Organic film forming composition, organic film forming method, pattern forming method, and polymer

Abstract

To provide an organic film forming composition that achieves excellent film-forming performance (in-plane uniformity) and embedding characteristics on a substrate (wafer), suppresses hump formation during an EBR process, and exhibits excellent process margin when used as an organic underlayer film for a multilayer resist, and to provide an organic film forming method and a pattern forming method using the composition.SOLUTION: An organic film forming composition contains (A) an organic film forming resin or compound, (B) a polymer having, as a repeating unit, a partial structure (a1) represented by the following general formula (1), and (C) a solvent (where R1 and R2 are a hydrogen atom or a saturated or unsaturated organic group having a carbon number of 1 to 20, and have at least one structure containing fluorine represented by the following general formula (2), and at least one of R1 and R2 represents an organic group that is not a hydrogen atom. * represents a bonding site).SELECTED DRAWING: None

Description

[Technical Field]

[0001] 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.

[0002] 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.

[0003] In this three-layer resist method, for example, an organic film such as novolak is uniformly formed on a substrate to be processed as a resist underlayer, a silicon-containing film is formed on top of that as a resist middle layer, and a conventional organic photoresist film is formed on top of that as a resist upper layer. For dry etching using fluorine-based gas plasma, the organic resist upper layer has a good etching selectivity relative to the silicon-containing resist middle layer, so the resist pattern is transferred to the silicon-containing resist middle layer by dry etching using fluorine-based gas plasma. This method allows for pattern transfer to the silicon-containing film even when using a resist composition that is difficult to form a pattern with a sufficient thickness for directly processing the substrate to be processed, or a resist composition that does not have sufficient dry etching resistance for processing the substrate. Subsequent pattern transfer using dry etching using oxygen-based gas plasma allows for the formation of a novolak film pattern with sufficient dry etching resistance for processing.

[0004] 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.

[0005] 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).

[0006] 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.

[0007] 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.

[0008] 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.

[0009] 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.

[0010] 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.

[0011] 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).

[0012] 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]

[0013] [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]

[0014] The present invention has been made in view of the above circumstances, and aims to provide a composition for forming an organic film that has excellent film-forming properties (in-plane uniformity) and filling properties on a substrate (wafer), suppresses humps during an EBR process, and has excellent process tolerance when used as an organic underlayer film for a multilayer resist; an organic film-forming method using the composition; a pattern-forming method; and a polymer. [Means for solving the problem]

[0015] In order to achieve the above object, the present invention provides: An organic film-forming composition, (A) an organic film-forming resin or compound; (B) a polymer having a partial structure (a1) represented by the following general formula (1) as a repeating unit, and (C) Solvent The present invention provides a composition for forming an organic film, which comprises: [ka] (In the formula, R1 and R2 are hydrogen atoms or saturated or unsaturated organic groups having 1 to 20 carbon atoms, and have at least one fluorine-containing structure represented by the following general formula (2), and at least one of R1 and R2 is an organic group other than a hydrogen atom. * represents a bond.) [ka] (* represents a bond.)

[0016] In the case of an organic film-forming composition containing a polymer having such a partial structure in its repeating unit, the introduction of a specific fluorine structure into the repeating unit of the polymer can impart the necessary surface activity effect during organic film formation, thereby improving film formability during application. Furthermore, if an appropriate structure, such as a pentafluorobenzene or pentafluorosulfanyl group, is selected as the structure represented by R1 and R2 of the present invention, it does not belong to the PFAS classification, and is therefore advantageous from the perspective of preventing environmental pollution, and can be expected to be a highly versatile material as a surfactant for organic films.

[0017] The repeating unit (a1) of the polymer (B) is preferably a repeating unit represented by the following general formula (3) or (4). [ka] (In the formula, R1 and R2 are the same as above, R3 represents a hydrogen atom or a methyl group, and n1 represents an integer of 2 to 10.) [ka] (In the formula, R1 and R2 are the same as above, and R4 represents a divalent organic group having 2 to 30 carbon atoms, which may contain an ether bond, ester bond, amide bond, or sulfide bond.)

[0018] In an organic film-forming composition containing a polymer having such a structure, the substituents R1 and R2 in the repeating unit can enhance the interaction of the fluorine structure, thereby imparting good surfactant performance. Therefore, the organic film-forming material of the present invention can provide an organic film-forming material with excellent film-forming properties even when various polymers and compounds are used.

[0019] The polymer (B) is preferably a copolymer having repeating units of the general formula (3) and the following general formula (5). [ka] (In the formula, R3 is the same as defined above, R5 and R6 each represent a linear or branched divalent alkylene group having 1 to 4 carbon atoms, R7 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, m1 represents 0 to 23, m2 represents 0 to 23, and 23≧m1+m2≧2.)

[0020] As described above, the organic film-forming composition of the present invention is an organic film-forming material with excellent film-forming properties, but by forming it into a copolymer containing a repeating unit having a linking group such as (5), the repeating unit (5) contributes as a unit for relaxing the aggregation structure to an appropriate degree, making it possible to adjust the surface activity. Therefore, it is possible to provide an organic film-forming material that can accommodate various film thicknesses (independent of solution concentration) and that combines filling properties and film-forming properties.

[0021] Furthermore, the fluorine-containing organic group represented by R1 or R2 of the polymer (B) preferably has at least one structure of any one of the following general formulas (6). [ka]

[0022] As mentioned above, chemical substance management regarding PFAS regulations has been strengthened, and the fluorine atom, pentasulfanyl group, and aromatic group substituted with a pentasulfanyl group shown above are not classified as PFAS in REACH. In addition, difluoromethoxy group and aromatic group substituted with a fluorine atom are not classified as PFAS in OECD. Therefore, the organic film-forming composition using the polymer of the present invention as a surfactant not only provides excellent film-forming properties, but can also be expected to be an environmentally friendly material.

[0023] Furthermore, the weight average molecular weight of the polymer (B) is preferably 1,500 to 30,000.

[0024] Within this weight-average molecular weight range, it is possible to form an organic film with excellent film-forming and filling properties, and it is also possible to control the contact angle of the film surface after film formation within an appropriate range, thereby forming an organic underlayer film suitable for use in a multilayer resist process.

[0025] Furthermore, when the organic film-forming resin or compound (A) is taken as 100 parts by mass, the content of the polymer (B) is preferably 0.01 to 5 parts by mass.

[0026] A composition for forming an organic film containing the polymer in such an amount is preferable because the formed organic film has better in-plane uniformity.

[0027] The present invention also provides a method for forming an organic film used in the manufacturing process of a semiconductor device, which comprises spin-coating the above-described composition for forming an organic film on a workpiece, and heat-treating the substrate coated with the composition for forming an organic film at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds, thereby forming a cured film.

[0028] 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.

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

[0030] The organic film-forming composition of the present invention can be suitably used in a pattern formation method using a three-layer resist process that uses such a silicon-containing resist intermediate film.

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

[0032] The organic film-forming composition of the present invention can be suitably used in a pattern formation method using a four-layer resist process that uses such a silicon-containing resist intermediate film and an organic anti-reflective film or adhesive film.

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

[0034] The organic film-forming composition of the present invention can be suitably used in a pattern formation method using a three-layer resist process that uses such an inorganic hard mask intermediate film.

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

[0036] The organic film-forming composition of the present invention can be suitably used in a pattern formation method using a four-layer resist process using such an inorganic hard mask intermediate film and an organic anti-reflective film or adhesive film.

[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 intermediate film, and a four-layer resist process using an organic antireflective film or an adhesive film in addition to these. Such a pattern formation method of the present invention makes it possible to transfer and form the circuit pattern of the resist upper layer film onto the workpiece with high precision.

[0038] The inorganic hard mask intermediate film is preferably 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 intermediate film can be formed by such a method.

[0040] Furthermore, in forming the circuit pattern, the circuit pattern can be formed 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] The pattern forming method of the present invention makes it possible to form a circuit pattern in this manner.

[0042] In forming the circuit pattern, it is preferable to develop the circuit pattern using an alkali developer or an organic solvent.

[0043] In the pattern forming method of the present invention, such circuit pattern forming means and developing means can be suitably used.

[0044] The present invention also provides the above-described pattern formation method, in which 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.

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

[0046] The present invention provides a pattern formation method in which silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum, or an alloy thereof is used as the metal constituting the workpiece.

[0047] In the pattern forming method of the present invention, a pattern can be formed using the above-mentioned metals.

[0048] The present invention provides a polymer having a partial structure (a1) represented by the following general formula (1) as a repeating unit. [ka] (In the formula, R1 and R2 are hydrogen atoms or saturated or unsaturated organic groups having 1 to 20 carbon atoms, and have at least one fluorine-containing structure represented by the following general formula (2), and at least one of R1 and R2 is an organic group other than a hydrogen atom. * represents a bond.) [ka] (* represents a bond.)

[0049] The present invention provides a polymer characterized in that the repeating unit (a1) of the polymer is a repeating unit represented by the following general formula (3) or (4). [ka] (In the formula, R1 and R2 are the same as above, R3 represents a hydrogen atom or a methyl group, and n1 represents an integer of 2 to 10.) [ka] (In the formula, R1 and R2 are the same as above, and R4 represents a divalent organic group having 2 to 30 carbon atoms, which may contain an ether bond, ester bond, amide bond, or sulfide bond.)

[0050] A polymer having such a structure can enhance the interaction due to the action of R1 and R2, which contain fluorine atoms as substituents in the repeating unit, and when the polymer of the present invention is used as a surfactant, it can impart good film-forming properties.

[0051] In this case, the polymer is preferably a copolymer having repeating units of the above general formula (3) and the following general formula (5). [ka] (In the formula, R3 is the same as defined above, R5 and R6 each represent a linear or branched divalent alkylene group having 1 to 4 carbon atoms, R7 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, m1 represents 0 to 23, m2 represents 0 to 23, and 23≧m1+m2≧2.)

[0052] As described above, when the copolymer contains the repeating unit shown in (5), it functions as a unit that relaxes the aggregation structure of the repeating unit containing the fluorine unit when the polymer of the present invention is used as a surfactant, and is expected to be a material that can be used to form a film independently of organic compounds or resins when the polymer of the present invention is used as a surfactant.

[0053] Furthermore, the polymer preferably has at least one structure of the following general formula (6) as the fluorine-containing structure represented by R1 or R2. [ka]

[0054] As mentioned above, polymers with the above-mentioned fluorine structure are expected to be environmentally friendly materials, particularly those that can comply with recent PFAS regulations. [Effects of the Invention]

[0055] As described above, the present invention can provide an organic film-forming composition that exhibits excellent film-forming properties (in-plane uniformity) and filling characteristics on a substrate (wafer), exhibits excellent film-forming properties on an organic film when used as an organic underlayer film, and suppresses hump formation during the EBR process. Furthermore, by combining specific units to form a copolymer, the composition can be applied to a variety of organic film-forming materials. In particular, the organic film-forming composition of the present invention exhibits excellent film-forming properties, filling characteristics, and suppresses hump formation during the EBR process. Therefore, the composition is particularly useful as an 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 an inorganic hard mask interlayer, or a four-layer resist process using a silicon-containing resist interlayer or an inorganic hard mask interlayer and an organic antireflective film, or as a film-forming material for semiconductor device manufacturing, such as a photoresist material or a silicon-containing resist interlayer material. Therefore, the organic film forming method of the present invention can form an organic film in which humps are suppressed, and therefore semiconductor devices and the like can be manufactured efficiently. [Brief explanation of the drawings]

[0056] [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

[0057] The present invention will be described in more detail below. As mentioned above, there has been a demand for a material that not only provides film-forming properties as an organic film material but also has a surfactant effect with a low environmental impact. There has also been a demand for the development of an organic film-forming composition that, when used as an organic underlayer film material, has excellent film-forming properties (in-plane uniformity) and filling properties on a substrate (wafer), and that suppresses humps during the EBR process.

[0058] Typically, when forming an organic film, a resin for forming the organic film and additives are dissolved in an organic solvent to form a composition, which is then applied using a coater / developer onto a substrate on which structures, wiring, etc. have been formed. The composition is spread as the substrate rotates, and the composition at the edges is removed in an EBR process, followed by baking to form the organic film. If the surfactant effect of the above composition is insufficient, uneven distribution of the surfactant in the film occurs, resulting in the formation of voids when filling holes or trenches with very high aspect ratios. In addition, if the resin or additives used to form the organic film have poor solubility in the remover used in the EBR process, humps may form on the periphery of the organic film. The present inventors further conducted extensive research and found that by incorporating a polymer having a specific repeating unit into a composition for forming an organic film, a composition for forming an organic film having excellent film-forming properties, high-level embedding properties, and hump suppression during the EBR process can be obtained, thereby completing the present invention. Furthermore, by selecting a specific substituent structure, it is expected that the environmental load will be reduced, and the composition for forming an organic film will be industrially useful.

[0059] That is, the present invention provides a composition for forming an organic film, (A) an organic film-forming resin or compound; (B) a polymer having a partial structure (a1) represented by the following general formula (1) as a repeating unit, and (C) Solvent The organic film-forming composition is characterized by comprising: [ka] (In the formula, R1 and R2 are hydrogen atoms or saturated or unsaturated organic groups having 1 to 20 carbon atoms, and have at least one fluorine-containing structure represented by the following general formula (2), and at least one of R1 and R2 is an organic group other than a hydrogen atom. * represents a bond.) [ka] (* represents a bond.)

[0060] The present invention also provides a polymer having a partial structure (a1) represented by the following general formula (1) as a repeating unit. [ka] [ka]

[0061] The present invention will be described in detail below, but the present invention is not limited thereto.

[0062] [Polymer (B)] The polymer (B) of the present invention is a polymer having the partial structure (a1) represented by the following general formula (1) as a repeating unit. [ka] (In the formula, R1 and R2 are hydrogen atoms or saturated or unsaturated organic groups having 1 to 20 carbon atoms, and have at least one fluorine-containing structure represented by the following general formula (2), and at least one of R1 and R2 is an organic group other than a hydrogen atom. * represents a bond.) [ka] (* represents a bond.)

[0063] The fluorine-containing substituents R1 and R2 contained in the repeating units of the polymer (B) are preferably polymers having an aromatic group substituted with a fluorine atom, an aromatic group substituted with a trifluoromethoxy group, an aromatic group substituted with a pentasulfanyl group, or an aromatic group substituted with a pentasulfanyloxy group, as shown below. [ka]

[0064] Since the above structure does not fall under PFAS regulations, it is expected to be used as a polymer for forming organic films with a fluorine structure.

[0065] The repeating unit (a1) of the polymer (B) is preferably a repeating unit represented by the following general formula (3) or (4). [ka] (In the formula, R1 and R2 are the same as above, R3 represents a hydrogen atom or a methyl group, and n1 represents an integer of 2 to 10.) [ka] (In the formula, R1 and R2 are the same as above, and R4 represents a divalent organic group having 2 to 30 carbon atoms, which may contain an ether bond, ester bond, amide bond, or sulfide bond.)

[0066] [Polymer: Polymer (a1-1) having a repeating unit represented by general formula (3)] Monomers used to obtain the polymer (a1-1) having the repeating unit represented by general formula (3) include, but are not limited to, the following: In the following formula, R1 is the same as defined above. [ka]

[0067] [ka]

[0068]

change

[0069]

change

[0070]

change

[0071]

change

[0072]

change

[0073]

change

[0074]

change

[0075]

change

[0076]

change

[0077]

change

[0078]

change

[0079]

change

[0080]

change

[0081]

change

[0082]

change

[0083]

change

[0084]

change

[0085]

change

[0086]

change

[0087] The polymer (a1-1) preferably has a weight-average molecular weight (Mw) in terms of polystyrene, as determined by gel permeation chromatography (GPC) using THF as a solvent, of 1,000 to 500,000, more preferably 1,500 to 30,000, and even more preferably 2,000 to 30,000. Furthermore, if the molecular weight distribution (Mw / Mn) of the polymer (a1-1) is broad, the presence of low-molecular-weight and high-molecular-weight polymers may result in the deposition of foreign matter due to the ultrahigh molecular weight in the coating film, or the in-plane uniformity of the coating film may be impaired due to the low molecular weight. Furthermore, as miniaturization progresses, substrate shapes become more complex, requiring high-precision film-forming capabilities for various substrate shapes, so Mw and Mw / Mn must also be controlled. Therefore, to obtain an organic film material suitable for fine pattern processing, the Mw / Mn of the polymer (a1-1) is preferably narrowly distributed, i.e., 1.0 to 4.0, particularly 1.0 to 3.0. There are concerns that the surfactant effect will be reduced due to low molecular weight components, and that the hump characteristics will be deteriorated due to the reduced solubility of ultra-high molecular weight components. Therefore, it is preferable to narrow the degree of dispersion to the extent that these components are not contained in large amounts.

[0088] The polymer (a1-1) may contain two or more polymers having different composition ratios, Mw, and Mw / Mn.

[0089] The polymer (a1-1) can be obtained by polymerizing a monomer that gives a repeating unit selected from the repeating unit (a1-1) by a method such as radical polymerization, anionic polymerization, or cationic polymerization.

[0090] When the polymer (a1-1) contains two or more types of repeating units, it may be a random copolymer or a block copolymer, but the block copolymer has the advantage of being more effective as a surfactant. In particular, a block copolymer containing repeating units (a1) and (b1) is 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.

[0091] The polymer (a1-1) is preferably a copolymer further comprising a repeating unit having a hydrophilic group with an ether bond, as represented by general formula (5). By including a highly water-repellent repeating unit having a fluorine atom, as represented by general formula (3), and a repeating unit (5) having a hydrophilic group, the polymer can be sufficiently effective in improving film-forming properties. [ka] (In the formula, R3 is the same as defined above, R5 and R6 each represent a linear or branched divalent alkylene group having 1 to 4 carbon atoms, R7 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, m1 represents 0 to 23, m2 represents 0 to 23, and 23≧m1+m2≧2.)

[0092] The above R5 and R6 each represent a divalent alkylene group having 1 to 4 carbon atoms, which may be linear or branched. Specific examples of the divalent alkylene group having 1 to 4 carbon atoms, which may be linear or branched, include methylene, ethylene, propylene, butylene, trimethylene, and tetramethylene. Among these, an ethylene group is more preferred from the viewpoint of eliminating voids in film formation. The arrangement of (R5O) and (R6O) may be random, block, or multiblock.

[0093] The above R7 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group. Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an allyl group, an n-butyl group, an s-butyl group, a t-butyl group, and an isobutyl group. Among these, a hydrogen atom, a methyl group or an ethyl group, and a phenyl group are more preferred. A hydrogen atom or a methyl group is preferred from the viewpoint of ease of obtaining raw materials.

[0094] The above m1 is 0 to 23, m2 is 0 to 23, and 23≧m1+m2≧2. Here, m1 and m2 represent the average number of repetitions. The upper limit of m1+m2 is 23, and from the viewpoint of low-temperature storage stability, it is preferably 2≦m1+m2≦13, and more preferably 9≦m1+m2≦13.

[0095] Specific examples of the monomers used to obtain a polymer having a repeating unit represented by the above general formula (5) include the following. [ka]

[0096] [ka]

[0097] [ka]

[0098] In the copolymer, when the ratio of the repeating unit represented by general formula (3) is (a1-1) and the ratio of the polymer represented by general formula (5) is (b1), the content ratio is preferably 0≦(a1-1)<1.0 and 0<(b1)<1.0, more preferably 0.1≦(a1-1)≦0.9 and 0.1≦(b1)≦0.9, and even more preferably 0.2≦(a1-1)≦0.8 and 0.2≦(b1)≦0.8, where (a1-1)+(b1)=1.0.

[0099] Furthermore, the polymer can be prepared by combining one or more monomers that provide a structural unit represented by general formula (3) and one or more monomers that provide a structural unit represented by general formula (5). For example, to improve film-forming properties, a combination of monomers that provide multiple repeating units of (3) can be used, or multiple monomers that provide a repeating unit represented by (5) can be used, or multiple monomers that provide repeating units of (3) and (5) can be used. This allows for appropriate selection based on the properties of the resin or compound used in the organic film to be applied. This allows for performance adjustment to obtain the desired film-forming properties, even for single compounds such as phenolic resins, radical polymers, polyimides, polyimines, polycarbonates, and other polyfunctional phenolic compounds, depending on the resin or compound used in the organic film-forming material.

[0100] [Method for producing polymer (a1-1)] The polymer (a1-1) can be produced by polymerization using a method such as radical polymerization, anionic polymerization, or cationic polymerization, as described above. An example is shown below:

[0101] Examples of organic solvents used during polymerization include toluene, benzene, THF, diethyl ether, dioxane, cyclohexane, cyclopentane, methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), and γ-butyrolactone (GBL). Examples of the polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2-azobis(2-methylpropionate), 1,1'-azobis(1-acetoxy-1-phenylethane), benzoyl peroxide, and lauroyl peroxide. The amount of these initiators added is preferably 0.01 to 25 mol% based on the total amount of monomers to be polymerized. The reaction temperature is preferably 50 to 150°C, more preferably 60 to 100°C. The reaction time is preferably 2 to 24 hours, and more preferably 2 to 18 hours from the viewpoint of production efficiency.

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

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

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

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

[0144] to

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

[0106] When the polymer is used as a polymer solution, the concentration of the polymer in the solution is preferably 0.1 to 60% by mass, more preferably 1 to 50% by mass. If the concentration is too high, the viscosity increases and handling performance deteriorates. If the concentration is too low, the polymer and compound solution must be diluted to a large extent in order to add a predetermined amount of surfactant to the product when the polymer and compound are used as a material for forming an organic film, which narrows the film thickness range that can be produced, which is inconvenient.

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

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

[0109] Furthermore, random copolymerization using 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 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 using radical polymerization. In the living radical polymerization method known as reversible addition fragmentation chain transfer (RAFT) polymerization, radicals at the polymer end are always alive. Therefore, by initiating polymerization with the first monomer and adding the second monomer once the first monomer is consumed, it is possible to form a block copolymer consisting of the first and second repeating units. Initiating polymerization with the first monomer, adding the second monomer once the first monomer is consumed, and then adding the third monomer can form a triblock copolymer. RAFT polymerization is also characterized by the formation of narrow-dispersity polymers.

[0110] 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.

[0111] 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.

[0112] When the monomers are added all at once and RAFT polymerization is performed, random and narrowly dispersed polymers can be synthesized.

[0113] [Another method for producing polymer (a1-1) having a repeating unit represented by formula (3)] Another method for producing the polymer (a1-1) is to add a radical polymerization initiator to a monomer having an acetylacetone structure in an organic solvent, heat the mixture, and polymerize (Step 1), followed by an addition reaction with a halide, mesylate, or tosylate having R1 or R2 as a substituent in the presence of a base catalyst (Step 2). (In the formula below, X represents a halide, mesylate, or tosylate, and R1, R2 (where R2 is other than a hydrogen atom), R3, and n1 are the same as above.) [ka]

[0114] When the above reaction method is used, due to the reaction selectivity and the presence of two reaction sites for the repeating unit of the polymer, a reaction rate of 100% means that R1 and R2 are completely introduced as substituents. When R1≠R2, three types as follows are obtained, and when R1 = R2 = R’, one type is obtained. Also, when the reaction rate is less than 100%, a polymer with a repeating unit having a plurality of combinations as follows can be obtained. When R1≠R2, six types as follows are obtained, and when R1 = R2 = R’, two types are obtained. By adjusting the overall charge ratio, it becomes possible to control the reaction rate with respect to the overall reaction sites, and substituents corresponding to a plurality or a single R1 and R2 can be combined and used according to the required performance. For example, when the substitution rate in the repeating unit of the polymer is 100, when the ratio substituted by R1 and R2 is a and the ratio present as an unmodified hydrogen atom is b, 0≦a + b≦100, 0.5 < a≦1.0 is preferable, and 0.7≦a≦1.0 is more preferable. At this time, a polymer containing the repeating unit shown below is obtained depending on the relationship between R1 and R2.

[0115] [In the case of a reaction rate of 100%] [Chemical formula] [In the case of a reaction rate < 100%] [Chemical formula]

[0116] As a method for obtaining the above polymer, for the polymerization in Step1, only the monomer is changed to the one corresponding to the precursor, and it can be obtained by the method described in paragraphs

[0100] ~

[0112] . The polymer obtained in Step1 can be used for the addition reaction in Step2.

[0117] Examples of base catalysts used in the substitution reaction of Step 2 include inorganic base compounds such as sodium bicarbonate, sodium carbonate, potassium carbonate, calcium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride, and potassium phosphate, and organic amine compounds such as triethylamine, pyridine, and N-methylmorpholine. These may be used alone or in combination of two or more. The amount of the catalyst used is in the range of 0.1 to 20 moles, preferably 0.2 to 10 moles, relative to the number of moles of the starting amic acid.

[0118] The solvent used in this reaction is not particularly limited as long as it is inert to the reaction, but examples include ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; aromatic solvents such as benzene, toluene, and xylene; acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, and water, which can be used alone or in combination. These solvents can be used in an amount of 0 to 2000 parts by mass per 100 parts by mass of the reaction raw materials, and the reaction temperature is preferably from -50°C to the boiling point of the solvent, more preferably from room temperature to 150°C. The reaction time is appropriately selected from the range of 0.1 to 100 hours.

[0119] Reaction methods include charging the polymer obtained in step 1, a halide, mesylate, or tosylate having R1 and R2 as substituents, and a catalyst all at once, dispersing or dissolving the polymer obtained in step 1 and the halide, mesylate, or tosylate having R1 and R2 as substituents, and then adding the catalyst all at once or diluting it with a solvent and adding it dropwise, or dispersing or dissolving the catalyst, and then adding the polymer obtained in step 1 and the halide, mesylate, or tosylate having R1 and R2 as substituents all at once or diluting it with a solvent and adding it dropwise. After the reaction is complete, the product may be used as is as an organic film material, or it may be recovered by diluting it with an organic solvent and then separating and washing to remove unreacted raw materials, catalyst, etc. present in the system.

[0120] The organic solvent used here is not particularly limited as long as it can dissolve the compound and separate into two layers when mixed with water. Examples include hydrocarbons such as hexane, heptane, benzene, toluene, and xylene; esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate; ketones such as methyl ethyl ketone, methyl amyl ketone, cyclohexanone, and methyl isobutyl ketone; ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, and ethyl cyclopentyl methyl ether; chlorinated solvents such as methylene chloride, chloroform, dichloroethane, and trichloroethylene; and mixtures thereof. The washing water used here is typically what is known as deionized water or ultrapure water. The number of washes may be one or more times, but washing 10 or more times does not necessarily provide the desired effect, so washing is preferably performed 1 to 5 times.

[0121] In order to remove unreacted raw materials or acidic components from the system during separation and washing, washing may be performed with a basic aqueous solution. Specific examples of the base include alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates, ammonia, and organic ammonium.

[0122] Furthermore, in order to remove unreacted raw materials, metal impurities, or basic components from the system during separation and washing, washing with an acidic aqueous solution may be performed. Specific examples of the acid include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropolyacids, and organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid.

[0123] The separation washing with the basic aqueous solution or the acidic aqueous solution may be carried out either alone or in combination. From the viewpoint of removing metal impurities, the separation washing is preferably carried out in the order of the basic aqueous solution and the acidic aqueous solution.

[0124] After the separation washing with the basic aqueous solution or acidic aqueous solution, washing with neutral water may be carried out subsequently. The number of washings may be one or more times, but is preferably about 1 to 5 times. As the neutral water, the above-mentioned deionized water or ultrapure water may be used. The number of washings may be one or more times, but if the number of washings is too few, the basic components and acidic components may not be removed. Washing 10 or more times does not necessarily provide the effect of washing alone, so it is preferably about 1 to 5 times.

[0125] Furthermore, the reaction product after the separation operation can be recovered as a powder by concentrating the solvent to dryness or crystallizing it under reduced or normal pressure, but it can also be left in a solution state with a moderate concentration to improve operability when preparing an organic film material. The concentration in this case is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by weight. At such a concentration, the viscosity is unlikely to increase, preventing a loss of operability, and the amount of solvent is not excessive, making it economical.

[0126] The solvent used in this case is not particularly limited as long as it can dissolve the compound, and specific examples include ketones such as cyclohexanone and methyl 2-amyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, and propylene glycol mono tert-butyl ether acetate. These can be used alone or in combination of two or more. Furthermore, the obtained polymer can be used by filtering the obtained polymerization solution as described in

[0107] and

[0108] .

[0127] Furthermore, in producing the polymer obtained by this method, it is possible to combine halides, mesylates, or halides other than tosylate, tosylates, and mesylates having R1 and R2 as substituents, depending on the required performance.

[0128] [Polymer: Polymer (a1-2) having a repeating unit represented by general formula (4)] The polymer (a1-2) having the repeating unit represented by general formula (4) is a so-called polyester. The polymer can be obtained by a dehydration condensation reaction between a diol and a biscarboxylic acid, or by transesterification with an acid halide or anhydride corresponding to the biscarboxylic acid, or a biscarboxylic acid ester.

[0129] Examples of the diol compound include the following: Among these, diols linked by glyme chains or diols linked by alkyl groups are preferred from the viewpoint of surfactant effect. [ka]

[0130] Examples of the biscarboxylic acid compound include the following. [ka]

[0131] [ka]

[0132] [ka]

[0133] As with polymer (a1-1), the Mw and Mw / Mn of polymer (a1-2) must be controlled within appropriate ranges for microfabrication. Specifically, the weight-average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) using THF as a solvent is preferably 1,000 to 500,000, more preferably 1,500 to 30,000, and even more preferably 2,000 to 30,000. The Mw / Mn is preferably 1.0 to 4.0, particularly 1.0 to 3.0, with a narrow dispersity.

[0134] [Method for producing polymer (a1-2)] As a method for producing the polymer (a1-2), as described above, the polymer can be obtained by the dehydration condensation reaction between a diol and a biscarboxylic acid, or by transesterification with an acid halide or acid anhydride corresponding to the biscarboxylic acid, or a biscarboxylic acid ester. Reaction schemes for dehydration condensation, acid halide, and transesterification are shown below as examples of the reaction scheme. These can be appropriately selected taking into consideration the stability of the raw materials used, etc. (In the following formula, R1, R2, and R4 are the same as above, X1 is a halogen atom, and R″ is an alkyl group having 1 to 5 carbon atoms.) [Dehydration condensation] [ka] [Interesterification] [ka] [Acid halides] [ka]

[0135] When the polymer (a1-2) is produced by dehydration condensation or transesterification as described above, it can be obtained by reacting a diol with a biscarboxylic acid or an ester compound corresponding to the biscarboxylic acid in the absence or presence of a catalyst while removing the water or alcohol produced.

[0136] Although the reaction can proceed without a catalyst, catalysts can be used, such as metal hydroxides (e.g., sodium hydroxide, potassium hydroxide), alkali metal or alkaline earth metal carbonates (e.g., sodium carbonate, potassium carbonate, cesium carbonate), amines (e.g., imidazoles, benzotriazoles), phosphines (e.g., triphenylphosphine), tetraalkylammonium halides (e.g., tetraethylammonium chloride, tetraethylammonium bromide), quaternary ammonium salts (e.g., benzyltrimethylammonium chloride, benzyltriethylammonium chloride), quaternary phosphonium salts (e.g., benzyltriphenylphosphonium chloride), aluminum compounds (e.g., trialkylaluminum), tin compounds (e.g., tin chloride, tin carboxylates), and titanium compounds (e.g., titanium alkoxides). The amount of catalyst used can be selected from the range of 0.001 to 1.0 mol per 1.0 mol of the total amount of diol and bisdicarboxylic acid, preferably 0.003 to 0.3 mol, and more preferably 0.005 to 0.1 mol.

[0137] The reaction can be carried out without a solvent, or a solvent can be used to reduce the viscosity of the resulting polymer. There are no particular limitations on the solvent as long as it is inert to the reaction. Examples include aromatic solvents such as benzene, toluene, and xylene, as well as acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, diphenyl sulfone, diphenyl ether, trichlorobiphenyl, trichlorobenzene, and dichlorobenzene, which can be used alone or in combination. These solvents can be used in an amount of 0 to 2000 parts by mass per 100 parts by mass of the reaction raw materials. The reaction temperature is preferably from -50°C to the boiling point of the solvent, more preferably 100°C to 150°C. The reaction time is appropriately selected from the range of 0.1 to 100 hours. It is preferable to carry out the reaction while removing water or alcohol produced by the reaction from the system.

[0138] The polymer can be obtained by the method described in paragraphs

[0100] to

[0112] , simply by changing the reacting substrate to a biscarboxylic acid or an ester compound corresponding to the biscarboxylic acid.

[0139] When the polymer (a1-2) is produced using an acid halide as described above, it can be obtained by reacting an acid halide, such as an acid chloride, corresponding to the biscarboxylic acid in the presence of a base catalyst.

[0140] Examples of the base catalyst used in this case include amines, specifically tertiary amines such as trimethylamine, triethylamine, tripropylamine, diisopropylethylamine, tributylamine, tripentylamine, and trihexylamine; aliphatic amines having an aromatic ring such as N,N-dimethylaniline, phenyldimethylamine, diphenylmethylamine, and triphenylamine; cyclic aliphatic amines such as 1-methylpyrrolidine, 1-methylpiperidine, and 4-methylmorpholine; 1,8-diazabicyclo[5.4. Examples of suitable catalysts include amidines such as 1,5-diazabicyclo[4.3.0]-7-undecene and 1,5-diazabicyclo[4.3.0]-5-nonene; guanidines such as guanidine, 1,1,3,3-tetramethylguanidine, and 1,2,3-triphenylguanidine; aromatic amines such as 1-methylpyrrole, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,6-dimethylpyridine, and N,N-dimethyl-5-aminopyridine; and quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. These catalysts can be used alone or in combination of two or more. The amount of catalyst used is 0.1 to 20 moles, preferably 0.2 to 10 moles, relative to the number of moles of the acid halide starting material.

[0141] The solvent used in this reaction is not particularly limited as long as it is inert to the reaction, but examples include ether solvents such as diethyl ether, tetrahydrofuran, and dioxane; aromatic solvents such as benzene, toluene, and xylene; acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, and water, which can be used alone or in combination. These solvents can be used in an amount of 0 to 2000 parts by mass per 100 parts by mass of the reaction raw materials, and the reaction temperature is preferably from -50°C to the boiling point of the solvent, more preferably from room temperature to 150°C. The reaction time is appropriately selected from the range of 0.1 to 100 hours.

[0142] The polymer can be obtained by the method described in paragraphs

[0100] to

[0112] , simply by changing the reacting substrates to a diol and an acid halide of the corresponding biscarboxylic acid.

[0143] [Another method for producing polymer (a1-2) having a repeating unit represented by formula (3)] Another method for producing the polymer (a1-2) is to obtain a polymer by replacing the raw materials used to obtain the polymer (a1-2), such as biscarboxylic acid, biscarboxylic acid ester, or biscarboxylic acid halide, with a malonic acid derivative [Step 1], and then subjecting the resulting polymer to an addition reaction [Step 2] with a halide, mesylate, or tosylate having R1 or R2 as a substituent in the presence of a base catalyst. (In the following formula, X represents a halide, mesylate, or tosylate, and R1, R2 (where R2 is other than a hydrogen atom), and R4 are the same as above.)

[0144] [STEP 1] [ka]

[0145] [STEP 2] [ka]

[0146] When using the above reaction method, similar to the polymer (a1-1), due to the reaction selectivity, there are two reaction sites for the repeating unit of the polymer. When the reaction rate is 100%, R1 and R2 are completely introduced as substituents. When R1≠R2, three types as follows are obtained, and when R1 = R2 = R’, one type is obtained. Also, when the reaction rate is less than 100%, a polymer with a repeating unit having a plurality of combinations as follows can be obtained. When R1≠R2, six types as follows are obtained, and when R1 = R2 = R’, two types are obtained. By adjusting the overall charge ratio, it becomes possible to control the reaction rate for the overall reaction sites, and substituents corresponding to multiple or single R1 and R2 can be combined and used according to the required performance. For example, when the substitution rate in the repeating unit of the polymer is 100, when the ratio substituted by R1 and R2 is a and the ratio existing as an unmodified hydrogen atom is b, 0≦a + b≦100, and 0.5 < a≦1.0 is preferable, and 0.7≦a≦1.0 is more preferable. In this case, a polymer containing the repeating unit shown below is obtained depending on the relationship between R1 and R2.

[0147] [In the case of a reaction rate of 100%] [Chemical formula]

[0148] [In the case of a reaction rate < 100%] [Chemical formula]

[0149] [ As a method for obtaining the above polymer, for the polymerization in [Step1], only the raw material in (a1-2) needs to be changed to a corresponding one of malonic acid from bis-carboxylic acid, and it can be obtained by the method described in paragraphs

[0143] ~

[0148] . The polymer obtained in [Step1] can be used in the addition reaction in Step2. Further, for the reaction in [Step2], only the obtained polymer needs to be changed to the polymer obtained in [Step1] from the polymer obtained in step1 of the alternative method (a-1), and the polymer can be obtained by the method described in paragraphs

[0143] ~

[0148] .

[0150] In producing the polymers used in the organic film-forming compositions obtained by these methods, it is possible to obtain polymers that meet the required performance requirements by combining the structures and incorporation ratios of R1 and R2 in the polymer, as well as the polymer production method. For example, it is possible to arbitrarily combine polymers having side chain structures that contribute to improved planarization characteristics, or fluorine-containing substituents that control surface tension and other properties to change the surfactant properties. Therefore, these polymers not only have excellent surfactant effects that contribute to improved film-forming properties, but also can achieve high levels of compatibility between various properties such as film-forming properties and embedding properties when used in an underlayer film as an organic film-forming composition.

[0151] [Composition for organic film formation] The organic film-forming composition contains (A) an organic film-forming resin or compound, (B) the polymer explained above, and (C) a solvent.

[0152] In the organic film-forming composition of the present invention, the (B) polymer, 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 (B) polymer of the present invention functions as a surfactant that imparts excellent film-forming properties and high leveling performance. Its applications are not limited to organic underlayer films; it can be used in general photolithography coating materials, including 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 intermediate films, and can be used as a surfactant suitable for achieving highly versatile film-forming properties that can be applied to a variety of film-forming materials.

[0153] Furthermore, the polymer (B) having the repeating unit (1) of the present invention can be used alone or in combination of two or more. The amount of these compounds added is such that the content of the polymer (B) is 0.01 to 5 parts by mass per 100 parts by mass of the resin or compound (A) for forming an organic film.

[0154] [(A) Organic film-forming resin or compound] The organic film-forming resin or compound (A) used in the organic film-forming composition of the present invention is not particularly limited as long as it is a resin or compound that satisfies the film-forming properties and curing properties of spin coating. However, from the viewpoints of etching resistance, optical properties, heat resistance, etc., a resin or compound containing an aromatic skeleton is more preferred.

[0155] 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.

[0156] 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. [ka] (In formula (1-1), 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.)

[0157] [ka] (In formula (2-1), the ring structures Ar1 and Ar2 represent benzene rings or naphthalene rings. n represents any natural number such that the weight-average molecular weight, calculated as polystyrene by gel permeation chromatography, is 100,000 or less. Note that the symbols in the formula are used only within this formula.)

[0158] 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. [ka] (In formula (3-1) and formula (4-1), 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.

[0159] [ka] (In formula (5-1), 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.)

[0160] [ka] In formula (6-1), 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. R5 , R 6R 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.

[0161] [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.)

[0162] 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. [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.

[0163] [ka] (In formula (10), R 1 , R 6 is a hydrogen atom or a methyl group. 2 , R3 and R 4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a hydroxy group, an acetoxy group or an alkoxycarbonyl group, or an aryl group having 6 to 10 carbon atoms, and R 5 is a condensed polycyclic hydrocarbon group having 13 to 30 carbon atoms, -O-R 7 , -C(=O)-O-R 7 , -O-C(=O)-R 7 , or -C(=O)-NR 8 -R 7 where m is 1 or 2, n is an integer of 0 to 4, and p is an integer of 0 to 6. R 7 is an organic group having 7 to 30 carbon atoms, R 8 is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Z is any one of a methylene group, -O-, -S-, and -NH-. a, b, c, d, and e are respectively in the ranges of 0 < a < 1.0, 0 ≤ b ≤ 0.8, 0 ≤ c ≤ 0.8, 0 ≤ d ≤ 0.8, 0 ≤ e ≤ 0.8, and 0 < b + c + d + e < 1.0. Note that the symbols in the formula are applicable only within this formula.)

[0164]

Chemical formula

[0165] Examples of the formula (11) include the following resins: [ka]

[0166] [ka]

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

[0168] [ka] (In formula (13), R 1 and R 2are 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.

[0169] [ka] (In formula (14), ring Z 1 and ring Z 2 is a fused polycyclic aromatic hydrocarbon ring, R 1a , R 1b , R 2a , and R 2b are the same or different and represent a substituent. k1 and k2 are the same or different and represent an integer of 0 or 1 to 4, m1 and m2 are each an integer of 0 or 1 or more, and n1 and n2 are each an integer of 0 or 1 or more, provided that n1+n2≧1. The symbols in the formulae are only applicable within this formula.

[0170] [ka] (In formula (15), R 1 , R 2 R are the same or different and are hydrogen atoms, linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, or alkenyl groups having 2 to 10 carbon atoms. 3 , R 4 are hydrogen atoms or glycidyl groups, and R 5 is a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms, and R 6 , R 7It is a benzene ring or a naphthalene ring. p and q are each 1 or 2. n is 0 < n ≤ 1. Note that the symbols in the formula are applicable only within this formula.)

[0171] As the formula (15), for example, the following resins are exemplified.)

Chemical formula

[0172]

Chemical formula

[0173] <000!1023>

Chemical formula

[0174]

Chemical formula

[0175] [[ID=3!]]Examples of the resin or compound (A) for forming an organic film used in the present invention include resins containing the following structures described in JP-A-2012-214720.) <!001039>

Chemical formula

[0176] Examples of the resin or compound (A) for forming an organic film used in the present invention include resins described in JP-A-2014-29435.)

Chemical formula

[0177] 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. [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.

[0178] [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.

[0179] 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. [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.

[0180] 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. [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.)

[0181] 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): [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.)

[0182] 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. [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.)

[0183] [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.)

[0184] Further, examples of the polymers include those obtained by condensing one or more compounds represented by the above general formula (23-1) and / or (23-2), one or more compounds represented by the above general formula (24-1) and / or (24-2) and / or equivalents thereof, and one or more compounds represented by the following general formula (25) and / or equivalents thereof. [ka] (In formula (25), Y represents a hydrogen atom or a monovalent organic group having 30 or less carbon atoms which may have a substituent, and formula (25) is different from general formula (24-1) and general formula (24-2). Note that the symbols in the formula apply only within this formula.)

[0185] 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. [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.)

[0186] [ka] (In the formula, X 2 is a divalent organic group having 1 to 10 carbon atoms, n1 is 0 or 1, n2 is 1 or 2, and X 3 is a group represented by the following general formula (26-3), and n5 is 0, 1, or 2. The symbols in the formula apply only within this formula. [ka] (In the formula, R 10 is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom on the benzene ring in the formula may be substituted with a methyl group or a methoxy group. Note that the symbols in the formula apply only within this formula.

[0187] Examples of compounds containing the above structure include the following compounds. [ka]

[0188] 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. [ka] In formula (27-1), AR1 and AR2 are benzene rings or naphthalene rings which may have a substituent, and R 1 , R 2 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R 1 and R 2 If is an organic group, R 1 and R 2 may form a cyclic organic group by bonding intramolecularly. n is 0 or 1, and when n=0, AR1 and AR2 do not form a bridged structure between the aromatic rings of AR1 and AR2 via Z, and when n=1, AR1 and AR2 form a bridged structure between the aromatic rings of AR1 and AR2 via Z, and Z is either a single bond or the following formula (27-2). Y is a group represented by the following formula (27-3). Note that the symbols in the formula apply only within this formula. [ka] [ka] (In the formula, R 3 is a single bond or a divalent organic group having 1 to 20 carbon atoms, and R 4 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and the dashed line represents a bond. Note that the symbols in the formula are only applicable within this formula.

[0189] Examples of polymers having a repeating unit represented by the above general formula (27-1) include the following polymers. [ka]

[0190] [ka]

[0191] (A) The organic film-forming resin or compound may be synthesized by a known method, or a commercially available product may be used.

[0192] 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.

[0193] Furthermore, the content of the (B) polymer is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the (A) organic film-forming resin or compound. When the organic film-forming composition contains the polymer in such a content, the formed organic film has better in-plane uniformity.

[0194] The solvent (C) that can be used in the organic film-forming material of the present invention is not particularly limited as long as it can dissolve the (A) organic film-forming resin or compound and the (B) compound, and is preferably one that can also dissolve the acid generator, crosslinking agent, surfactant, etc., which will be described later. Specifically, solvents with a boiling point of less than 180°C, such as those described in paragraphs (0091) and (0092) of JP-A No. 2007-199653, can be used. Among these, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclopentanone, cyclohexanone, and mixtures of two or more of these are preferably used.

[0195] 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.

[0196] 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.

[0197] 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.

[0198] 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.

[0199] In the case of such an organic film-forming material, the addition of a high-boiling point solvent to the above-mentioned organic film-forming resin or compound gives it thermal fluidity, thereby making it an organic film-forming material that also has high-level filling / planarizing properties.

[0200] [Other ingredients] In addition, an acid generator or crosslinking agent can be added to the organic film-forming composition of the present invention to further promote the crosslinking reaction. Acid generators include those that generate acid upon thermal decomposition and those that generate acid upon light irradiation, and either can be added. Specific examples of acid generators include those described in paragraphs

[0061] to

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

[0201] 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.

[0202] 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.

[0203] Furthermore, a basic compound can be added to the organic film-forming composition of the present invention to improve storage stability. The basic compound acts as an acid quencher to prevent a small amount of acid generated by the acid generator from promoting a crosslinking reaction. Specific examples of such basic compounds include those described in paragraphs

[0086] to

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

[0204] 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.

[0205] [Organic film formation method] The present invention provides a method for forming an organic film used in the manufacturing process of a semiconductor device, which comprises spin-coating the above-described composition for forming an organic film of the present invention onto a substrate to be processed, and then heat-treating the substrate coated with the composition for forming an organic film at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds to harden the composition, thereby forming an organic film.

[0206] 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.

[0207] Baking is preferably performed at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds, more preferably at a temperature of 200°C or higher and 500°C or lower for 10 to 300 seconds. Considering the effects on device damage and wafer deformation, the upper limit of the heating temperature in the lithography wafer process is preferably 600°C or lower, more preferably 500°C or lower. 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.

[0208] [Pattern formation method] A pattern forming method using the organic film-forming composition of the present invention will be described below.

[0209] [Trilayer resist process using silicon-containing resist interlayer] In the present invention, there is provided a pattern forming method, comprising the steps of: forming an organic film on a workpiece using the organic film-forming composition described above; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material; forming a resist upper layer film on the silicon-containing resist intermediate film using a resist upper layer film material comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the silicon-containing resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern to the organic film by etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; Furthermore, the present invention provides a pattern forming method in which the organic film onto which the pattern has been transferred is used as a mask to transfer the pattern onto the workpiece by etching.

[0210] 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.

[0211] 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.

[0212] 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.

[0213] 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.

[0214] 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-reflection 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-reflection 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.

[0215] 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.

[0216] 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.

[0217] 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.

[0218] In forming the circuit pattern, it is preferable to develop the circuit pattern using an alkali developer or an organic solvent.

[0219] 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.

[0220] 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.

[0221] 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.

[0222] 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.

[0223] [Four-layer resist process using silicon-containing resist interlayer and organic anti-reflective or adhesive coating] Further, the present invention provides a pattern forming method, comprising the steps of: forming an organic film on a workpiece using the organic film-forming composition described above; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist intermediate film material; forming an organic anti-reflective film or an adhesion film on the silicon-containing resist intermediate film; forming a resist upper layer film on the organic antireflective film or the adhesion film using a resist upper layer film material comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; a resist upper layer film on which the circuit pattern is formed is used as a mask to transfer the pattern to the organic anti-reflective film or the adhesive film and the silicon-containing resist intermediate film by etching; transferring the pattern to the organic film by etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; Furthermore, the present invention provides a pattern forming method in which the organic film onto which the pattern has been transferred is used as a mask to transfer the pattern onto the workpiece by etching.

[0224] This method can be performed in the same manner as the three-layer resist process using the silicon-containing resist intermediate film described above, except that an organic antireflective coating (BARC) or an adhesive film is formed between the silicon-containing resist intermediate film and the resist top layer film.

[0225] The organic anti-reflection film and the adhesive film can be formed by spin coating using known organic anti-reflection film materials.

[0226] [Trilayer resist process using inorganic hard mask intermediate film] Further, the present invention provides a pattern forming method, comprising the steps of: forming an organic film on a workpiece using the organic film-forming composition described above; forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film; forming a resist upper layer film on the inorganic hard mask intermediate film using a resist upper layer film material comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the inorganic hard mask intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern to the organic film by etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; Furthermore, the present invention provides a pattern forming method in which the organic film onto which the pattern has been transferred is used as a mask to transfer the pattern onto the workpiece by etching.

[0227] 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.

[0228] 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.

[0229] [Four-layer resist process using inorganic hard mask intermediate film and organic anti-reflective or adhesive film] Further, the present invention provides a pattern forming method, comprising the steps of: forming an organic film on a workpiece using the organic film-forming composition described above; forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film; forming an organic anti-reflective film or an adhesion film on the inorganic hard mask intermediate film; forming a resist upper layer film on the organic antireflective film or the adhesion film using a resist upper layer film material comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; a resist upper layer film on which the circuit pattern is formed is used as a mask to transfer the pattern to the organic anti-reflective film or the adhesive film and the inorganic hard mask intermediate film by etching; transferring the pattern to the organic film by etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; Furthermore, the present invention provides a pattern forming method in which the organic film onto which the pattern has been transferred is used as a mask to transfer the pattern onto the workpiece by etching.

[0230] 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.

[0231] 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.

[0232] 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).

[0233] 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.

[0234] As described above, the pattern formation method of the present invention makes it possible to form a fine pattern on a workpiece with high precision by a multilayer resist process, and also to reduce defects resulting from humps in the organic film by suppressing hump formation in the organic film. [Example]

[0235] 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.

[0236] [Synthesis of polymers (A1) to (A18)] The polymers (A1) to (A18) used as polymers for organic film-forming materials were synthesized using the following monomers (m1) to (m15).

[0237] [Monomer] [ka]

[0238] [Synthesis Example 1] Synthesis of polymer (A1) 10.0 g of propylene glycol monomethyl ether acetate (PGMEA) was heated and stirred at 80°C under a nitrogen atmosphere. To this was added dropwise 5.91 g (15.0 mmol) of monomer (m1), 0.345 g (1.5 mmol) of dimethyl 2,2-azobis(2-methylpropionate) as a polymerization initiator, 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 target polymer (A1). Analysis revealed that the weight-average molecular weight (Mw) of polymer (A1) was 14,900 and the polydispersity (Mw / Mn) was 1.65. [ka]

[0239] [Synthesis Examples 2-18] Polymers (A2)-(A18) Polymers (A2) to (A18) shown below were obtained by a method similar to Synthesis Example 1, except that the monomers, their amounts, and the amount of polymerization initiator used were changed to those shown in Table 1. The weight average molecular weight (Mw) and dispersity (Mw / Mn) determined by GPC are also shown. Synthesis Example 1 is also shown. [Table 1] [ka] [ka]

[0240] [Synthesis of polymers (A19) to (A25)] The polymers (A19) to (A25) used as polymers for organic film-forming materials were synthesized using the diol compounds and acetoacetic acid ester derivatives (M1) to (M8) shown below.

[0241] [Monomer] [ka]

[0242] [Synthesis Example 19] Synthesis of polymer (A19) [ka] Under a nitrogen atmosphere, 1.0 g of monomer (M1), 9.1 g of monomer (M5), and 20 g of xylene were added to a flask. The reaction was carried out at an internal temperature of 140 °C for 2 hours while removing t-butyl alcohol produced by transesterification from the system. The temperature was then raised to 160 °C while removing t-butyl alcohol and o-xylene from the system, and the reaction was carried out at this temperature for 6 hours. After cooling to an internal temperature of 50 °C, 200 g of hexane was added to precipitate a polymer in the form of a gum. The mixture was then cooled to room temperature and allowed to stand for 1 hour, after which the supernatant was decanted. 100 g of PGMEA (propylene glycol monomethyl ether acetate) was added to the residue to form a homogeneous solution. Water and low-boiling point solvents were distilled off, and the concentration was further adjusted to recover a 50% PGMEA solution of stabilizer compound (A19). (A19): Mw = 14800, Mw / Mn = 1.79

[0243] [Synthesis Example 20] Synthesis of polymer (A20) [ka] Under a nitrogen atmosphere, 1.0 g of monomer (M1), 8.9 g of monomer (M6), and 20 g of xylene were added to a flask. The reaction was carried out at an internal temperature of 140 °C for 2 hours while removing t-butyl alcohol produced by transesterification from the system. The temperature was then raised to 160 °C while removing t-butyl alcohol and o-xylene from the system, and the reaction was carried out at this temperature for 6 hours. After cooling to an internal temperature of 50 °C, 200 g of hexane was added to precipitate a polymer in the form of a gum. The mixture was then cooled to room temperature and allowed to stand for 1 hour, after which the supernatant was decanted. 100 g of PGMEA (propylene glycol monomethyl ether acetate) was added to the residue to form a homogeneous solution. Water and low-boiling point solvents were distilled off, and the concentration was further adjusted to recover a 50% PGMEA solution of stabilizer compound (A20). (A20): Mw = 18100, Mw / Mn = 1.88

[0244] [Synthesis Example 21] Synthesis of polymer (A21) [ka] Under a nitrogen atmosphere, 1.0 g of monomer (M1), 10.2 g of monomer (M7), and 20 g of xylene were added to a flask. The reaction was carried out at an internal temperature of 140 °C for 2 hours while removing t-butyl alcohol produced by transesterification from the system. The temperature was then raised to 160 °C while removing t-butyl alcohol and o-xylene from the system, and the reaction was carried out at this temperature for 6 hours. After cooling to an internal temperature of 50 °C, 200 g of hexane was added to precipitate a polymer in the form of a gum. The mixture was then cooled to room temperature and allowed to stand for 1 hour, after which the supernatant was decanted. 100 g of PGMEA (propylene glycol monomethyl ether acetate) was added to the residue to form a homogeneous solution. Water and low-boiling point solvents were distilled off, and the concentration was further adjusted to recover a 50% PGMEA solution of stabilizer compound (A21). (A21): Mw = 17300, Mw / Mn = 1.67

[0245] [Synthesis Example 22] Synthesis of polymer (A22) [ka] Under a nitrogen atmosphere, 1.0 g of monomer (M1), 6.5 g of monomer (M8), and 20 g of xylene were added to a flask. The reaction was carried out at an internal temperature of 140 °C for 2 hours while removing t-butyl alcohol produced by transesterification from the system. The temperature was then raised to 160 °C while removing t-butyl alcohol and o-xylene from the system, and the reaction was carried out at this temperature for 6 hours. After cooling to an internal temperature of 50 °C, 200 g of hexane was added to precipitate a polymer in the form of a gum. The mixture was then cooled to room temperature and allowed to stand for 1 hour, after which the supernatant was decanted. 100 g of PGMEA (propylene glycol monomethyl ether acetate) was added to the residue to form a homogeneous solution. Water and low-boiling point solvents were distilled off, and the concentration was further adjusted to recover a 50% PGMEA solution of stabilizer compound (A22). (A22): Mw = 21000, Mw / Mn = 1.46

[0246] [Synthesis Example 23] Synthesis of polymer (A23) [ka] Under a nitrogen atmosphere, 1.5 g of monomer (M2), 9.4 g of monomer (M5), and 20 g of xylene were added to a flask. The reaction was carried out at an internal temperature of 140 °C for 2 hours while removing t-butyl alcohol produced by transesterification from the system. The temperature was then raised to 160 °C while removing t-butyl alcohol and o-xylene from the system, and the reaction was carried out at this temperature for 6 hours. After cooling to an internal temperature of 50 °C, 200 g of hexane was added to precipitate a polymer in the form of a gum. The mixture was then cooled to room temperature and allowed to stand for 1 hour, after which the supernatant was decanted. 100 g of PGMEA (propylene glycol monomethyl ether acetate) was added to the residue to form a homogeneous solution. Water and low-boiling point solvents were distilled off, and the concentration was further adjusted to recover a 50% PGMEA solution of stabilizer compound (A23). (A23): Mw = 12400, Mw / Mn = 1.66

[0247] [Synthesis Example 24] Synthesis of polymer (A24) [ka] Under a nitrogen atmosphere, 2.0 g of monomer (M3), 9.4 g of monomer (M6), and 20 g of xylene were added to a flask. The reaction was carried out at an internal temperature of 140 °C for 2 hours while removing t-butyl alcohol produced by transesterification from the system. The temperature was then raised to 160 °C while removing t-butyl alcohol and o-xylene from the system, and the reaction was carried out at this temperature for 6 hours. After cooling to an internal temperature of 50 °C, 200 g of hexane was added to precipitate a polymer in the form of a gum. The mixture was then cooled to room temperature and allowed to stand for 1 hour, after which the supernatant was decanted. 100 g of PGMEA (propylene glycol monomethyl ether acetate) was added to the residue to form a homogeneous solution. Water and low-boiling point solvents were distilled off, and the concentration was further adjusted to recover a 50% PGMEA solution of stabilizer compound (A24). (A24): Mw = 19200, Mw / Mn = 1.91

[0248] [Synthesis Example 25] Synthesis of polymer (A25) [ka] Under a nitrogen atmosphere, 2.0 g of monomer (M4), 12.0 g of monomer (M7), and 20 g of xylene were added to a flask. The reaction was carried out at an internal temperature of 140 °C for 2 hours while removing t-butyl alcohol produced by transesterification from the system. The temperature was then raised to 160 °C while removing t-butyl alcohol and o-xylene from the system, and the reaction was carried out at this temperature for 6 hours. After cooling to an internal temperature of 50 °C, 200 g of hexane was added to precipitate a polymer in the form of a gum. The mixture was then cooled to room temperature and allowed to stand for 1 hour, after which the supernatant was decanted. 100 g of PGMEA (propylene glycol monomethyl ether acetate) was added to the residue to form a homogeneous solution. Water and low-boiling point solvents were distilled off, and the concentration was further adjusted to recover a 50% PGMEA solution of stabilizer compound (A25). (A25): Mw = 16100, Mw / Mn = 1.55

[0249] [Synthesis of comparative polymers (R1) to (R5)] The comparative polymers (R1) to (R5) used to prepare the organic film-forming compositions were synthesized using the following monomers (mr1) to (mr6). [ka]

[0250] [Comparative Synthesis Example 1] Synthesis of Comparative Polymer (R1) [ka] Under a nitrogen atmosphere, 6.0 g of PGMEA was heated and stirred at 80°C. To this was added dropwise a mixture of 3.44 g (0.011 mol) of monomer (mr1), 7.46 g (0.034 mol) of monomer (mr3), 0.350 g of dimethyl 2,2-azobis(2-methylpropionate), and 34 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (R1). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (R1): Mw = 13500, Mw / Mn = 1.56

[0251] [Comparative Synthesis Example 2] Synthesis of Comparative Polymer (R2) [ka] Under a nitrogen atmosphere, 6.0 g of PGMEA was heated and stirred at 80°C. To this was added dropwise a mixture of 1.43 g (0.005 mol) of monomer (mr1), 5.76 g (0.041 mol) of monomer (mr4), 0.250 g of dimethyl 2,2-azobis(2-methylpropionate), and 34 g of PGMEA over 4 hours. After heating and stirring for an additional 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (R2). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (R2): Mw = 12800, Mw / Mn = 1.57

[0252] [Comparative Synthesis Example 3] Synthesis of Comparative Polymer (R3) [ka] Under a nitrogen atmosphere, 6.0 g of PGMEA was heated and stirred at 80°C. To this was added dropwise a mixture of 7.00 g (0.032 mol) of monomer (mr2), 1.92 g (0.014 mol) of monomer (mr3), 0.250 g of dimethyl 2,2-azobis(2-methylpropionate), and 34 g of PGMEA over 4 hours. After further heating and stirring for 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (R3). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (R3): Mw = 16400, Mw / Mn = 1.75

[0253] [Comparative Synthesis Example 4] Synthesis of Comparative Polymer (R4) [ka] Under a nitrogen atmosphere, 6.0 g of PGMEA was heated and stirred at 80°C. To this was added dropwise a mixture of 5.00 g (0.023 mol) of (mr2), 3.20 g (0.023 mol) of (mr5), 0.345 g of dimethyl 2,2-azobis(2-methylpropionate), and 34 g of PGMEA over 4 hours. After further heating and stirring for 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (R4). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (R4): Mw = 13300, Mw / Mn = 1.39

[0254] [Comparative Synthesis Example 5] Synthesis of Comparative Polymer (R5) [ka] Under a nitrogen atmosphere, 6.0 g of PGMEA was heated and stirred at 80°C. To this was added dropwise a mixture of 2.00 g (0.009 mol) of (mr2), 5.41 g (0.036 mol) of (mr6), 0.300 g of dimethyl 2,2-azobis(2-methylpropionate), and 34 g of PGMEA over 4 hours. After further heating and stirring for 16 hours, the mixture was cooled to room temperature to obtain a PGMEA solution of the target polymer (R5). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (R5): Mw = 9800, Mw / Mn = 1.55

[0255] [Resin or compound for forming organic film] C1: Resin represented by the following formula (C1): C2: Resin represented by the following formula (C2) C3: A compound represented by the following formula (C3): C4: A compound represented by the following formula (C4): C5: Resin represented by the following formula (C5): C6: Resin represented by the following formula (C6):

[0256] [ka]

[0257] [solvent] D1: Propylene glycol monomethyl ether acetate D2: Propylene glycol monoethyl ether

[0258] [Preparation of Organic Film-Forming Compositions (UDL-1 to 89, Comparative UDL-1 to 16)] The polymers (A1) to (A25), comparative polymers (R1) to (R5), organic film-forming resins or compounds (C1) to (C6), and solvents were dissolved in the proportions shown in Tables 2 to 4, 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 89, comparative examples UDL-1 to 16). [Table 2]

[0259] [Table 3]

[0260] [Table 4]

[0261] [Preparation of Silicon Wafers with Organic Cured Films Formed Using Organic Film-Forming Compositions (UDL-1 to 89, Comparative UDL-1 to 16)] Using a Tokyo Electron Limited coater / developer "CLEAN TRACK LITHIUS Pro AP," 2 mL of each of the organic film-forming compositions (UDL-1 to 89, comparative UDL-1 to 18) was dispensed onto the center of a silicon wafer. After baking, the wafer was rotated at a speed sufficient to achieve the average film thickness shown in Tables 5 to 7. 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.

[0262] [Solvent Resistance Evaluation: Examples 1-1 to 1-89, Comparative Examples 1-1 to 1-16] Using the method described above, organic film-forming compositions (UDL-1 to 89, Comparative UDL-1 to 16) were deposited on silicon wafers, the film thickness was measured, PGMEA solvent was dispensed onto the film, the film was left for 30 seconds, spin-dried, and baked at 100°C for 60 seconds to evaporate the PGMEA, and the film thickness was measured. The film thickness before dispensing the PGMEA solvent was defined as X, and the film thickness after dispensing the PGMEA solvent was defined as X1. The absolute value of the value calculated by {(X1 - X) / X} x 100 was used as the film thickness change rate (%). A film thickness change rate of less than 0.5% was considered good, and a film thickness change rate of 0.5% or more was considered poor.

[0263] [In-plane uniformity evaluation: Examples 1-1 to 1-89, Comparative Examples 1-1 to 1-16] The organic film-forming compositions (UDL-1 to 89, comparative UDL-1 to 16) were formed on silicon wafers using the above method, and the thickness of the organic cured film was measured at 225 concentric points within a radius of 145 mm from the center of the wafer using an optical film thickness meter. max , minimum X min , average value X average As, {(X max -X min ) / X average The value calculated by multiplying the square root of the square root by 100 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).

[0264] [Table 5]

[0265] [Table 6]

[0266] [Table 7]

[0267] [Hump suppression evaluation: Examples 2-1 to 2-89, Comparative Examples 2-1 to 2-10] Using the method described above, organic film-forming compositions (UDL-1 to 89, comparative UDL-1 to 10) 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.

[0268] [Embedding Evaluation-1: Examples 2-1 to 2-89, Comparative Examples 2-1 to 2-10] As shown in Figure 4, organic film-forming compositions (UDL-1 to 89, Comparative UDL-1 to 10) were deposited by the above method on a SiO2 wafer substrate with a dense hole pattern (hole diameter 0.2 μm, hole depth 1.0 μm, center-to-center distance between adjacent holes 0.4 μm) to form a resist underlayer film 8. The substrate used was a base substrate (SiO2 wafer substrate) 7 with a dense hole pattern as shown in Figure 4(G) (overhead view) and (H) (cross-sectional view). The cross-sectional shape of each wafer substrate was observed using a scanning electron microscope (SEM) to confirm whether the holes were filled with the resist underlayer film without any voids. When a resist underlayer film material with poor filling properties was used, voids were generated within the holes. When a resist underlayer film material with good filling properties was used, the holes were filled with the resist underlayer film without any voids, as shown in Figure 4(I). A sample was rated as good if no voids were generated, and as poor if voids were generated.

[0269] [Embedding Evaluation-2: Examples 2-65 to 2-89] As shown in Figure 4, organic film-forming compositions (UDL-65 to 89) were deposited by the above method on a SiO2 wafer substrate with a dense hole pattern (hole diameter 0.2 μm, hole depth 2.0 μm, center-to-center distance between adjacent holes 0.4 μm) to form a resist underlayer film 8. The substrate used was a base substrate (SiO2 wafer substrate) 7 with a dense hole pattern as shown in Figure 4(G) (overhead view) and (H) (cross-sectional view). The cross-sectional shape of each wafer substrate was observed using a scanning electron microscope (SEM) to confirm whether the holes were filled with the resist underlayer film without any voids. When a resist underlayer film material with poor filling properties was used, voids were generated within the holes. When a resist underlayer film material with good filling properties was used, the holes were filled with the resist underlayer film without any voids, as shown in Figure 4(I). A sample was rated as good if no voids were generated, and as poor if voids were generated. In addition, in order to evaluate the quality of filling performance, the evaluation conditions are strict, making it easier for voids to be filled, even with a rating of -1.

[0270] [Table 8]

[0271] [Table 9]

[0272] [Table 10]

[0273] As shown in Tables 5 to 10, it was confirmed that the organic film-forming compositions of the present invention (UDL-1 to 89) were excellent in solvent resistance, in-plane uniformity, hump suppression, and filling properties.

[0274] [Pattern formation test: Examples 3-1 to 3-74] Using the above method, a resist underlayer film was formed on a SiO2 wafer substrate using an organic film-forming composition (UDL-1 to 74). The following silicon-containing resist intermediate film material (SOG1) was then applied on top of the resist underlayer 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 resist upper layer film material and baked at 105°C for 60 seconds to form a 100 nm thick resist upper layer film. The following immersion protective film material (TC-1) was then applied on top of the resist upper layer film and baked at 90°C for 60 seconds to form a 50 nm thick protective film.

[0275] 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 11, and filtering the solution through a 0.1 μm fluororesin filter. [Table 11]

[0276] The polymer (SP1) is shown below. [ka]

[0277] TMPNO3: Trimethylphenylammonium nitrate PGEE: Propylene glycol ethyl ether

[0278] 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 12, and filtering the solution through a 0.1 μm fluororesin filter. [Table 12]

[0279] The polymer (RP1), acid generator (PAG1), and basic compound (Amine1) are shown below. [ka]

[0280] The immersion protective film material (TC-1) was prepared by dissolving the polymer (PP1) in an organic solvent in the ratio shown in Table 13 and filtering the solution through a 0.1 μm fluorine resin filter. [Table 13]

[0281] The polymer (PP1) is shown below. [ka]

[0282] 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).

[0283] Next, using the resist upper layer film pattern as a mask, the silicon-containing resist intermediate film was dry-etched (pattern transferred) using a Tokyo Electron etching system, Telius, and using the resulting silicon-containing resist intermediate film pattern as a mask, the resist underlayer film was dry-etched (pattern transferred), and using the resulting resist underlayer film pattern as a mask, the SiO2 wafer substrate (SiO2 film) was dry-etched (pattern transferred). The etching conditions are as shown below.

[0284] (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

[0285] (Conditions for transferring silicon-containing resist intermediate film pattern to resist underlayer film) Chamber pressure 2.0Pa RF power 500W Ar gas flow rate: 75 mL / min O2 gas flow rate: 45mL / min Time 120sec

[0286] (Conditions for transferring resist underlayer film pattern onto SiO2 wafer substrate) Chamber pressure 2.0Pa RF power 2,200W C5F 12Gas 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

[0287] 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 14 and 15. [Table 14]

[0288] [Table 15]

[0289] As shown in Tables 14 and 15, in Examples 3-1 to 3-74 in which the organic film-forming compositions (UDL-1 to 74) of the present invention were used, the resist upper layer film pattern was ultimately transferred successfully to the SiO2 wafer substrate, confirming that the organic film-forming compositions of the present invention are suitable for use in microfabrication using the multilayer resist method.

[0290] [Preparation of resist top layer materials (PR1 to 25, comparative PR)] Resist top layer film materials (PR1 to 25, comparative PR) were prepared by dissolving polymer (P-1), acid generator (PAG-2), quencher (Q-1), and polymers (A1 to A25) in a solvent in the proportions shown in Table 16 and filtering through a 0.1 μm fluororesin filter. [Table 16]

[0291] The polymer (P-1), acid generator (PAG-2), quencher (Q-1), and solvent are shown below. [ka] PGMEA: Propylene glycol monomethyl ether acetate EL: Ethyl lactate

[0292] [Preparation of silicon wafers with resist top layer films formed using resist top layer film materials (PR1-25, comparative PR)] Using a Tokyo Electron Co., Ltd. coater / developer "CLEAN TRACK LITHIUS Pro AP," 2 ml of the resist top layer material (PR1-25, comparative PR) prepared above was dispensed onto the center of a silicon wafer, and the wafer was rotated and spread at a rotation speed that resulted in an average film thickness of 45 nm after baking. Next, the silicon wafer coated with the resist top layer film was heated at 110°C for 30 seconds to obtain a silicon wafer with a resist top layer film formed thereon.

[0293] [Evaluation of in-plane uniformity of resist top layer film: Examples 4-1 to 4-25, Comparative Example 4-1] The thickness of the resist top layer films (PR1 to 25, 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 calculated by the formula}×100 was taken as the in-plane uniformity (%). In-plane uniformity of less than 3% was considered good, and in-plane uniformity of 3% or more was considered poor. [Table 17]

[0294] As shown in Table 17, the resist top layer film materials (PR1 to 25) 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.

[0295] [EUV Lithography Evaluation: Examples 5-1 to 5-25] Each resist top layer material (PR1-25) listed in Table 16 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.

[0296] [Table 18]

[0297] As shown in Table 18, in Examples 5-1 to 5-25, in which the organic film-forming composition of the present invention (PR1 to 25) 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.

[0298] [Preparation of silicon-containing resist intermediate film materials (SOG2-26)] 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 19, and then filtering the mixture through a 0.1 μm fluororesin filter to prepare silicon-containing resist underlayer film materials (SOG2 to SOG26).

[0299] [Table 19] PGEE: Propylene glycol monoethyl ether

[0300] [Evaluation of Coatability of Silicon-Containing Resist Interlayer: Examples 6-1 to 6-25, Comparative Example 6-1] Using the above method, a resist underlayer film was formed on a silicon wafer substrate using an organic film-forming composition (Comparative UDL-1), and the following silicon-containing resist interlayer materials (SOG2-26, Comparative SOG1) were applied thereon and baked at 200°C for 60 seconds to form silicon-containing resist interlayer films. The state of the silicon-containing resist interlayer film coating was then visually observed and evaluated. If the coating condition was good, it was rated as good, and if pinholes were found, it was rated as bad. In this evaluation, in order to evaluate the superiority or inferiority of the coating properties of the silicon-containing resist interlayer, the thickness of the silicon-containing resist interlayer was set to 5 nm, which was a special and strict evaluation condition. [Table 20]

[0301] As shown in Table 20, the silicon-containing resist intermediate film materials (SOG2 to 26) 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.

[0302] From the above, the organic film-forming composition of the present invention has excellent film-forming properties, high-level filling characteristics, and hump-suppressing properties, and is therefore extremely useful as an organic film material for use in multilayer resist processes. Furthermore, the pattern formation method of the present invention using this composition is capable of filling holes and trenches with very high aspect ratios without voids, and is also capable of forming fine patterns with high precision. In addition, it is possible to form an organic film with suppressed humps, and therefore semiconductor elements and the like can be efficiently manufactured. Furthermore, the polymer of the present invention can be widely used as a surfactant, as it exhibits high film-forming properties.

[0303] The present specification includes the following aspects. [1] A composition for forming an organic film, (A) an organic film-forming resin or compound; (B) a polymer having a partial structure (a1) represented by the following general formula (1) as a repeating unit, and (C) Solvent A composition for forming an organic film, comprising: [ka] (In the formula, R1 and R2 are hydrogen atoms or saturated or unsaturated organic groups having 1 to 20 carbon atoms, and have at least one fluorine-containing structure represented by the following general formula (2), and at least one of R1 and R2 is an organic group other than a hydrogen atom. * represents a bond.) [ka] (* represents a bond.) [2] The organic film-forming composition according to [1], wherein the repeating unit (a1) of the polymer (B) is a repeating unit represented by the following general formula (3) or (4): [ka] (In the formula, R1 and R2 are the same as above, R3 represents a hydrogen atom or a methyl group, and n1 represents an integer of 2 to 10.) [ka] (In the formula, R1 and R2 are the same as above, and R4 represents a divalent organic group having 2 to 30 carbon atoms, which may contain an ether bond, ester bond, amide bond, or sulfide bond.) [3] The organic film-forming composition according to [2], wherein the polymer (B) is a copolymer having repeating units of the general formula (3) and the following general formula (5): [ka] (In the formula, R3 is the same as defined above, R5 and R6 each represent a linear or branched divalent alkylene group having 1 to 4 carbon atoms, R7 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, m1 represents 0 to 23, m2 represents 0 to 23, and 23≧m1+m2≧2.) [4] The composition for forming an organic film according to any one of [1] to [3], characterized in that the polymer (B) has at least one structure of the following general formula (6) as an organic group having fluorine represented by R1 or R2: [ka] [5] The composition for forming an organic film according to any one of [1] to [4], wherein the polymer (B) has a weight average molecular weight of 1,500 to 30,000. [6] The composition for forming an organic film according to any one of [1] to [5], characterized in that the content of the polymer (B) is 0.01 to 5 parts by mass when the resin for forming an organic film or the compound (A) is taken as 100 parts by mass. [7] A method for forming an organic film used in a manufacturing process of a semiconductor device, comprising spin-coating the composition for forming an organic film according to any one of [1] to [6] onto a workpiece, and heat-treating the substrate coated with the composition for forming an organic film at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds, thereby forming a cured film. [8] A pattern formation method comprising: forming an organic film on a workpiece using the organic film-forming composition according to any one of [1] to [6]; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist material containing silicon atoms; forming a resist upper layer film on the silicon-containing resist intermediate film using a resist upper layer film material consisting of a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the silicon-containing resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern to the organic film by etching using the silicon-containing resist intermediate film on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask. [9] A pattern formation method comprising: forming an organic film on a workpiece using the organic film-forming composition according to any one of [1] to [6]; forming a silicon-containing resist intermediate film on the organic film using a silicon-containing resist material containing silicon atoms; forming an organic antireflective film or an adhesive film on the silicon-containing resist intermediate film; forming a resist upper layer film on the organic antireflective film or the adhesive film using a resist upper layer film material comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern by etching to the organic antireflective film or the adhesive film and the silicon-containing resist intermediate film using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern by etching to the organic film using the silicon-containing resist intermediate film on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

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

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

[12] The pattern forming method according to

[10] or

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

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

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

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

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

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

[14] , characterized in that the workpiece is a semiconductor device substrate, or a semiconductor device substrate having any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film formed thereon.

[16] The pattern forming method according to

[15] , 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.

[17] A polymer having a partial structure (a1) represented by the following general formula (1) as a repeating unit: [ka] (In the formula, R1 and R2 are hydrogen atoms or saturated or unsaturated organic groups having 1 to 20 carbon atoms, and have at least one fluorine-containing structure represented by the following general formula (2), and at least one of R1 and R2 is an organic group other than a hydrogen atom. * represents a bond.) [ka] (* represents a bond.)

[18] The polymer according to

[17] , wherein the repeating unit (a1) of the polymer is a repeating unit represented by the following general formula (3) or (4): [ka] (In the formula, R1 and R2 are the same as above, R3 represents a hydrogen atom or a methyl group, and n1 represents an integer of 2 to 10.) [ka] (In the formula, R1 and R2 are the same as above, and R4 represents a divalent organic group having 2 to 30 carbon atoms, which may contain an ether bond, ester bond, amide bond, or sulfide bond.)

[19] The polymer according to

[18] , wherein the polymer is a copolymer having repeating units of the general formula (3) and the following general formula (5): [ka] (In the formula, R3 is the same as defined above, R5 and R6 each represent a linear or branched divalent alkylene group having 1 to 4 carbon atoms, R7 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, m1 represents 0 to 23, m2 represents 0 to 23, and 23≧m1+m2≧2.)

[20] The polymer according to any one of

[17] to

[19] , characterized in that the polymer has at least one structure represented by the following general formula (6) as a fluorine-containing structure represented by R1 or R2: [ka]

[0304] The present invention is not limited to the above-described embodiments, which are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that provides similar effects is included within the technical scope of the present invention. [Explanation of symbols]

[0305] 1...substrate, 2...processed layer, 2a...pattern formed on the processed layer, 3...organic film, 3'...organic film-forming composition, 3a...organic film pattern, 4...silicon-containing resist intermediate film, 4a...silicon-containing resist intermediate film pattern, 5...resist upper layer film, 5a...resist upper layer film pattern, 6...exposed portion 7...Base substrate (SiO2 wafer substrate) with dense hole pattern 8...Resist underlayer film

Claims

1. An organic film-forming composition, (A) an organic film-forming resin or compound; (B) a polymer having a partial structure (a1) represented by the following general formula (1) as a repeating unit, and (C) Solvent A composition for forming an organic film, comprising: 【Chemistry 1】 (In the formula, R １ , R ２ is a hydrogen atom or a saturated or unsaturated organic group having 1 to 20 carbon atoms, and has at least one structure having fluorine represented by the following general formula (2), and R １ , R ２ At least one of the groups represents an organic group other than a hydrogen atom. * represents a bond.) 【Chemistry 2】 (* represents a bond.)

2. 2. The organic film-forming composition according to claim 1, wherein the repeating unit (a1) of the polymer (B) is a repeating unit represented by the following general formula (3) or (4): 【Transformation 3】 (In the formula, R １ , R ２ is the same as above, and R ３ represents a hydrogen atom or a methyl group. n1 represents an integer of 2 to 10. 【Chemistry 4】 (In the formula, R １ , R ２ is the same as above, and R ４ represents a divalent organic group having 2 to 30 carbon atoms, which may contain an ether bond, an ester bond, an amide bond, or a sulfide bond.

3. 3. The organic film-forming composition according to claim 2, wherein the polymer (B) is a copolymer having repeating units of the general formula (3) and the following general formula (5): 【Transformation 5】 (In the formula, R ３ is the same as above, R ５ and R ６ are each a linear or branched divalent alkylene group having 1 to 4 carbon atoms, R ７ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, m1 is 0 to 23, m2 is 0 to 23, and 23≧m1+m2≧2.

4. R of the polymer (B) １ or R ２ 2. The composition for forming an organic film according to claim 1, wherein the organic group having fluorine represented by the following formula (6) has at least one structure represented by the following formula (6): 【Transformation 6】

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

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

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

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

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

10. a resist upper layer film formed on the inorganic hard mask intermediate film using a resist upper layer film material comprising a photoresist composition; a circuit pattern formed on the resist upper layer film; a pattern transfer step using the resist upper layer film on which the circuit pattern has been formed as a mask to transfer the pattern to the inorganic hard mask intermediate film by etching; a pattern transfer step using the inorganic hard mask intermediate film on which the pattern has been transferred as a mask to transfer the pattern to the organic film by etching; and a pattern transfer step using the organic film on which the pattern has been transferred as a mask to transfer the pattern to the workpiece by etching.

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

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

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

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

15. 8. The pattern forming method according to claim 7, wherein the workpiece is a semiconductor device substrate, or a semiconductor device substrate having any one of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film formed thereon.

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

17. A polymer having a partial structure (a1) represented by the following general formula (1) as a repeating unit: 【Transformation 7】 (In the formula, R １ , R ２ is a hydrogen atom or a saturated or unsaturated organic group having 1 to 20 carbon atoms, and has at least one structure having fluorine represented by the following general formula (2), and R １ , R ２ At least one of the groups represents an organic group other than a hydrogen atom. * represents a bond.) 【Transformation 8】 (* represents a bond.)

18. 18. The polymer according to claim 17, wherein the repeating unit (a1) of the polymer is a repeating unit represented by the following general formula (3) or (4): 【Chemistry 9】 (In the formula, R １ , R ２ is the same as above, and R ３ represents a hydrogen atom or a methyl group. n1 represents an integer of 2 to 10. 【Chemistry 10】 (In the formula, R １ , R ２ is the same as above, and R ４ represents a divalent organic group having 2 to 30 carbon atoms, which may contain an ether bond, an ester bond, an amide bond, or a sulfide bond.

19. The polymer according to claim 18, wherein the polymer is a copolymer having repeating units of the general formula (3) and the following general formula (5): 【Chemistry 11】 (In the formula, R ３ is the same as above, R ５ and R ６ are each a linear or branched divalent alkylene group having 1 to 4 carbon atoms, R ７ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, m1 represents 0 to 23, m2 represents 0 to 23, and 23≧m1+m2≧2.

20. R of the polymer １ or R ２ The polymer according to any one of claims 17 to 19, characterized in that the polymer has at least one structure represented by the following general formula (6) as a fluorine-containing structure represented by the following general formula (6): 【Chemistry 12】

Images