition, in order to evaluate the coatability of the silicon-containing resist interlayer.

[0543] 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.

[0544] [Table 3] PGEE: Propylene glycol monoethyl ether

[0545] The polymer (SP1) is shown below. [ka]

[0546] TMPANO3: Trimethylphenylammonium nitrate PGEE: Propylene glycol ethyl ether

[0547] [Table 4-1]

[0548] [Table 4-2]

[0549] [Table 4-3]

[0550] [Table 4-4]

[0551] As shown in Tables 2-1 to 2-5 and Tables 4-1 to 4-4, it was confirmed that the organic film-forming compositions of the present invention (UDL-1 to 109) are excellent in solvent resistance, in-plane uniformity, hump suppression, embedding properties, and coatability of silicon-containing resist underlayer films.

[0552] [Evaluation of Organic Thin Film Coatability: Examples 3-1 to 3-29, Comparative Examples 3-1 to 3-7] Organic film-forming compositions (UDL-110 to 138, comparative UDL-20 to 26) were applied to silicon wafer substrates and baked at 200°C for 60 seconds to form 20 nm organic films. The condition of the organic film coating was then observed and evaluated using an optical microscope. If the coating condition was good, it was rated as good, and if pinholes were present, it was rated as poor. In this evaluation, the thickness of the organic film was set to 20 nm, which was a strict evaluation condition, in order to evaluate the superiority or inferiority of the coatability of the organic film.

[0553] [Table 5]

[0554] As shown in Table 5, it was confirmed that the organic film-forming compositions of the present invention (UDL-110 to 138) had excellent coating properties.

[0555] [Pattern formation test: Examples 4-1 to 4-80] Using the above method, an organic cured film was formed on a SiO2 wafer substrate using an organic film-forming composition (UDL-1 to 80). The following silicon-containing resist intermediate film material (SOG2) was then applied on top of the organic cured film and baked at 200°C for 60 seconds to form a 35 nm thick silicon-containing resist intermediate film. The following ArF single-layer resist was then applied on top of the organic cured film as a resist top layer material and baked at 105°C for 60 seconds to form a 100 nm thick photoresist film. The following immersion protective film material (TC-1) was then applied on top of the photoresist film and baked at 90°C for 60 seconds to form a 50 nm thick protective film.

[0556] 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 6, and filtering the resultant mixture through a 0.1 μm fluororesin filter.

[0557] [Table 6] PGEE: Propylene glycol monoethyl ether

[0558] The resist top layer material (ArF single-layer resist) was prepared by dissolving a polymer (RP1), an acid generator (PAG1), and a basic compound (Amine1) in a solvent containing 0.1 mass% of FC-430 (manufactured by Sumitomo 3M Limited) in the proportions shown in Table 7, and filtering the solution through a 0.1 μm fluororesin filter.

[0559] [Table 7] PGMEA: Propylene glycol monomethyl ether acetate

[0560] The polymer (RP1), acid generator (PAG1), and basic compound (Amine1) are shown below.

[0561] [ka]

[0562] The immersion protective film material (TC-1) was prepared by dissolving the polymer (PP1) in an organic solvent in the ratio shown in Table 8 and filtering the solution through a 0.1 μm fluorine resin filter.

[0563] [Table 8]

[0564] The polymer (PP1) is shown below. [ka]

[0565] 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).

[0566] Next, using the resist upper layer film pattern as a mask, the silicon-containing resist lower layer film was dry-etched (pattern transferred) using a Tokyo Electron etching system, Telius, and using the resulting silicon-containing resist lower layer film pattern as a mask, the organic film was dry-etched (pattern transferred), and using the resulting organic film pattern as a mask, the SiO2 wafer substrate (SiO2 film) was dry-etched (pattern transferred). The etching conditions are as shown below.

[0567] (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

[0568] (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

[0569] (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

[0570] The cross section of the obtained pattern was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd. The results are shown in Tables 9-1 to 9-3.

[0571] [Table 9-1]

[0572] [Table 9-2]

[0573] [Table 9-3]

[0574] As shown in Tables 9-1 to 9-3, in Examples 4-1 to 4-80 in which the organic film-forming compositions (UDL-1 to 80) of the present invention were used, the resist upper layer film pattern was successfully transferred to the SiO2 wafer substrate, confirming that the organic film-forming compositions of the present invention are suitable for use in microfabrication using the multilayer resist method.

[0575] [Preparation of resist top layer materials (PR1 to 29, comparative PR)] Resist top layer film materials (PR1 to 29, comparative PR) were prepared by dissolving polymer (P-1), acid generator (PAG-2), quencher (Q-1), and polymers (B1 to B29) in a solvent in the proportions shown in Table 10 and filtering the solution through a 0.1 μm fluororesin filter.

[0576] [Table 10]

[0577] The polymer (P-1), acid generator (PAG-2), quencher (Q-1), and solvent are shown below.

[0578] [ka]

[0579] [ka] PGMEA: Propylene glycol monomethyl ether acetate EL: Ethyl lactate

[0580] [Preparation of silicon wafers with resist top layer films formed using resist top layer film materials (PR1-29, comparative PR)] Using a Tokyo Electron Co., Ltd. coater / developer "CLEAN TRACK LITHIUS Pro AP," 2 ml of the resist top layer material (PR1-29, comparative PR) prepared above was dispensed onto the center of a silicon wafer and spread by rotating it at a rotation speed that would result in an average film thickness of 45 nm after baking. Next, the silicon wafer coated with the resist top layer film was heated at 110°C for 30 seconds to obtain a silicon wafer with a resist top layer film formed thereon.

[0581] [Evaluation of In-Wafer Uniformity of Resist Top Layer Film: Examples 5-1 to 5-29, Comparative Example 5-1] The thickness of the resist top layer films (PR1 to 29, comparative PR) formed on the silicon wafers by the above method was measured at 225 concentric points within a radius of 145 mm from the center of the wafer using an optical film thickness meter. The maximum value Xmax, minimum value Xmin, and average value X average As, (X max -X min ) / X 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.

[0582] [Table 11]

[0583] As shown in Table 11, the resist top layer film materials (PR1 to 29) of the present invention have excellent in-plane uniformity, which indicates that the polymer of the present invention functions as a surfactant that imparts excellent leveling performance and can be used in various organic film-forming compositions regardless of the type of resin combined.

[0584] [EUV Lithography Evaluation: Examples 6-1 to 6-29] Each resist top layer material (PR1-29) listed in Table 10 was spin-coated onto a Si substrate with a 20 nm thick silicon-containing spin-on hard mask (SHB-A940, manufactured by Shin-Etsu Chemical Co., Ltd.) (43% silicon by weight) and prebaked at 110°C for 30 seconds using a hot plate to produce a 45 nm thick resist film. The resist film was exposed to light using an ASML EUV scanner NXE3400 (NA 0.33, σ 0.9 / 0.7, dipole illumination), subjected to PEB on a hot plate at 80°C for 60 seconds, and developed in a 2.38% by weight TMAH aqueous solution for 30 seconds to form a line-and-space pattern with a 40 nm pitch and a 20 nm line width. The pattern was observed using a Hitachi High-Technologies Corporation critical dimension SEM (CG6300). A line pattern with dimensions of 20 nm ± 2.0 nm was considered satisfactory.

[0585] [Table 12]

[0586] As shown in Table 12, in Examples 6-1 to 6-29 in which the organic film-forming composition of the present invention (PR1 to 29) was used, a resist upper layer film pattern of 20 nm was formed in all cases, confirming that the resist upper layer film material, which is the organic film-forming composition of the present invention, is suitable for use in fine processing.

[0587] [Preparation of silicon-containing resist intermediate film materials (SOG3-31)] Silicon-containing resist intermediate film materials were prepared by dissolving the polymer (SP1), crosslinking catalyst, and acid in an organic solvent and water in the proportions shown in Table 13, and then filtering the mixture through a 0.1 μm fluororesin filter to prepare silicon-containing resist underlayer film materials (SOG3 to SOG31).

[0588] [Table 13] PGEE: Propylene glycol monoethyl ether

[0589] [Evaluation of Coatability of Silicon-Containing Resist Interlayer: Examples 7-1 to 7-29, Comparative Example 7-1] Using the above method, an organic cured film was formed on a silicon wafer substrate using an organic film-forming composition (Comparative UDL-1), and the following silicon-containing resist interlayer film materials (SOG1, 3-31) were applied thereon and baked at 200°C for 60 seconds to form a silicon-containing resist interlayer film. The condition of the silicon-containing resist interlayer film was then visually observed and evaluated. A good coating was rated as good, and a poor coating was rated as poor if pinholes were present. In this evaluation, the thickness of the silicon-containing resist interlayer film was set to 5 nm, a special and strict evaluation condition, in order to evaluate the coatability of the silicon-containing resist interlayer film.

[0590] [Table 14]

[0591] As shown in Table 14, the silicon-containing resist intermediate film materials (SOG3 to 31) have excellent film-forming properties without generating pinholes. This indicates that the polymers of the present invention can be used as surfactants that impart high film-forming properties to various film-forming compositions, not just organic films.

[0592] [ArF Immersion Lithography Resist Patterning Evaluation: Examples 8-1 to 8-14, Comparative Examples 8-1 and 8-2] Resist top layer film materials (PR-30 to 43, comparative PR-2) were prepared by dissolving polymer (P-2), acid generator (PAG-3), quencher (Q-2), polymers (B4, B30 to B42) as resist surface water repellents, and polymers (B9 to B18) as surfactants in a solvent in the proportions shown in Table 15 and filtering through a 0.1 μm fluororesin filter.

[0593] PGMEA: Propylene glycol monomethyl ether acetate GBL: gamma butyrolactone

[0594] [ka]

[0595] [Table 15]

[0596] UDL-1 was coated onto a silicon substrate and baked at 350°C for 60 seconds to form a 500 nm thick underlayer film. A silicon-containing resist interlayer material (SOG2) was then coated on top of this and baked at 200°C for 60 seconds to form a 35 nm thick silicon-containing resist interlayer film. The following ArF single-layer resist was coated on top of this as the resist toplayer material shown in Table 15 and baked at 105°C for 60 seconds to form a 100 nm thick photoresist film. The water contact angle of the photoresist film after baking was measured. The results are shown in Table 16.

[0597] This was exposed to an ArF excimer laser immersion scanner (Nikon Corporation NSR-S610C, NA 1.30, σ 0.90 / 0.72, aperture 35°, azimuthally polarized illumination, 6% halftone phase-shift mask, dipole illumination) to create a line-and-space pattern (LS pattern) with 45 nm wafer dimensions and a 90 nm pitch, while varying the exposure dose and focus. After exposure, the wafer was subjected to PEB at 90°C for 60 seconds. For Example 8-1 and Comparative Example 8-1, paddle development was performed using n-butyl acetate for 30 seconds, followed by spin drying to form a negative pattern. For Examples 8-2 to 8-14 and Comparative Example 8-2, paddle development was performed using a 2.38 wt% TMAH aqueous solution for 30 seconds after PEB, followed by rinsing with pure water and spin drying to form a positive pattern. The optimum exposure dose (Eop) was determined by measuring the line size to 40 nm ± 4 nm using a Hitachi High-Technologies Corporation critical dimension SEM (CG-6300). After development, the wafer was cut and the cross section of the LS pattern at the optimum exposure dose was observed using an SEM. The results are shown in Table 16.

[0598] [Table 16]

[0599] As shown in Table 16, it is clear that the film-forming composition of the present invention can form a good pattern even by immersion exposure.

[0600] From the above, the organic film-forming composition of the present invention has excellent film-forming properties, high-level filling properties, and hump suppression properties, and is excellent in coatability of silicon-containing resist intermediate films, making it extremely useful as an organic film material for use in multilayer resist processes. Furthermore, the pattern formation method of the present invention using this composition makes it possible to fill holes and trenches with very high aspect ratios without voids, and to form fine patterns with high precision, and is also able to form an organic film with suppressed humps. When used in resists, this provides excellent coating uniformity and a good pattern shape, and in immersion lithography applications, it enhances the water repellency of the resist film surface, making it possible to efficiently manufacture semiconductor elements and the like. Furthermore, the polymer of the present invention can be widely used as a surfactant, as it exhibits high film-forming properties.

[0601] This specification includes the following inventions.

[0602] [1]: A film-forming composition, characterized in that the film-forming composition contains a polymer having an aromatic group having a pentafluorosulfanyl group as a substituent.

[0603] [2]: The film-forming composition according to [1] above, wherein the polymer is a polymer (a) having a repeating unit a having an aromatic group having a pentafluorosulfanyl group as a substituent.

[0604] [3]: The film-forming composition according to the above [2], wherein the repeating unit a is represented by any one of the following formulas (a1) to (a4): [ka] (In the above formula, p is an integer of 1 to 3, n is an integer of 0 to 5, and m is an integer of 0 to 4. R1 is a hydrogen atom or a methyl group, R2 is a hydrocarbyl group having 1 to 6 carbon atoms, a hydrocarbyloxy group having 1 to 12 carbon atoms, a hydrocarbyloxycarbonyl group having 2 to 6 carbon atoms, a hydrocarbylcarbonyloxy group having 2 to 12 carbon atoms, a hydroxy group, a carboxy group, a halogen atom, a trifluoromethoxy group, a cyano group, or a nitro group. X1 is a single bond, an ester bond, an ether bond, a sulfonate ester group, a sulfonamide group, an amide bond, or is a phenylene group; X2, when p is 1, is a single bond or a hydrocarbylene group having 1 to 20 carbon atoms; when p is 2 or 3, is a (p+1)-valent hydrocarbon group having 1 to 20 carbon atoms; these hydrocarbylene groups and (p+1)-valent hydrocarbon groups may contain at least one atom selected from oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms. X3 is a single bond or an ether bond. Ar1 is each independently a (m+n+1)-valent group derived from benzene or naphthalene, provided that at least one of the n's in the formula is 1 or greater. [ka] (In the above formula, n and m are the same as defined above, l is an integer of 0 to 3, and at least one of the two n's and two l's in the formula is 1 or greater. R2 and X3 are the same as defined above, and R3 is the following general formula (a2-1). Ar2's are each independently an (n+m+l+2)-valent aromatic hydrocarbon group having 6 to 30 carbon atoms. Ar3 is an (n+m+l+1)-valent group derived from benzene or naphthalene.) [ka] (In the above formula, X3 and n are the same as defined above, X4 is a single bond or a hydrocarbylene group having 1 to 12 carbon atoms, and the hydrocarbylene group may have at least one of a hydroxy group, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, an ether bond, an ester bond, and an amide bond. Ar4 is an (n+1)-valent group derived from benzene or naphthalene.) [ka] (In the above formula, n, m, l, Ar2, R2, R3, and X3 are the same as defined above, and R4 is a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms, and the hydrocarbyl group may contain an oxygen atom. However, it does not contain a substituent containing SF5. Also, at least one of n and l in the formula is 1 or greater.) [ka] (wherein R3 and R4 are the same as above.)

[0605] [4]: The film-forming composition according to the above [3], wherein the repeating unit a is represented by the formula (a1).

[0606] [5]: The film-forming composition according to any one of the above [2] to [4], wherein the polymer (a) further comprises a repeating unit (b1) having a hydrophilic group selected from an ether bond, an ester bond, a hydroxy group, a carboxy group, a sulfonamide bond, a sulfonimide bond, a sulfo group, a lactone ring, a sultone ring, a carbonate bond, a urethane bond, and an amide bond.

[0607] [6]: The film-forming composition according to any one of the above [2] to [5], characterized in that the film-forming composition is a composition for forming an organic film, comprising (A) an organic film-forming resin or compound, (B) the polymer (a), and (C) a solvent.

[0608] [7]: The film-forming composition according to [6] above, characterized in that the content of the component (B) is 0.01 to 5 parts by mass when the component (A) is taken as 100 parts by mass.

[0609] [8]: The film-forming composition according to the above [6] or [7], further comprising (D) a photoacid generator or (E) a thermal acid generator.

[0610] [9]: A method for forming an organic film used in the manufacturing process of a semiconductor device, comprising spin-coating the film-forming composition according to any one of [6] to [8] above onto a substrate to be processed, and heat-treating the substrate coated with the 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.

[0611]

[10] : A pattern forming method comprising the steps of forming an organic film on a workpiece using the film-forming composition according to any one of [6] to [8] 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.

[0612]

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

[0613]

[12] : A pattern forming method comprising the steps of forming an organic film on a workpiece using the film-forming composition according to any one of [6] to [8] 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.

[0614]

[13] : A pattern forming method comprising the steps of forming an organic film on a workpiece using the film-forming composition according to any one of [6] to [8] above, forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming an organic antireflective film or an adhesive film on the inorganic hard mask, forming a resist upper layer film on the organic antireflective film or 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 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.

[0615]

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

[12] or

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

[0616]

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

[10] to

[13] above, 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.

[0617]

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

[10] to

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

[0618]

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

[10] to

[13] , characterized in 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.

[0619]

[18] : The pattern forming method according to

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

[0620]

[19] : A pattern forming method comprising the steps of: forming a resist film on a substrate using the film-forming composition according to any one of [6] to [8] above; exposing the resist film to high-energy rays; and developing the exposed resist film using a developer.

[0621]

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

[19] , wherein the high-energy radiation is g-ray, i-ray, KrF excimer laser, ArF excimer laser, ultraviolet light, electron beam, or extreme ultraviolet light having a wavelength of 3 to 15 nm.

[0622]

[21] : A monomer represented by the following general formula (a5): [ka] (In the formula, R x is a hydrogen atom or a methyl group, and X a is a linking group having 1 to 12 carbon atoms which is a single bond, a phenylene group, a naphthylene group, or an ester bond, an ether bond, or a lactone ring, and may have an oxygen atom, a nitrogen atom, a sulfur atom, and / or a halogen atom; La is an acid labile group which has an aromatic group having at least one pentafluorosulfanyl group as a substituent.

[0623]

[22] : The monomer according to the above

[21] , which is represented by the following general formula (a6): [ka] (In the formula, X a , R x As mentioned above. R 11 , R 12 are each independently a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkenyl group having 2 to 12 carbon atoms, a linear, branched, or cyclic alkynyl group having 2 to 12 carbon atoms, or an aryl group having 5 to 10 carbon atoms, which may have an oxygen atom and / or a sulfur atom; R 11 and R 12 may be bonded to form a ring. 13 are each independently a hydrogen atom, a halogen atom, or an alkyl or alkoxy group having 1 to 4 carbon atoms. m is an integer of 0 to 4, and n is an integer of 1 to 3.

[0624]

[23] : A polymer comprising a repeating unit represented by the following general formula (a7) and having a weight average molecular weight in the range of 100 to 500,000: [ka] (In the formula, R x is a hydrogen atom or a methyl group, and X ais a linking group having 1 to 12 carbon atoms which is a single bond, a phenylene group, a naphthylene group, or an ester bond, an ether bond, or a lactone ring, and may have an oxygen atom, a nitrogen atom, a sulfur atom, and / or a halogen atom; La is an acid labile group which has an aromatic group having at least one pentafluorosulfanyl group as a substituent.

[0625]

[24] : The polymer according to the above

[23] , which contains a repeating unit represented by the following general formula (a8) and has a weight-average molecular weight in the range of 100 to 500,000: [ka] (In the formula, X a , R x As mentioned above. R 11 , R 12 are each independently a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkenyl group having 2 to 12 carbon atoms, a linear, branched, or cyclic alkynyl group having 2 to 12 carbon atoms, or an aryl group having 5 to 10 carbon atoms, which may have an oxygen atom and / or a sulfur atom; R 11 and R 12 may be bonded to form a ring. 13 are each independently a hydrogen atom, a halogen atom, or an alkyl or alkoxy group having 1 to 4 carbon atoms. m is an integer of 0 to 4, and n is an integer of 1 to 3.

[0626] 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]

[0627] 1...substrate, 2...processed layer, 2a...pattern formed on the processed layer, 3...organic film, 3a...organic film pattern, 4...silicon-containing resist intermediate film, 4a...silicon-containing resist intermediate film pattern, 5...resist upper layer film, 5a...resist upper layer film pattern, 6...exposed portion, 7...underlying substrate, 8...Resist underlayer film.

Claims

1. A film-forming composition, The film-forming composition is characterized in that the film-forming composition contains a polymer having an aromatic group having a pentafluorosulfanyl group as a substituent.

2. 2. The film-forming composition according to claim 1, wherein the polymer (a) is a polymer having a repeating unit a having an aromatic group having a pentafluorosulfanyl group as a substituent.

3. 3. The film-forming composition according to claim 2, wherein the repeating unit a is represented by any one of the following formulas (a1) to (a4): 【Chemical 1】 (In the above formula, p is an integer of 1 to 3, n is an integer of 0 to 5, and m is an integer of 0 to 4. R １ is a hydrogen atom or a methyl group, and R ２ is a hydrocarbyl group having 1 to 6 carbon atoms, a hydrocarbyloxy group having 1 to 12 carbon atoms, a hydrocarbyloxycarbonyl group having 2 to 6 carbon atoms, a hydrocarbylcarbonyloxy group having 2 to 12 carbon atoms, a hydroxy group, a carboxy group, a halogen atom, a trifluoromethoxy group, a cyano group, or a nitro group. １ is a single bond, an ester bond, an ether bond, a sulfonate ester group, a sulfonamide group, an amide bond or a phenylene group, and X ２ When p is 1, X is a single bond or a hydrocarbylene group having 1 to 20 carbon atoms, and when p is 2 or 3, X is a (p+1)-valent hydrocarbon group having 1 to 20 carbon atoms, and these hydrocarbylene groups and (p+1)-valent hydrocarbon groups may contain at least one atom selected from an oxygen atom, a sulfur atom, a nitrogen atom, and a halogen atom. ３ is a single bond or an ether bond. １ are each independently an (m+n+1)-valent group derived from benzene or naphthalene, provided that at least one of the n's in the formula is 1 or greater. 【Chemistry 2】 (In the above formula, n and m are the same as above, and l is an integer of 0 to 3, and at least one of the two n's and two l's in the formula is 1 or more. R ２ , X ３ is the same as above, and R ３ is the following general formula (a2-1): ２ are each independently an aromatic hydrocarbon group having 6 to 30 carbon atoms and a valence of (n+m+l+2). ３ is an (n+m+l+1)-valent group derived from benzene or naphthalene. 【Chemistry 3】 (In the above formula, X ３ , n is the same as above, X ４ is a single bond or a hydrocarbylene group having 1 to 12 carbon atoms, and the hydrocarbylene group may have at least one of a hydroxy group, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, an ether bond, an ester bond, and an amide bond. ４ is an (n+1)-valent group derived from benzene or naphthalene. 【Chemistry 4】 (In the above formula, n, m, l, Ar ２ , R ２ , R ３ , X ３ is the same as above, R ４ is a hydrogen atom or a hydrocarbyl group having 1 to 10 carbon atoms, and the hydrocarbyl group may contain an oxygen atom. ５ In addition, at least one of n and l in the formula is 1 or greater.) 【Chemistry 5】 (In the formula, R ３ , R ４ is the same as above.)

4. 4. The film-forming composition according to claim 3, wherein the repeating unit a is represented by formula (a1).

5. 3. The film-forming composition according to claim 2, wherein the polymer (a) further comprises a repeating unit (b1) having a hydrophilic group selected from an ether bond, an ester bond, a hydroxy group, a carboxy group, a sulfonamide bond, a sulfonimide bond, a sulfo group, a lactone ring, a sultone ring, a carbonate bond, a urethane bond, and an amide bond.

6. 3. The film-forming composition according to claim 2, wherein the film-forming composition is an organic film-forming composition comprising (A) an organic film-forming resin or compound, (B) the polymer (a), and (C) a solvent.

7. 7. The film-forming composition according to claim 6, wherein the content of the component (B) is 0.01 to 5 parts by mass relative to 100 parts by mass of the component (A).

8. 7. The film-forming composition according to claim 6, further comprising (D) a photoacid generator or (E) a thermal acid generator.

9. A method for forming an organic film used in a manufacturing process of a semiconductor device, comprising spin-coating the film-forming composition according to any one of claims 6 to 8 onto a substrate to be processed, and heat-treating the substrate coated with the 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.

10. 10. A pattern forming method comprising the steps of: forming an organic film on a workpiece using the film-forming composition according to claim 6; 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.

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

12. 10. A pattern forming method comprising the steps of: forming an organic film on a workpiece using the film-forming composition according to claim 6; 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.

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

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

15. 14. The pattern formation method according to claim 10, 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.

16. 14. The pattern forming method according to claim 10, wherein the circuit pattern is developed using an alkali developer or an organic solvent in forming the circuit pattern.

17. 14. The pattern forming method according to claim 10, wherein the workpiece is a semiconductor device substrate, or a semiconductor device substrate having any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film formed thereon.

18. 18. The pattern formation method according to claim 17, 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.

19. 9. A pattern forming method comprising the steps of: forming a resist film on a substrate using the film-forming composition according to claim 6; exposing the resist film to high-energy rays; and developing the exposed resist film using a developer.

20. 20. The pattern formation method according to claim 19, wherein the high-energy radiation is g-ray, i-ray, KrF excimer laser, ArF excimer laser, ultraviolet ray, electron beam, or extreme ultraviolet ray having a wavelength of 3 to 15 nm.

21. A monomer represented by the following general formula (a5): 【Chemistry 6】 (In the formula, R ｘ is a hydrogen atom or a methyl group, and X ａ is a linking group having 1 to 12 carbon atoms which contains a single bond, a phenylene group, a naphthylene group, an ester bond, an ether bond, or a lactone ring, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, and / or a halogen atom; La is an acid labile group which contains an aromatic group having at least one pentafluorosulfanyl group as a substituent.

22. The monomer according to claim 21, characterized in that it is represented by the following general formula (a6): 【Chemistry 7】 (In the formula, X ａ , R ｘ As mentioned above. １１ , R １２ are each independently a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkenyl group having 2 to 12 carbon atoms, a linear, branched, or cyclic alkynyl group having 2 to 12 carbon atoms, or an aryl group having 5 to 10 carbon atoms, which may have an oxygen atom and / or a sulfur atom; R １１ and R １２ may be bonded to form a ring. １３ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group; m is an integer of 0 to 4, and n is an integer of 1 to 3.

23. A polymer comprising a repeating unit represented by the following general formula (a7) and having a weight average molecular weight in the range of 100 to 500,000: 【Chemistry 8】 (In the formula, R ｘ is a hydrogen atom or a methyl group, and X ａ is a linking group having 1 to 12 carbon atoms which contains a single bond, a phenylene group, a naphthylene group, an ester bond, an ether bond, or a lactone ring, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, and / or a halogen atom; La is an acid labile group which contains an aromatic group having at least one pentafluorosulfanyl group as a substituent.

24. The polymer according to claim 23, characterized in that it contains a repeating unit represented by the following general formula (a8) and has a weight average molecular weight in the range of 100 to 500,000: 【Chemistry 9】 (In the formula, X ａ , R ｘ As mentioned above. １１ , R １２ are each independently a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkenyl group having 2 to 12 carbon atoms, a linear, branched, or cyclic alkynyl group having 2 to 12 carbon atoms, or an aryl group having 5 to 10 carbon atoms, which may have an oxygen atom and / or a sulfur atom; R １１ and R １２ may be bonded to form a ring. １３ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group; m is an integer of 0 to 4, and n is an integer of 1 to 3.

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