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

Abstract

To provide a composition for forming an organic film having both filling and flattening characteristics, and to provide a method for forming an organic film and a method for forming a pattern using the composition.SOLUTION: The composition for forming an organic film contains (A) an aromatic ring-containing resin, (B) a polymer containing a repeating unit containing a β diketone structure represented by formula (1), and (C) a solvent. (In the above formula (1), L1 is a saturated or unsaturated, linear or branched divalent hydrocarbyl group having 2 to 20 carbon atoms. RA and RB are each a hydrogen atom, a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a thiol group, a hydroxy group, an amino group, a carboxy group, or a halogen group. ) SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] The advancement of semiconductor device processing performance has been driven by the miniaturization of pattern dimensions due to the use of shorter wavelength light sources in lithography technology. However, since the advent of ArF light sources, the sensitivity of shorter wavelengths has declined, necessitating the need for higher performance instead of miniaturization. Accordingly, development of technologies that can improve semiconductor device performance by implementing three-dimensional semiconductor structures and arranging transistors at higher densities is underway. Substrates for semiconductor devices with such three-dimensional structures require deeper and thinner circuit patterns than conventional substrates. Therefore, lithography techniques optimized for the formation of planar structures cannot provide practical process tolerances. Therefore, it is necessary to create a flat surface using a material capable of planarizing the substrate on which the three-dimensional structure is formed, and then pattern the resulting surface using lithography to ensure process tolerances.

[0003] As a technology that can form such a flat surface, there is a technology for forming a flattened film using a spin-coated organic film. Many deposition techniques are already known (Patent Documents 1-5), but organic films formed from these materials are not compatible with all patterns on substrates used in semiconductor device manufacturing. The addition of pyrolytic polyacetal and other materials has also been proposed (Patent Document 6), but these materials induce film shrinkage through thermal decomposition, raising concerns about poor film formation and poor fillability. Furthermore, one practical method for planarization is to fill in the irregularities on the substrate and then planarize it using a chemical mechanical polishing (CMP) process (Patent Document 7), but CMP is a costly process. Under these circumstances, a low-cost method for highly planarizing substrates used in semiconductor device manufacturing using organic films is needed. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-292528 [Patent Document 2] Japanese Patent Application Laid-Open No. 2008-65081 [Patent Document 3] Japanese Patent Application Laid-Open No. 2008-242492 [Patent Document 4] Japanese Patent Application Laid-Open No. 2014-24831 [Patent Document 5] Japanese Patent Application Laid-Open No. 2014-219559 [Patent Document 6] International Publication No. WO2008 / 026468 Pamphlet [Patent Document 7] Japanese Patent Application Laid-Open No. 2004-335873 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition for forming an organic film having both high filling and planarizing properties, and a pattern forming method using the composition. [Means for solving the problem]

[0006] In order to solve the above problems, the present invention provides: (A) Aromatic ring-containing resin (B) A polymer containing a repeating unit containing a β-diketone structure represented by the following formula (1): (C) Solvent The present invention provides a composition for forming an organic film, which comprises: [ka] In the above formula (1), L1 is a saturated or unsaturated, straight-chain or branched divalent hydrocarbon group having 2 to 20 carbon atoms, and the hydrocarbon group may be interrupted one or more times by an atom selected from oxygen, nitrogen, and sulfur. A and R B may be the same or different and are a hydrogen atom, a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a thiol group, a hydroxyl group, an amino group, a carboxy group, or a halogen group.

[0007] If an aromatic ring-containing resin such as (A) is contained, etching resistance and processing resistance will be good. Furthermore, the polymer (B) containing a β-diketone structure as a repeating unit can be imparted with fluidity by appropriately selecting the structure represented by L1 contained in the polymer main chain, filling the uneven pattern after spin coating. Furthermore, heat promotes flow, which improves the flatness of the uneven surface when baked at high temperatures. While concerns about ordinary polyethylene and polyethylene glycol include poor solvent solubility, poor compatibility with the main resin, and poor film formation due to sublimation, the inclusion of a β-diketone structure eliminates these issues and makes sublimation less likely due to the interaction with the main polymer. Furthermore, the β-diketone structure and L1 are less susceptible to thermal decomposition, suppressing the sublimation of small molecules due to thermal decomposition, thereby providing an organic film-forming composition with excellent film-forming properties.

[0008] The aromatic ring-containing resin (A) preferably contains hydrogen at the diarylmethylene position or hydrogen at the trityl position.

[0009] If the aromatic ring-containing resin (A) contains hydrogen at the diarylmethylene position or hydrogen at the trityl position, the inclusion of these as a partial structure causes an oxidative coupling reaction accompanied by dehydrogenation due to heat, making it possible to harden the film through a crosslinking reaction.

[0010] Furthermore, it is preferable that the aromatic ring in the aromatic ring-containing resin (A) contains a hydroxyl group as a substituent.

[0011] If hydroxyl groups are included as substituents on the aromatic rings in the aromatic ring-containing resin (A), not only is oxidative coupling promoted, but dehydration reactions between hydroxyl groups also occur, resulting in more effective thermal curing and a composition that can form films with a high crosslinking group density and high processing resistance.Furthermore, the inclusion of hydroxyl groups strengthens the interaction with the β-diketone structure (B), resulting in a composition that is less likely to sublimate when baked and can form films with excellent film-forming properties.

[0012] The aromatic ring-containing resin (A) preferably contains a polymer having repeating units represented by the following formulas (P-1) and (P-2), and a compound selected from the group consisting of compounds represented by formulas (P-3) to (P-6). [ka] (In the following formulas (P-1) and (P-2), R is a hydrogen atom or a substituted or unsubstituted benzene ring or naphthalene ring. In (P-1) to (P-6), R1 is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. In (P-1), (P-3), (P-4) and (P-5), m1 is an integer of 0 or 1. In (P-1), (P-3), (P-4) and (P-6), n1 is an integer of 1 to 4. In (P-2) and (P-5), n2 is an integer of 1 or 2. In (P-3) and (P-5), n3 is an integer of 0 to 2. In (P-3) to (P-6), l is an integer of 5 to 20. Here, l represents the feed ratio.)

[0013] If the aromatic ring-containing resin (A) has a structure represented by any of the following formulas (P-1) to (P-6), the structure contains hydrogen at the diarylmethylene position or hydrogen at the trityl position, resulting in excellent thermosetting properties. Furthermore, if R1 is hydrogen, the structure contains a hydroxyl group, allowing for dense crosslinking, and furthermore, the interaction with the (B) β-diketone structure is stronger, resulting in a composition that can form a film with excellent film-forming properties.

[0014] In the above formula (1), R A and R B is preferably a hydrogen atom, a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds.

[0015] In the above formula (1), R A and R B is preferably a hydrogen atom.

[0016] In the above formula (1), if RA and RB are hydrogen atoms, substituted or unsubstituted linear alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted branched or cyclic alkyl groups having 3 to 20 carbon atoms, or substituted or unsubstituted aliphatic unsaturated hydrocarbon groups having 2 to 20 carbon atoms and containing one or more double or triple bonds, the resulting structure is more fluid, and the improvement in flatness due to thermal flow during embedding in an uneven substrate or high-temperature baking is more pronounced. A and R B is a hydrogen atom, which is more preferable since it facilitates raw material management.

[0017] In the above formula (1), L1 is preferably a saturated or unsaturated, straight-chain or branched hydrocarbon group having 2 to 20 carbon atoms and containing no heteroatoms.

[0018] In the above formula (1), if L1 is a saturated or unsaturated, straight-chain or branched hydrocarbon group having 2 to 20 carbon atoms and no heteroatoms, the bond is less likely to be dissociated by heat, and sublimation can be suppressed, resulting in a film with excellent film formability. Furthermore, from the viewpoint of raw material availability, it is preferable that L1 is a straight-chain hydrocarbon group having 2 to 20 carbon atoms.

[0019] It is preferable that the (B) polymer containing a β-diketone structure as a repeating unit is contained in an amount of 0.5 to 30 parts by mass per 100 parts by mass of the (A) aromatic ring-containing resin.

[0020] When the amount of (B) is 0.5 to 30 parts by mass relative to 100 parts by mass of the aromatic ring-containing resin (A), the planarization characteristics can be improved without impairing the processing resistance and etching resistance of the aromatic ring-containing resin (A), and the amount is more preferably 0.5 to 15 parts by mass.

[0021] The solvent (C) in the organic film-forming composition is preferably a mixture of a high-boiling point solvent and a low-boiling point solvent.

[0022] Such a solvent mixture does not volatilize too quickly during baking (heat treatment), so sufficient thermal fluidity can be obtained during film formation, making it possible to form an organic film with excellent filling / planarization properties.

[0023] The organic film-forming composition preferably further contains at least one of (D) a crosslinking agent and (E) a surfactant.

[0024] The present invention provides a method for forming an organic film that functions as an organic flat film used in the manufacturing process of a semiconductor device, which comprises spin-coating the organic film-forming composition described above onto a substrate to be processed, and then heat-treating the substrate coated with the organic film-forming composition at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds, thereby forming a cured film.

[0025] By carrying out the heat treatment under these conditions, flattening due to thermal flow and crosslinking reaction are promoted, and an organic film can be formed that does not mix with the film formed on top.

[0026] The present invention also provides a method for forming an organic film that functions as an organic flat film used in the manufacturing process of a semiconductor device, which comprises spin-coating the above-mentioned organic film-forming composition on a substrate to be processed, and heat-treating the substrate coated with the organic film-forming composition in an atmosphere having an oxygen concentration of 0.1% or more and 21% or less, thereby forming a cured film.

[0027] By baking in an oxygen atmosphere in this way, a sufficiently hardened organic film can be formed. Cut.

[0028] Furthermore, it is preferable that the substrate to be processed has a structure or step having a height of 30 nm or more.

[0029] The organic film-forming composition of the present invention has excellent filling / planarizing properties and is therefore particularly useful when forming a flat organic film on such a substrate to be processed.

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

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

[0032] The present invention also provides a pattern formation method, which includes forming an organic film on a workpiece using the above-mentioned organic film-forming composition, forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming a resist upper layer film on the inorganic hard mask using a resist upper layer film material consisting of a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the inorganic hard mask by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

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

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

[0035] Furthermore, it is preferable that the inorganic hard mask be formed by a CVD method or an ALD method.

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

[0037] As described above, the present invention can provide an organic film-forming composition having high-level filling / planarization properties. Furthermore, such an organic film-forming composition of the present invention not only has excellent filling / planarization properties, but also has excellent other properties such as heat resistance and etching resistance. Therefore, it is extremely useful as an organic film material used in multilayer resist processes such as a two-layer resist process, a three-layer resist process using a silicon-containing resist interlayer or an inorganic hard mask, or a four-layer resist process using a silicon-containing resist interlayer or an inorganic hard mask and an organic antireflective film, or as a planarization material for semiconductor device manufacturing. Furthermore, the organic film-forming method of the present invention can form an organic film on a workpiece substrate that has sufficient organic solvent resistance and is very flat. Furthermore, the pattern-forming method of the present invention can form a fine pattern on a workpiece with high precision using a multilayer resist process. [Brief explanation of the drawings]

[0038] [Figure 1] 1A to 1C are explanatory diagrams illustrating an example of a pattern formation method using a three-layer resist process according to the present invention. [Figure 2] FIG. 2 is an explanatory diagram of a method for evaluating the filling characteristics and the planarization characteristics. DETAILED DESCRIPTION OF THE INVENTION

[0039] As described above, there has been a demand for the development of an organic film-forming composition having high filling / planarization properties, and an organic film-forming compound useful for such a composition.

[0040] Usually, when forming an organic film, an organic film-forming compound is dissolved in an organic solvent to form a composition, which is then applied to a substrate on which the structure, wiring, etc. of a semiconductor device are formed, and baked to form an organic film. Immediately after applying the composition, a coating film is formed that conforms to the shape of the structure on the substrate, but when the coating film is baked, most of the organic solvent evaporates before it hardens, and an organic film is formed by the organic film-forming compound remaining on the substrate. The inventors have found that if the organic film-forming compound remaining on the substrate has sufficient thermal fluidity, the thermal fluidity will cause the organic film to We came to the conclusion that it is possible to flatten the uneven shape immediately after coating and form a flat film. The inventors further conducted extensive research and discovered that if a polymer with a specific structure (B) having a β-diketone structure in the repeating unit is added to a general composition of (A) an aromatic ring-containing resin and (C) a solvent, the polymer will be more likely to remain in the film due to the interaction between the β-diketone structure and (A) the aromatic ring-containing resin, and if a hydrocarbon group is further included in the repeating unit, the structure will be more susceptible to thermal flow, resulting in the formation of a film with excellent planarization properties, and thus completed the present invention.

[0041] The polymer containing a repeating unit having a β-diketone structure according to the present invention is a polyester in which the β-diketone structure constitutes the polymer main chain. There are no known examples of polyesters having such a structure being used in compositions for organic films used in lithography or the like.

[0042] That is, the present invention provides: (A) Aromatic ring-containing resin (B) A polymer containing a repeating unit containing a β-diketone structure represented by the following formula (1): (C) Solvent The organic film-forming composition is characterized by comprising: [ka] In the above formula (1), L1 is a saturated or unsaturated, straight-chain or branched divalent hydrocarbon group having 2 to 20 carbon atoms, and the hydrocarbon group may be interrupted one or more times by an atom selected from oxygen, nitrogen, and sulfur. R A and RB may be the same or different and are a hydrogen atom, a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a thiol group, a hydroxyl group, an amino group, a carboxy group, or a halogen group.

[0043] The present invention will be described in detail below, but the present invention is not limited thereto.

[0044] Hereinafter, the essential components of the organic film-forming composition of the present invention will be explained in the order of (B) the polymer containing a β-diketone structure as a repeating unit, (A) the aromatic ring-containing resin, and (C) the solvent.

[0045] [(B) Polymer containing β-diketone structure as a repeating unit] The polymer (B) containing a β-diketone structure as a repeating unit of the present invention is a polymer represented by the following formula (1). [ka] In the above formula (1), L1 is a saturated or unsaturated, straight-chain or branched divalent hydrocarbon group having 2 to 20 carbon atoms, and the hydrocarbon group may be interrupted one or more times by an atom selected from oxygen, nitrogen, and sulfur. R A and R B may be the same or different and are a hydrogen atom, a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a thiol group, a hydroxyl group, an amino group, a carboxy group, or a halogen group.

[0046] In the above formula (1), L1 is a saturated or unsaturated, straight-chain or branched divalent hydrocarbon group having 2 to 20 carbon atoms, and the hydrocarbon group may be interrupted one or more times by an atom selected from oxygen, nitrogen, and sulfur.

[0047] Specific examples of L1 include, but are not limited to, the following: [ka] (* represents the bond to the oxygen atom, and n is an integer of 1 to 10.)

[0048] In consideration of thermal stability, L1 is preferably a pure hydrocarbon group not interrupted by heteroatoms, and more preferably a linear hydrocarbon group in terms of thermal fluidity. In terms of raw material availability, L1 is preferably a linear hydrocarbon group having 2 to 20 carbon atoms.

[0049] In the above formula (1), R A and R B may be the same or different and are a hydrogen atom, a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a thiol group, a hydroxyl group, an amino group, a carboxy group, or a halogen group.

[0050] R A and R BSpecific examples of the substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and an octyl group. Specific examples of the substituted or unsubstituted branched alkyl group having 3 to 20 carbon atoms include an isopropyl group, an isobutyl group, and an isopentyl group. Specific examples of the cyclic alkyl group having 3 to 20 carbon atoms include cyclohexane, cyclopentyl, and methylcyclohexyl. Specific examples of the substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds include an allyl group and a propargyl group. Specific examples of the substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms include an alkyl group which may be interrupted once or multiple times by an atom selected from oxygen, nitrogen, and sulfur. Specific examples of the substituted or unsubstituted aryl group having 6 to 30 carbon atoms include a phenyl group and a tolyl group. R A and R B The substituent represented by is not limited to these specific examples.

[0051] R A and R B The following structures are also given as specific examples. [ka]

[0052] Also, when thermal fluidity is taken into consideration, R A and R B is preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, and is more preferably a hydrogen atom from the viewpoint of raw material availability.

[0053] The (B) polymer having a β-diketone structure in the repeating unit preferably has a weight-average molecular weight Mw of 1,000 to 20,000 in terms of polystyrene as determined by gel permeation chromatography. If the weight-average molecular weight Mw falls within this range, the polymer is less likely to sublimate at high temperatures, contributes to improved flatness due to thermal flow without causing film formation defects, and also has good solvent solubility.

[0054] From the viewpoint of processing resistance and etching resistance, it is preferable that the (B) polymer having a β-diketone structure as a repeating unit is contained in an amount of 0.5 to 50 parts by mass, more preferably 0.5 to 30 parts by mass, per 100 parts by mass of the (A) aromatic ring-containing resin.

[0055] [Method for producing polymer (B)] The polymer (B) having the repeating unit represented by formula (1) is a so-called polyester. A , R B A polymer can be obtained by a dehydration condensation reaction with a biscarboxylic acid having the formula (I), or by transesterification with an acid halide or acid anhydride or biscarboxylic acid ester corresponding to the biscarboxylic acid. Reaction formulae for dehydration condensation, acid halide, and transesterification are shown below as examples of reaction formulae. These can be appropriately selected taking into consideration the stability of the raw materials used. The amount of diol used is preferably 0.8 to 1.2 equivalents relative to the biscarboxylic acid or biscarboxylic acid derivative, and more preferably 0.9 to 1.1 equivalents from the viewpoints of reducing the molecular weight of the finished polymer and unreacted raw materials. (R in the following formula A , R B L1 is the same as above, X1 is a halogen atom, and R'' is an alkyl group having 1 to 5 carbon atoms.

[0056] [ka]

[0057] When the polymer (B) 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.

[0058] The reaction can proceed without a catalyst, but catalysts can be used, such as metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, etc.); alkali metal or alkaline earth metal carbonates (e.g., sodium carbonate, potassium carbonate, cesium carbonate, etc.); amines (e.g., imidazoles, benzotriazoles, etc.); phosphines (e.g., triphenylphosphine, etc.); quaternary ammonium salts (e.g., tetraalkylammonium halides (e.g., tetraethylammonium chloride, tetraethylammonium bromide, etc.), benzyltrialkylammonium chlorides (e.g., benzyltrimethylammonium chloride, benzyltriethylammonium chloride, etc.); quaternary phosphonium salts (e.g., benzyltriphenylphosphonium chloride, etc.); aluminum compounds (e.g., trialkylaluminum, etc.); tin compounds (e.g., tin chloride, tin carboxylates, etc.); and titanium compounds (e.g., titanium alkoxides, etc.). 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.

[0059] The reaction may be carried out without a solvent, or a solvent may 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 2,000 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 from 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.

[0060] When the polymer (B) 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.

[0061] 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.

[0062] The solvent used in this reaction is not particularly limited as long as it is inert to the reaction, and examples thereof 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.

[0063] After the completion of the dehydration condensation, transesterification, and acid halide-based reactions, unreacted raw materials, catalysts, etc., present in the system can be removed by raising the temperature of the reactor to 130 to 230°C and removing volatiles at about 1 to 50 mmHg, or by adding an appropriate poor solvent or water to precipitate or fractionate the polymer. These procedures can be applied depending on the properties of the raw materials used and the resulting reaction product. Finally, the resulting polymer can be diluted with an organic solvent and then recovered by separation and washing.

[0064] 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. Washing at least once is preferable because it provides a good purification effect. Washing up to 10 times is economical. The preferred number of washes is about 1 to 5 times.

[0065] 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.

[0066] 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.

[0067] The separation washing with the basic aqueous solution and the acidic aqueous solution may be carried out either alone or in combination. From the viewpoint of removing metal impurities, the separation washing is preferably carried out in the order of the basic aqueous solution and the acidic aqueous solution.

[0068] 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, preferably about one to five times. As the neutral water, deionized water or ultrapure water as mentioned above may be used. Washing at least once is preferable as it provides a good purification effect. Washing up to 10 times is economical. Preferably, washing is carried out about one to five times.

[0069] 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, making it easy to operate, and it is also economical because the amount of solvent is not excessive.

[0070] 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, and these can be used alone or in combination of two or more.

[0071] 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.

[0072] 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.

[0073] [Alternative method for producing polymer (B)] In addition, as another method for producing the polymer (B), the raw materials used in obtaining the polymer (B) described above, such as biscarboxylic acid, biscarboxylic acid ester, and biscarboxylic acid halide, are changed to a malonic acid derivative to obtain a polymer [STEP 1], and then the obtained polymer is subjected to a base catalyst treatment to form a partial structure of R A , R B and a method of obtaining it by addition reaction with a halide, mesylate, or tosylate having R A , R B If both are hydrogen, the reaction can be terminated at [STEP 1]. (In the following formula, X represents a halogenated group, mesylate, or tosylate. R A , R B , L1 is the same as above.) [ka]

[0074] When using the above reaction method, there are two reaction sites for each repeating unit of the polymer due to the reaction selectivity, so the reaction rate is 100%. A, R B is completely introduced as a substituent, and R A ≠R B when, there are the following three types of R A =R B =R’, one type can be obtained. Also, when the reaction rate is less than 100%, a polymer having repeating units with the following multiple combinations can be obtained. R A ≠R B when, there are the following six types of R A =R B =R’ when two types can be obtained. By adjusting the overall charging ratio, it becomes possible to control the reaction rate with respect to the overall reaction sites, and multiple or single R A , R B corresponding substituents can be used in combination. For example, when the substitution rate in the repeating unit of the polymer is 100, R A , R B when the ratio substituted by is a and the ratio present as an unmodified hydrogen atom is b, 0≦a + b≦100, 0.5 < b≦1.0 is preferable, and 0.7≦b≦1.0 is more preferable. At this time, R A and R B results in a polymer containing the repeating units shown below in relation to.

[0075]

Chemical formula

[0076] As a method for obtaining the above polymer, for the polymerization in STEP1, only the biscarboxylic acid which is the raw material of (B) is changed to the corresponding malonic acid, and it can be obtained by the method described in the above [Method for producing polymer (B)]. The polymer obtained in STEP1 can be used for the addition reaction in STEP2.

[0077] 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 these catalysts used is in the range of 0.1 to 2.5 moles, preferably 0.2 to 2.0 moles, relative to the number of moles of α-hydrogen in the raw material.

[0078] The solvent used in this reaction is not particularly limited as long as it is inert to the reaction, and examples thereof 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.

[0079] The reaction method is to use the polymer obtained in STEP 1 and the partial structure R A , R B A method of charging a halide, mesylate or tosylate having the formula (I), and a catalyst all at once, and the polymer obtained in STEP 1 and a partial structure R A , R B a method of dispersing or dissolving a halide, mesylate or tosylate having R and then adding the catalyst all at once or diluting it with a solvent and adding it dropwise; or a method of dispersing or dissolving a catalyst and then mixing the polymer obtained in STEP 1 with R A , R B A method in which a halide, mesylate or tosylate having the following substituent is added all at once or diluted with a solvent and added dropwise is given.

[0080] After the reaction is completed, steps such as separation and washing and filtration as described in the above [Method for producing polymer (B)] can be added.

[0081] In the production of the polymers used in the organic film-forming compositions obtained by these methods, the R of the polymer is adjusted to suit the required performance. A , R B By combining the structure, incorporation ratio, and polymer manufacturing method, it is possible to obtain polymers that meet the required performance. For example, it is possible to arbitrarily combine those with side chain structures that contribute to improving planarization properties, or those with fluorine-containing substituents that control surface tension and change surfactant properties.

[0082] [(A) Aromatic ring-containing resin] The (A) aromatic ring-containing resin is not particularly limited as long as it is a polymer containing an aromatic ring, and examples thereof include novolak resins, polyether resins, polyester resins, polystyrene resins, polymethacrylate resins, etc. Here, novolak resins refer to resins that can be synthesized by subjecting an aromatic ring-containing compound and an aldehyde compound or a compound having a benzyl alcohol unit, etc., to acidic or basic conditions and condensing them, while polyether resins and polyester resins refer to resins that contain ether or ester in the repeating unit, and polystyrene resins and polymethacrylate resins are resins obtained by polymerizing monomers having a styrene or methacrylic (acrylic) structure through radical polymerization.

[0083] Furthermore, the aromatic ring-containing resin (A) of the present invention includes not only the polymer having a repeating unit of a specific structure as described above, but also a compound having a structure in which multiple types of aromatic compounds are bonded. The polymer having a repeating unit and the compound having a structure in which multiple types of aromatic compounds are bonded are described below.

[0084] The aromatic ring may include not only a structure in which benzene rings are condensed, such as a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a chrysene ring, a benzopyrene ring, or a coronene ring, but also a heterocycle, such as pyrrole, pyridine, furan, or thiophene. Furthermore, it may include a structure in which multiple aromatic rings are bonded via hydrocarbons, ethers, esters, or the like, such as biphenyl, diaryl ether, or fluorene.

[0085] Examples of the aromatic ring-containing resin (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), 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.)

[0086] [ka] (In formula (2), the ring structures Ar1 and Ar2 represent a benzene ring or a naphthalene ring. n represents any natural number such that the weight average molecular weight, as calculated using polystyrene standards by gel permeation chromatography, is 100,000 or less. Note that the symbols in the formula are used only within this formula.)

[0087] Further examples of the aromatic ring-containing resin (A) used in the present invention include resins containing the following structures described in JP-A Nos. 2004-264710, 2005-043471, 2005-250434, 2007-293294, and 2008-065303. [ka] (In formula (3) and formula (4), R 1 and R 2represents 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.

[0088] [ka] (In formula (5), R1 is a monovalent atom or group other than a hydrogen atom, and n is an integer of 0 to 4. However, when n is 2 to 4, multiple R1s may be the same or different. R2 and R3 are independently a monovalent atom or group. X is a divalent group. Note that the symbols in the formula apply only within this formula.)

[0089] [ka] In formula (6), R1 is a hydrogen atom or a methyl group. R2 is a single bond, a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 10 carbon atoms, and may have any of ether, ester, lactone, and amide. R 3 , R 4 are each a hydrogen atom or a glycidyl group. X represents a polymer of any one of hydrocarbons containing an indene skeleton, cycloolefins having 3 to 10 carbon atoms, and maleimide, and may have any one of ethers, esters, lactones, and carboxylic acid anhydrides. R 5 , R 6 R is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. 7 is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a hydroxy group, or an alkoxycarbonyl group. p and q are each an integer of 1 to 4. r is an integer of 0 to 4. a, b, and c are in the ranges of 0.5≦a+b+c≦1, 0≦a≦0.8, 0≦b≦0.8, 0.1≦a+b≦0.8, and 0.1≦c≦0.8, respectively. Note that the symbols in the formula apply only within this formula.

[0090] [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.)

[0091] Specific examples of the aromatic ring-containing resin (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.

[0092] [ka] (In formula (10), R 1 , R 6 is a hydrogen atom or a methyl group. 2 , R 3 , R 4 is a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, an acetoxy group, or an alkoxycarbonyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and R 5 is a condensed polycyclic hydrocarbon group having 13 to 30 carbon atoms, -OR 7 , -C(=O)-OR 7 , -OC(=O)-R 7 or -C(=O)-NR 8 -R 7 where m is 1 or 2, n is an integer of 0 to 4, and p is an integer of 0 to 6.7 is an organic group 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-, -NH-. a, b, c, d, 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, 0 < b + c + d + e < 1.0. Note that the symbols in the formula are applicable only within this formula.)

[0093] [Chemical formula] (In formula (11), n represents 0 or 1. R 1 represents an optionally substituted methylene group, an optionally substituted alkylene group having 2 to 20 carbon atoms, or an optionally substituted arylene group having 6 to 20 carbon atoms. R 2 represents a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms. R 3 ~R 7 represents a hydroxyl group, an optionally substituted alkyl group having 1 to 6 carbon atoms, an optionally substituted alkoxy group having 1 to 6 carbon atoms, an optionally substituted alkoxycarbonyl group having 2 to 10 carbon atoms, an optionally substituted aryl group having 6 to 14 carbon atoms, or an optionally substituted glycidyl ether group having 2 to 6 carbon atoms. R 9 represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic alkyl ether group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Note that the symbols in the formula are applicable only within this formula.)

[0094] Examples of formula (11) include the following resins. [Chemical formula]

[0095] [Chemical formula]

[0096] Examples of the aromatic ring-containing resin (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.

[0097] [ka] (In formula (13), R 1 and R 2 are independently the same or different hydrogen atoms, linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, or alkenyl groups having 2 to 10 carbon atoms, and R 3 is a single bond or an alkylene group having a linear, branched or cyclic structure and having 1 to 30 carbon atoms, which may have a bridged cyclic hydrocarbon group, a double bond, a heteroatom or an aromatic group having 6 to 30 carbon atoms; R 4 and R 5 are each independently a hydrogen atom or a glycidyl group, and R 6 is a single bond or a linear or branched alkylene group having 1 to 10 carbon atoms. The symbols in the formula are applicable only within this formula.

[0098] [ka] (In formula (14), ring Z 1 and ring Z 2 are fused polycyclic aromatic hydrocarbon rings, R 1a , R 1b , R 2a , and R 2b represent the same or different substituents. k1 and k2 represent the same or different integers of 0 or 1 to 4, m1 and m2 each represent an integer of 0 or 1 or more, and n1 and n2 each represent an integer of 0 or 1 or more. However, n1 + n2 ≥ 1. Note that the symbols in the formula are applicable only within this formula.)

[0099]

Chemical formula

[0100] As formula (15), for example, the following resins are exemplified.

Chemical formula

[0101]

Chemical formula

[0102]

Chemical formula

[0103] [ka]

[0104] Examples of the aromatic ring-containing resin (A) used in the present invention include resins containing the following structure described in JP-A 2012-214720. [ka] (In formula (16), the ring structures Ar1 and Ar2 represent a benzene ring or a naphthalene ring. x and z each independently represent 0 or 1. Note that the symbols in the formula apply only within this formula.)

[0105] Examples of the aromatic ring-containing resin (A) used in the present invention include resins described in JP-A-2014-29435. [ka] (In formula (17), A represents a structure having carbazole, B represents a structure having an aromatic ring, and C represents a structure having a hydrogen atom, an alkyl group, or an aromatic ring, and B and C may form a ring together. The combined structure of A, B, and C contains 1 to 4 carboxyl groups or salts thereof, or carboxylate ester groups. Note that the symbols in the formula apply only within this formula.)

[0106] Furthermore, examples of the aromatic ring-containing resin (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.

[0107] [ka] In formula (19), Ar represents an aromatic ring group having 6 to 20 carbon atoms, R6 represents a hydroxy group, R7 represents a hydrogen atom, a halogen atom, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, or a combination of these groups which may contain an ether bond, a ketone bond, or an ester bond, and R8 represents a hydrogen atom, or a halogen atom which may be substituted with a nitro group, an amino group, or a hydroxy group. R8 represents an aryl group or heterocyclic group having 6 to 40 carbon atoms, R9 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, a nitro group, an amino group, or a hydroxy group, or an aryl group or heterocyclic group having 6 to 40 carbon atoms, and R8 and R9 may together form a ring. n6 represents an integer of 1 to p, and n7 represents an integer of p-n6, where p represents the maximum number of substituents that can be substituted on the aromatic ring group Ar. The symbols in the formula are only applicable within this formula.

[0108] An example of the aromatic ring-containing resin (A) used in the present invention is a polymer containing a unit structure represented by the following formula (20) described in WO 2010 / 147155. [ka] In formula (20), R1 and R2 are each selected from the group consisting of a hydrogen atom, a halogen group, a nitro group, an amino group, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a combination thereof, and the alkyl group, the alkenyl group, or the aryl group represents a group which may contain an ether bond, a ketone bond, or an ester bond; R3 is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 40 carbon atoms, and a combination thereof, and the alkyl group, the alkenyl group Alternatively, the aryl group represents a group which may contain an ether bond, a ketone bond, or an ester bond; R4 represents an aryl group or heterocyclic group having 6 to 40 carbon atoms which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxy group; R5 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an aryl group or a heterocyclic group having 6 to 40 carbon atoms which may be substituted with a halogen group, a nitro group, an amino group, or a hydroxy group; R4 and R5 may form a ring together with the carbon atoms to which they are bonded; and n1 and n2 are each an integer of 1 to 3. Note that the symbols in the formula apply only within this formula.

[0109] Examples of the aromatic ring-containing resin (A) used in the present invention include a novolak resin 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 a resin containing a repeating unit structure represented by the following formula (21), which is 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.)

[0110] Examples of the aromatic ring-containing resin (A) used in the present invention include novolak resins having a fluorene or tetrahydrospirobiindene structure described in JP-A Nos. 2005-128509, 2006-259249, 2006-259482, 2006-293298, and 2007-316282, which contain a repeating unit structure represented by the following formula (22-1) or (22-2): [ka] (In formula (22-1) and formula (22-2), R 1 , R 2 , R 6 , R 7 are independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an allyl group, or a halogen atom; R 3 , R 4 , R 8 , R 9 are independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a glycidyl group; R 5 , R 14 are independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. n, m, p and q are integers of 1 to 3. R 10 ~R 13 are independently a hydrogen atom, a halogen atom, a hydroxy group, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms. Note that the symbols in the formula apply only within this formula.)

[0111] The aromatic ring-containing resin (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, it can be a polymer obtained by condensing one or more compounds represented by the following formula (23-1) and / or (23-2) with one or more compounds represented by the following formula (24-1) and / or (24-2) and / or their equivalents. [ka] (In formula (23-1) and 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.)

[0112] [ka] (In formula (24-1) and 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 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.)

[0113] Further, examples of the polymers include those obtained by condensing one or more compounds represented by the above formula (23-1) and / or (23-2), one or more compounds represented by the above formula (24-1) and / or (24-2) and / or equivalents thereof, and one or more compounds represented by the following formula (25) and / or equivalents thereof. [ka] (In formula (25), Y is 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 formula (24-1) and formula (24-2). Note that the symbols in the formula apply only within this formula.)

[0114] Examples of the aromatic ring-containing resin (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 formula (26-2), and m1 is an integer satisfying 2≦m1≦10. Note that the symbols in the formula apply only within this formula.)

[0115] [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 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.

[0116] Examples of compounds containing the above structure include the following compounds. [ka]

[0117] Examples of the aromatic ring-containing resin (A) used in the present invention include polymers having a repeating unit represented by the following 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.

[0118] [ka]

[0119] [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.

[0120] Examples of polymers having a repeating unit represented by the above formula (27-1) include the following polymers. [ka]

[0121] [ka]

[0122] The aromatic ring-containing resin may be a single type, or multiple types of resins with different structures may be combined. By using multiple aromatic ring-containing resins in combination, crystallinity is suppressed compared to when a single resin is used, which is expected to improve thermal fluidity and flatness.

[0123] From the viewpoint of thermosetting properties, the aromatic ring-containing resin (A) preferably contains hydrogen at the diarylmethylene position or hydrogen at the trityl position.

[0124] The hydrogen atom at the diarylmethylene position is the remaining hydrogen atom in the structure in which two hydrogen atoms of methane are replaced with aryl groups, as shown in the formula below, and the hydrogen atom at the trityl position is the remaining hydrogen atom in the structure in which three hydrogen atoms of methane are replaced with aryl groups. By including these as partial structures, an oxidative coupling reaction accompanied by dehydrogenation occurs due to heat, and the film can be hardened by a crosslinking reaction. In the formula below, a phenyl group is used as a specific example of the aryl group, but this is not limiting. [ka]

[0125] Examples of the substituent on the aromatic ring in the aromatic ring-containing resin (A) above include various substituents such as a hydroxyl group, an ether group, a carboxy group, a ketone group, an amino group, an alkylamino group, a halogen group, an alkyl group, an alkenyl group, and an alkynyl group, and there are no particular limitations on the substituents that can be used.

[0126] If the aromatic ring-containing resin (A) contains a hydroxyl group as a substituent, not only is the oxidative coupling reaction more likely to occur, but dehydration reactions between the hydroxyl groups also occur, making it possible to form a film with a high crosslinking group density and providing a film with excellent processing resistance. Furthermore, the inclusion of a hydroxyl group strongly interacts with the β-diketone structure of (B), suppressing sublimation of the polymer containing the β-diketone structure of (B), making it possible to provide a film with excellent film-forming properties.

[0127] It is more preferable that the aromatic ring-containing resin (A) above contains a polymer having repeating units represented by the following formulas (P-1) and (P-2), and a compound selected from the group consisting of compounds represented by formulas (P-3) to (P-6). [ka] (In the following formulas (P-1) and (P-2), R is a hydrogen atom or a substituted or unsubstituted benzene ring or naphthalene ring. In (P-1) to (P-6), R1 is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. In (P-1), (P-3), (P-4) and (P-5), m1 is an integer of 0 or 1. In (P-1), (P-3), (P-4) and (P-6), n1 is an integer of 1 to 4. In (P-2) and (P-5), n2 is an integer of 1 or 2. In (P-3) and (P-5), n3 is an integer of 0 to 2. In (P-3) to (P-6), l is an integer of 5 to 20. Here, l represents the feed ratio.)

[0128] In the above formulas (P-1) and (P-2), R is a hydrogen atom or a substituted or unsubstituted benzene ring or a naphthalene ring, and is preferably a hydrogen atom or a substituted or unsubstituted benzene ring from the viewpoint of raw material availability. Furthermore, when R is a benzene ring, it is preferably the following structure from the viewpoint of thermosetting properties. [ka] (In the above formula, * represents the bond to the methylene moiety, and R1 is the same as R1 in the above formulas (P-1) to (P-6))

[0129] In (P-1) to (P-6), R1 is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. From the viewpoint of inhibiting sublimation due to interaction with (B) the polymer containing a β-diketone structure in its repeating unit, it is preferably a hydrogen atom. From the viewpoint of the curability of the resin alone, it is preferably a hydrogen atom or a hydrocarbon group containing an unsaturated bond. From the viewpoint of the thermal fluidity of the resin alone, it is preferably a long-chain saturated hydrocarbon group.

[0130] In (P-1) to (P-6), specific examples of R1 other than a hydrogen atom include, but are not limited to, the following structures. [ka] (In the above formula, * indicates the bond to the oxygen atom)

[0131] [Method for producing aromatic ring-containing resins (P-1) and (P-2)] The above formulas (P-1) and (P-2) are prepared by condensation reaction (STEP 1) using an aromatic ring-containing compound (X) containing a hydroxyl group as a substituent, formaldehyde, or a benzene or naphthalene ring (Y) containing an aldehyde as a substituent, and a catalyst. If R1 is subsequently etherified as a partial hydrocarbon group, the resulting condensate can be etherified (STEP 2) using an alkyl halide, alkyl tosylate, or alkyl mesylate (Z) and a catalyst. However, the resin can be completed without the STEP 2 reaction, with all hydroxyl groups remaining. When STEP 2 is performed, the charge ratio of (Z) used is 0.1 to 0.9 equivalents, more preferably 0.3 to 0.7 equivalents, per equivalent of hydroxyl groups. (R, R1, n1, and m1 are the same as above, and X represents a halogen group, mesyl group, or tosyl group. For convenience, the reaction formula is described using (P-1) as an example.)

[0132] [ka]

[0133] [ka]

[0134] The condensation reaction using the catalyst (X) or (Y) can be carried out in a solvent or without a solvent using an acid or a base as a catalyst at room temperature or, if necessary, under cooling or heating. Examples of the solvent include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ethers such as diethyl ether, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and 1,4-dioxane; and chlorinated solvents such as methylene chloride, chloroform, dichloroethane, and trichloroethylene. Examples of suitable solvents include solvents such as hexane, heptane, benzene, toluene, xylene, and cumene; nitriles such as acetonitrile; ketones such as acetone, ethyl methyl ketone, and isobutyl methyl ketone; esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate; lactones such as γ-butyrolactone; and aprotic polar solvents such as dimethyl sulfoxide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and hexamethylphosphoric triamide. These solvents can be used alone or in combination of two or more. These solvents can be used in an amount of 0 to 3,000 parts by mass per 100 parts by mass of the reaction raw materials.

[0135] Examples of the acid catalyst that can be used include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, and heteropolyacids; organic acids such as oxalic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid; and Lewis acids such as aluminum trichloride, aluminum ethoxide, aluminum isopropoxide, boron trifluoride, boron trichloride, boron tribromide, tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dibutyltin dimethoxide, dibutyltin oxide, titanium tetrachloride, titanium tetrabromide, titanium(IV) methoxide, titanium(IV) ethoxide, titanium(IV) isopropoxide, and titanium(IV) oxide. Examples of base catalysts that can be used include inorganic bases such as sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, lithium hydride, sodium hydride, potassium hydride, and calcium hydride; alkyl metals such as methyllithium, n-butyllithium, methylmagnesium chloride, and ethylmagnesium bromide; alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide; and organic bases such as triethylamine, diisopropylethylamine, N,N-dimethylaniline, pyridine, and 4-dimethylaminopyridine. The amount of base catalyst used is 0.001 to 100% by weight, preferably 0.005 to 50% by weight, based on the raw materials. The reaction temperature is preferably from -50°C to the boiling point of the solvent, more preferably from room temperature to 130°C.

[0136] Condensation reaction methods include charging (X), (Y), and a catalyst all at once, adding (Y) or a solution of (Y) dissolved in a reaction solvent in the presence of (X) and a catalyst dropwise, or adding (X) or a solution of (X) dissolved in a reaction solvent in the presence of (Y) and a catalyst dropwise. When synthesizing resins represented by formulas (P-1) and (P-2), the amount of (Y) used relative to (X) is preferably 0.7 to 1.2 equivalents, more preferably 0.8 to 1.05 equivalents. When synthesizing resins represented by formulas (P-3) to (P-6), the amount of (Y) relative to (X) is preferably 5.0 to 20 equivalents, more preferably 6.0 to 15.0 equivalents. After the condensation reaction is complete, unreacted raw materials, catalysts, etc. remaining in the system can be removed by raising the temperature of the reactor to 130-230°C and removing volatiles at about 1-50 mmHg, adding an appropriate poor solvent or water to reprecipitate the polymer, or fractionating the polymer. Depending on the properties of the raw materials used and the reaction product obtained, various methods can be used. Furthermore, a step can be added in which the resulting condensate is dissolved in methyl isobutyl ketone, ethyl acetate, etc., and washed with water.

[0137] The subsequent etherification can usually be carried out without a solvent or in a solvent using a base as a catalyst at room temperature or, if necessary, under cooling or heating. Examples of the solvent that can be used include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether, ethers such as diethyl ether, dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and 1,4-dioxane, and chlorinated solvents such as methylene chloride, chloroform, dichloroethane, and trichloroethylene. Examples of solvents include hydrocarbons such as hexane, heptane, benzene, toluene, xylene, and cumene; nitriles such as acetonitrile; ketones such as acetone, ethyl methyl ketone, and isobutyl methyl ketone; esters such as ethyl acetate, n-butyl acetate, and propylene glycol methyl ether acetate; lactones such as γ-butyrolactone; and aprotic polar solvents such as dimethyl sulfoxide, N,N-dimethylformamide, hexamethylphosphoric triamide, and N-methylpyrrolidone. These solvents can be used alone or in combination. These solvents can be used in an amount of 0 to 2,000 parts by mass per 100 parts by mass of the reaction raw materials.

[0138] Examples of base catalysts that can be used include inorganic bases such as sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, lithium hydride, sodium hydride, potassium hydride, and calcium hydride; alkyl metals such as methyllithium, n-butyllithium, methylmagnesium chloride, and ethylmagnesium bromide; alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide; and organic bases such as triethylamine, diisopropylethylamine, N,N-dimethylaniline, pyridine, and 4-dimethylaminopyridine. The amount of catalyst used is preferably 0.5 to 1.5 equivalents, more preferably 1.0 to 1.2 equivalents, relative to the equivalent of hydroxyl groups contained in the raw materials for the condensation reaction. The reaction temperature is preferably from -50°C to the boiling point of the solvent, and more preferably from room temperature to 130°C.

[0139] The reaction can be carried out by adding the condensate, R2-X(Z), and a catalyst all at once, by adding dropwise a solution of the condensate and the catalyst in the presence of (Z) or (Z) in a reaction solvent, or by adding dropwise a solution of the condensate in the presence of (Z) and a catalyst in a reaction solvent. In this case, the amount of (Z) used is preferably 0.1 to 0.9 equivalents, more preferably 0.3 to 0.7 equivalents, relative to the amount of hydroxyl groups in the condensate.

[0140] After the etherification is completed, steps such as separation and washing and filtration as described in the above [Method for producing polymer (B)] can be added, as in the case of polymer (B).

[0141] [Method for producing aromatic ring-containing resins (P-3) to (P-6)] The compounds represented by the above formulas (P-3) to (P-6) are synthesized by a condensation reaction (STEP 1) of an aromatic ring-containing compound (X) containing a hydroxyl group with a benzene ring, naphthalene ring, diphenyl ether, or the like (W) containing a methylol group or a methoxymethyl group, using a catalyst. R1 is then introduced by an etherification reaction. The condensate obtained by the reaction in STEP 1 is etherified with an alkyl halide, alkyl tosylate, or alkyl mesylate (Z) using a catalyst (STEP 2). However, the reaction in STEP 2 may be omitted, and the resin may be completed with all hydroxyl groups. When the reaction in STEP 2 is carried out, the charge ratio of (Z) used is 0.1 to 0.9 equivalents, more preferably 0.3 to 0.7 equivalents, based on 1 equivalent of hydroxyl groups. (R, R1, n1, n 3、 m1 and l are the same as above, X represents a halogen group, a mesyl group, or a tosyl group, and for convenience, the reaction formula is described using (P-3) as an example.

[0142] [ka]

[0143] [ka]

[0144] The notation of the aromatic ring-containing resins (P-3) to (P-6) in this specification will be explained below. In the formula for the condensation reaction of (X) and (W) described above, the product is written as having one mother nucleus condensed with an aromatic ring containing a methylol group or a methoxymethyl group, but in this specification, l represents the ratio of the synthetic raw materials used in the synthesis reaction of aromatic ring-containing resins (P-3) to (P-6). For example, if a condensation reaction is carried out using 1 equivalent of 2,3-dihydroxynaphthalene as (X) and 12 equivalents of 4-hydroxybenzyl alcohol as (W), l is written as 12. In the synthesis of this compound shown above, the condensation reaction (reaction formula (a)) of 2,3-dihydroxynaphthalene (X) with 4-hydroxybenzyl alcohol (W) can only react with a maximum of six equivalents of 4-hydroxybenzyl alcohol because the highly reactive position of 2,3-dihydroxynaphthalene (X) has six hydrogen atoms on the aromatic ring. Simultaneously, a condensation reaction (reaction formula (b)) between 4-hydroxybenzyl alcohols (W) also occurs. As a result, the product of this reaction is a complex mixture of the two reactions (a) and (b) above. Therefore, since the amount of 4-hydroxybenzyl alcohol reacted with respect to the product of this reaction is equal to the charge equivalent, the charge amount is set to 1, and the product is expressed as the following formula (c).

[0145] In this synthesis reaction, 2,3-dihydroxynaphthalene plays a role similar to that of a capping agent in the condensation reaction between 4-hydroxybenzyl alcohols, and is thought to have the effect of adjusting the Mw of the product, preventing an increase in molecular weight and a decrease in the fluidity of the resin.

[0146] As mentioned above, 2,3-dihydroxynaphthalene does not have any reactive functional groups, so if 0.5 equivalents of propargyl bromide as an alkyl halide are reacted with 1 equivalent of the hydroxyl groups in the entire resin after condensation, the reaction will be as shown in the following formula: In this case, the hydroxyl groups are randomly introduced into the hydroxyl groups of the resin, resulting in a mixture with different hydroxyl group equivalents, and the ratio of hydroxyl groups to propargyl ether in the entire resin is 0.5:0.5, which means that 50% have been propargylated. [ka]

[0147] [ka]

[0148] The condensation reaction using the above-mentioned (X), (W), and catalyst can be carried out by the method described in (STEP 1) above, simply by changing (Y) to (W).

[0149] The aromatic ring-containing resin (A) thus obtained preferably has a weight-average molecular weight Mw, calculated as polystyrene, by gel permeation chromatography (GPC), of 1,000 to 20,000. If the weight-average molecular weight Mw falls within this range, the resin is less likely to sublimate at high temperatures, does not cause film formation defects, and can suppress poor embedding due to an excessively large molecular weight and deterioration of flatness due to poor thermal fluidity.

[0150] Components that can be contained in the organic film-forming composition of the present invention other than the (A) aromatic ring-containing resin and (B) polymer having a β-diketone structure in the repeating unit will be described below.

[0151] <(C) Solvent> The solvent (C) that can be used in the organic film-forming composition of the present invention is not particularly limited as long as it dissolves the above-mentioned (A) one or more polymers containing an aromatic ring, (B) a polymer having a β-diketone structure in a repeating unit, (D) a crosslinking agent, (E) a surfactant, and other additives.

[0152] Specifically, the organic solvents described in paragraphs

[0091] and

[0092] of JP 2007-199653 A can be added. More specifically, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, 2-heptanone, cyclopentanone, cyclohexanone, γ-butyrolactone, or a mixture containing one or more of these is preferably used.

[0153] The amount of the organic solvent to be added is preferably in the range of 200 to 10,000 parts, more preferably 250 to 5,000 parts, per 100 parts by mass of the aromatic ring-containing resin (A).

[0154] <High boiling point solvent> In the organic film-forming composition of the present invention, the (C) solvent may be used as a mixture of one or more solvents having a boiling point of less than 180° C. and one or more solvents having a boiling point of 180° C. or higher (high boiling point solvents).

[0155] The high-boiling point solvent is not particularly limited as long as it can dissolve each component of the aromatic ring-containing resin of the present invention, 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, 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, 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 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, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, 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.

[0156] The high-boiling point solvent may be appropriately selected from, for example, those listed above, depending on the temperature at which the organic film-forming composition of the present invention is heat-treated. The boiling point of the high-boiling point solvent is preferably 180°C to 300°C, and more preferably 200°C to 300°C. Such a boiling point is unlikely to cause excessively rapid evaporation during baking (heat treatment), making it possible to obtain sufficient thermal fluidity during film formation and forming an organic film with excellent filling / planarization properties. Furthermore, such a boiling point prevents the solvent from volatilizing and remaining in the film after baking, eliminating the risk of adversely affecting film properties such as etching resistance.

[0157] When a high-boiling point solvent is used, the blending amount is preferably 1 to 30 parts by mass per 100 parts by mass of an organic solvent having a boiling point of less than 180° C. This blending amount is preferable because it can impart sufficient thermal fluidity during baking and does not remain in the film, leading to deterioration of film properties such as etching resistance.

[0158] The composition is a composition that can be used as an organic film for use in a multilayer resist method, and may further contain one or more of (D) a crosslinking agent and (E) a surfactant. The (D) crosslinking agent and (E) surfactant will be described below.

[0159] [(D) Crosslinking agent] The organic film-forming composition of the present invention may further contain a (D) crosslinking agent to enhance the film density and further suppress intermixing with the resist upper layer film. The crosslinking agent is not particularly limited, and a wide variety of known crosslinking agents can be used. Examples include melamine-based crosslinking agents, acrylate-based crosslinking agents, glycoluril-based crosslinking agents, benzoguanamine-based crosslinking agents, urea-based crosslinking agents, β-hydroxyalkylamide-based crosslinking agents, isocyanurate-based crosslinking agents, aziridine-based crosslinking agents, oxazoline-based crosslinking agents, phenol-based crosslinking agents (e.g., methylol or alkoxymethyl-type crosslinking agents of polynuclear phenols), epoxy-based crosslinking agents, and oxetane-based crosslinking agents. The content of the (D) crosslinking agent is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, per 100 parts by mass of the (A) one or more aromatic ring-containing polymers.

[0160] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylated melamine, hexabutoxymethylated melamine, alkoxy- and / or hydroxy-substituted products thereof, and partial self-condensates thereof. A specific example of the acrylate crosslinking agent is dipentaerythritol hexaacrylate. Specific examples of glycoluril crosslinking agents include tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, alkoxy and / or hydroxy substituted products thereof, and partial self-condensates thereof. Specific examples of benzoguanamine-based crosslinking agents include tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, alkoxy- and / or hydroxy-substituted products thereof, and partial self-condensates thereof. Specific examples of urea-based crosslinking agents include dimethoxymethylated dimethoxyethylene urea, its alkoxy and / or hydroxy substituted derivatives, and partial self-condensates thereof. A specific example of the β-hydroxyalkylamide crosslinking agent is N,N,N',N'-tetra(2-hydroxyethyl)adipamide. Specific examples of the isocyanurate crosslinking agent include triglycidyl isocyanurate and triallyl isocyanurate. Specific examples of the aziridine crosslinking agent include 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate]. Specific examples of the oxazoline-based crosslinking agent include 2,2'-isopropylidenebis(4-benzyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), 2,2'-methylenebis-4,5-diphenyl-2-oxazoline, 2,2'-methylenebis-4-phenyl-2-oxazoline, 2,2'-methylenebis-4-tertbutyl-2-oxazoline, 2,2'-bis(2-oxazoline), 1,3-phenylenebis(2-oxazoline), 1,4-phenylenebis(2-oxazoline), and 2-isopropenyloxazoline copolymer.

[0161] Specific examples of polynuclear phenol-based crosslinking agents include compounds represented by the following formula (XL-1). [ka] (In the formula, S is a single bond or an s-valent hydrocarbon group having 1 to 20 carbon atoms. R6 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. s is an integer of 1 to 5. The definition of R6 here relates to R6 in formula (XL-1).)

[0162] S is a single bond or an s-valent hydrocarbon group having 1 to 20 carbon atoms. s is an integer of 1 to 5, and more preferably 2 or 3. Specific examples of S include groups obtained by removing q hydrogen atoms from methane, ethane, propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, methylpentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylisopropylbenzene, diisopropylbenzene, methylnaphthalene, ethylnaphthalene, and eicosane. R6 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, an octyl group, an ethylhexyl group, a decyl group, and an eicosanyl group, with a hydrogen atom or a methyl group being preferred.

[0163] Specific examples of the compound represented by formula (XL-1) include the following compounds. Among these, hexamethoxymethylated triphenolmethane, triphenolethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene are preferred from the viewpoint of improving the curability and thickness uniformity of the organic film. R6 is the same as above. [ka]

[0164] [ka]

[0165] The epoxy-based crosslinking agent and the oxetane-based crosslinking agent may be of a monomer type or a polymer type, and specific examples of the monomer type include, but are not limited to, those shown below. [ka]

[0166] While some of the above compounds are commercially available, epoxy-based crosslinking agents and oxetane-based crosslinking agents can also be obtained by reacting hydroxyl groups with epibromohydrin, 3-bromomethyloxetane, or the like, as shown in the following formula. In the formula, R represents a substituted or unsubstituted saturated monovalent organic group having 1 to 20 carbon atoms or an unsaturated monovalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl-alkyl group having 7 to 31 carbon atoms. Alternatively, all hydroxyl groups can be left unreacted. In this case, the number of epoxy groups plus the number of oxetane groups is preferably greater than the number of hydroxyl groups, and more preferably, the number of epoxy groups plus the number of oxetane groups is greater than the number of hydroxyl groups * 2. The content of these compounds is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, per 100 parts by mass of the (a) aromatic ring-containing resin. [ka]

[0167] Specific examples of compounds having a hydroxyl group that can be used in the above reaction include, but are not limited to, the following: [ka]

[0168] Specific examples of the polymer type include polymers in which the molar fraction of repeating units represented by the following formulae (XL-2) and (XL-3) is 20% or more. When the molar fractions of the structural units represented by formulae (XL-2) and (XL-3) do not add up to 100%, other structural units may be used in combination with any of the following structural units: other acrylic acid esters, other methacrylic acid esters, other acrylic acid amides, other methacrylic acid amides, crotonates, maleates, itaconic acid esters, and other α,β-unsaturated carboxylic acid esters; α,β-unsaturated carboxylic acids such as methacrylic acid, acrylic acid, maleic acid, and itaconic acid; acrylonitrile; methacrylonitrile; α,β-unsaturated lactones such as 5,5-dimethyl-3-methylene-2-oxotetrahydrofuran; cyclic olefins such as norbornene derivatives and tetracyclo[4.4.0.12,5.17,10]dodecene derivatives; α,β-unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; allyl ethers; vinyl ethers; vinyl esters; and vinylsilanes. These polymers preferably have a weight average molecular weight of 1,000 to 20,000 and a GPC dispersion index of 2.0 or less. The content of these compounds is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, per 100 parts by mass of the (A) aromatic ring-containing resin.

[0169] [ka] (In the formula, R7 is a hydrogen atom or a methyl group, R8 is a hydrogen atom or a group selected from the following formulae (2-1) to (2-3), and L1 is a divalent organic group containing a single bond, —C(═O)O—, C(═O)NH—, or C(═O)NCH3—.)

[0170] In the above formula (XL-2), from the viewpoint of curability, it is preferable that the number of groups (2-1) to (2-3) in R8 is greater than the number of hydrogen atoms, and more preferably the number of groups (2-1) to (2-3) is greater than the number of hydrogen atoms*2. [ka] (In the formula, R7 is a hydrogen atom or a methyl group, and R9 is a group selected from the following formulae (2-1) to (2-3).)

[0171] [ka] (In the above formula, the dashed lines represent bonds.)

[0172] <(E) Surfactant> A surfactant (E) can be added to the organic film-forming composition of the present invention to improve the coating properties during spin coating. Examples of surfactants that can be used include those described in paragraphs

[0142] to

[0147] of JP-A No. 2009-269953. When a surfactant is added, the amount of surfactant added is preferably 0.01 to 10 parts, more preferably 0.05 to 5 parts, per 100 parts by mass of the one or more aromatic ring-containing polymers (A).

[0173] <Organic film formation method> The present invention provides a method for forming an organic film that functions as an organic flat film used in the manufacturing process of a semiconductor device, which comprises spin-coating the above-mentioned organic film-forming composition on a substrate to be processed, and then heat-treating the substrate coated with the organic film-forming composition at a temperature of 100°C or higher and 600°C or lower for 10 to 600 seconds, thereby forming a cured film.

[0174] The present invention also provides a method for forming an organic film that functions as an organic flat film used in the manufacturing process of a semiconductor device, which comprises spin-coating the above-mentioned organic film-forming composition on a substrate to be processed, and then heat-treating the substrate coated with the organic film-forming composition in an atmosphere with an oxygen concentration of 0.1% or more and 21% or less, thereby forming a cured film.

[0175] Furthermore, it is preferable that the substrate to be processed has a structure or step having a height of 30 nm or more.

[0176] <Pattern formation method> [Trilayer resist process using silicon-containing resist interlayer] The present invention provides a pattern formation method that includes forming an organic film using the above-mentioned organic film-forming composition, forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms, forming a resist upper layer film on the resist intermediate film using a resist upper layer film material consisting of a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the resist intermediate film on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0177] The workpiece may be a semiconductor device substrate, or a metal film, a metal carbide film, or a film formed on the semiconductor device substrate. Any of a metal oxide film, a metal nitride film, a metal oxide carbide film, and a metal oxide nitride film is formed. More specifically, although not particularly limited, substrates such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, and Al, and substrates on which the above-mentioned metal films or the like are formed as workpiece layers, can be used.

[0178] 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.

[0179] The metals constituting the workpiece include silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, aluminum, indium, gallium, Arsenic, palladium, iron, tantalum, iridium, molybdenum, or alloys thereof It is preferable that:

[0180] 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.

[0181] Next, a resist interlayer film (silicon-containing resist interlayer film) is formed on the organic film using a resist interlayer film material containing silicon atoms. For this purpose, polysiloxane-based underlayer materials are preferred. By providing an anti-reflection effect, reflection can be suppressed. As a composition for forming an organic film, it contains many aromatic groups and has high etching selectivity with respect to the substrate. When using a material, the k value becomes higher and the substrate reflection becomes higher, but as a silicon-containing resist intermediate film, By providing absorption that gives an appropriate k value, it is possible to suppress reflection, and The reflection can be reduced to 0.5% or less. For 248nm and 157nm exposure, anthracene is used, and for 193nm exposure, has a pendant structure containing a phenyl group or a light-absorbing group having a silicon-silicon bond, and is an acid or Preferably, a thermally crosslinkable polysiloxane is used.

[0182] Next, a resist top layer film is formed on the resist intermediate film using a resist top layer film material consisting 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.

[0183] 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.

[0184] The exposure light is a high-energy ray with a wavelength of 300 nm or less, specifically far ultraviolet light. 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 ( 126nm), 3-20nm soft X-ray (EUV), electron beam (EB), ion beam, Examples include X-rays.

[0185] In forming the circuit pattern, it is preferable to develop the circuit pattern using an alkali developer or an organic solvent.

[0186] Next, the circuit pattern is transferred to the resist intermediate film by etching using the resist upper layer film as a mask. The etching of the resist intermediate film using the resist upper layer film pattern as a mask is preferably carried out using a fluorocarbon gas. This results in the formation of a silicon-containing resist intermediate film pattern.

[0187] Next, the pattern is transferred to the organic film by etching using the resist interlayer film with the transferred pattern as a mask. Because the silicon-containing resist interlayer film exhibits etching resistance to oxygen gas or hydrogen gas, the etching of the organic film using the silicon-containing resist interlayer film pattern as a mask is preferably carried out using an etching gas mainly composed of oxygen gas or hydrogen gas. This forms an organic film pattern.

[0188] Next, the pattern is transferred to the workpiece by etching using the organic film with the transferred pattern as a mask. The subsequent etching of the workpiece (layer to be processed) can be performed using standard methods. For example, if the workpiece is made of SiO2, SiN, or a silica-based low-k dielectric insulating film, etching is performed primarily with fluorocarbon-based gases; if the workpiece is made of p-Si, Al, or W, etching is performed primarily with chlorine- or bromine-based gases. If the substrate is processed using fluorocarbon-based gases for etching, the silicon-containing resist intermediate film pattern is stripped simultaneously with the substrate processing. On the other hand, if the substrate is processed using chlorine- or bromine-based gases for etching, a separate dry etching stripping process using fluorocarbon-based gases is required after substrate processing to strip the silicon-containing resist intermediate film pattern.

[0189] 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.

[0190] [Four-layer resist process using silicon-containing resist interlayer and organic anti-reflective coating] The present invention also provides a pattern formation method, comprising: forming an organic film on a workpiece using the above-described organic film-forming composition; forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms; forming an organic antireflective film on the resist intermediate film; forming a resist upper layer film on the organic antireflective film using a resist upper layer film material comprising a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the organic antireflective film and the resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern to the organic film by etching using the resist intermediate film on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0191] This method can be carried out in the same manner as the three-layer resist process using the silicon-containing resist intermediate film, except that an organic antireflective coating (BARC) is formed between the resist intermediate film and the resist top layer film.

[0192] The organic anti-reflection film can be formed by spin coating using a known organic anti-reflection film material.

[0193] [Trilayer resist process using inorganic hard mask] The present invention also provides a pattern formation method by a three-layer resist process using an organic film-forming composition, which comprises forming an organic film on a workpiece using the above-mentioned organic film-forming composition, forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming a resist upper layer film on the inorganic hard mask using a resist upper layer film material consisting of a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the inorganic hard mask by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0194] This method can be carried out in the same manner as the three-layer resist process using the silicon-containing resist intermediate film described above, except that an inorganic hard mask is formed on the organic film instead of the resist intermediate film.

[0195] An inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film (SiON film) can be formed by a CVD method, an ALD method, or the like. Methods for forming a silicon nitride film are described, for example, in Japanese Patent Application Laid-Open No. 2002-334869 and International Publication No. 2004 / 066377. The thickness of the inorganic hard mask is preferably 5 to 200 nm, more preferably 10 to 100 nm. As the inorganic hard mask, a SiON film, which is highly effective as an anti-reflective film, is most preferably used. Since the substrate temperature during SiON film formation is 300 to 500°C, the underlayer film must be able to withstand temperatures of 300 to 500°C. The organic film formed using the organic film-forming composition of the present invention has high heat resistance and can withstand high temperatures of 300 to 500°C. Therefore, an inorganic hard mask formed by a CVD method or an ALD method can be combined with an organic film formed by a spin-coating method.

[0196] [Four-layer resist process using inorganic hard mask and organic anti-reflective coating] The present invention also provides a pattern formation method by a four-layer resist process using an organic film-forming composition, comprising the steps of forming an organic film on a workpiece using the above-mentioned organic film-forming composition, forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming an organic antireflective film on the inorganic hard mask, forming a resist upper layer film on the organic antireflective film using a resist upper layer film material comprising a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the organic antireflective film and the inorganic hard mask by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[0197] This method can be carried out in the same manner as the above-mentioned three-layer resist process using an inorganic hard mask, except that an organic antireflective coating (BARC) is formed between the inorganic hard mask and the resist top layer.

[0198] In particular, when a SiON film is used as the inorganic hard mask, the two-layer anti-reflection coating of the SiON film and BARC makes it possible to suppress reflection even in immersion lithography with a high NA exceeding 1.0. Another benefit of forming a BARC is that it reduces the footing of the resist top layer pattern directly above the SiON film.

[0199] An example of a pattern formation method using the three-layer resist process of the present invention is shown in Figures 1(A) to 1(F). In the three-layer resist process, as shown in Figure 1(A), an organic film 3 is formed on a processable layer 2 formed on a substrate 1 using the organic film-forming composition of the present invention, followed by the formation of a silicon-containing resist intermediate film 4, and then a resist upper layer film 5 is formed thereon. Next, as shown in Figure 1(B), the exposed portion 6 of the resist upper layer film 5 is exposed and subjected to PEB (post-exposure bake). Next, as shown in Figure 1(C), development is performed to form a resist upper layer film pattern 5a. Next, as shown in Figure 1(D), using the resist upper layer film pattern 5a as a mask, the silicon-containing resist intermediate film 4 is dry-etched using a fluorocarbon-based gas to form a silicon-containing resist intermediate film pattern 4a. Next, as shown in Figure 1(E), after removing the resist upper layer film pattern 5a, the organic film 3 is oxygen-plasma etched using the silicon-containing resist intermediate film pattern 4a as a mask to form an organic film pattern 3a. Furthermore, as shown in FIG. 1(F), after removing the silicon-containing resist intermediate film pattern 4a, the processable layer 2 is etched using the organic film pattern 3a as a mask to form a pattern 2a.

[0200] When forming an inorganic hard mask, the silicon-containing resist intermediate film 4 can be replaced with an inorganic hard mask, and when forming a BARC, the BARC can be formed between the silicon-containing resist intermediate film 4 and the resist upper layer film 5. Etching of the BARC can be performed prior to and consecutively with 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 alone, for example by changing the etching apparatus.

[0201] As described above, the pattern forming method of the present invention can achieve the following by a multilayer resist process: It is possible to form fine patterns on the workpiece with high precision. [Example]

[0202] The present invention will be described in more detail below with reference to Synthesis Examples, Examples, and Comparative Examples, but is not limited thereto. The molecular weight and dispersity were determined by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent, and the weight average molecular weight (Mw) was calculated in terms of polystyrene.

[0203] [Synthesis Example 1] Synthesis of aromatic ring-containing resin compound (A-1) Under a nitrogen atmosphere, 1.0 g of 2,3-dihydroxynaphthalene, 9.0 g of methanesulfonic acid, and 30 g of 1,2-dichloroethane were added to a flask and stirred at an internal temperature of 60°C. After forming a homogeneous solution, 18.8 g of 3-phenoxybenzyl alcohol was slowly added dropwise, and the reaction was carried out at an internal temperature of 70°C for 5 hours. After cooling to room temperature, the mixture was diluted with 200 g of methyl isobutyl ketone (MIBK) and washed five times with 50 g of ultrapure water. The organic layer was then recovered, the methyl isobutyl ketone was removed under reduced pressure, and 150 g of PGMEA was added to form a homogeneous solution. Water and low-boiling point solvents were distilled off, and the concentration was further adjusted to recover a PGMEA solution with a concentration of 20% of aromatic ring-containing resin compound (A-1). (A-1): Mw = 2080, Mw / Mn = 2.2 [ka]

[0204] [Synthesis Example 2] Synthesis of aromatic ring-containing resin compound (A-2) Under a nitrogen atmosphere, 1.0 g of 2,3-dihydroxynaphthalene, 9.0 g of methanesulfonic acid, and 30 g of 1,2-dichloroethane were added to a flask and stirred at an internal temperature of 60°C. After forming a homogeneous solution, 11.6 g of 4-hydroxybenzyl alcohol was slowly added dropwise, and the reaction was carried out at an internal temperature of 70°C for 5 hours. After cooling to room temperature, the mixture was diluted with 200 g of methyl isobutyl ketone (MIBK) and washed five times with 50 g of ultrapure water. The organic layer was then recovered, the methyl isobutyl ketone was removed under reduced pressure, and 150 g of PGMEA was added to form a homogeneous solution. Water and low-boiling point solvents were distilled off, and the concentration was further adjusted to recover a 20% PGMEA solution of aromatic ring-containing resin compound (A-2). (A-2): Mw = 1900, Mw / Mn = 2.3 [ka]

[0205] [Synthesis Example 3] Synthesis of aromatic ring-containing resin compound (A-3) Under a nitrogen atmosphere, 1.0 g of 4,4'-dihydroxydiphenyl ether, 5.9 g of methanesulfonic acid, and 30 g of 1,2-dichloroethane were added to a flask and stirred at an internal temperature of 60°C. After forming a homogeneous solution, 11.8 g of 3-phenoxybenzyl alcohol was slowly added dropwise, and the reaction was carried out at an internal temperature of 70°C for 5 hours. After cooling to room temperature, the mixture was diluted with 200 g of methyl isobutyl ketone (MIBK) and washed five times with 50 g of ultrapure water. The organic layer was then recovered, the methyl isobutyl ketone was removed under reduced pressure, and 150 g of PGMEA was added to form a homogeneous solution. Water and low-boiling point solvents were distilled off, and the concentration was further adjusted to recover a 20% PGMEA solution of aromatic ring-containing resin compound (A-3). (A-3): Mw = 1880, Mw / Mn = 2.1 [ka]

[0206] [Synthesis Example 4] Synthesis of aromatic ring-containing resin compound (A-4) Under a nitrogen atmosphere, 1.0 g of 4,4'-dihydroxydiphenyl ether, 5.9 g of methanesulfonic acid, and 30 g of 1,2-dichloroethane were added to a flask and stirred at an internal temperature of 60°C. After forming a homogeneous solution, a solution of 9.4 g of 2-naphthalenemethanol previously homogenized with 30 g of 1,2-dichloroethane was slowly added dropwise, and the reaction was carried out at an internal temperature of 70°C for 5 hours. After cooling to room temperature, the mixture was diluted with 200 g of methyl isobutyl ketone (MIBK) and washed five times with 50 g of ultrapure water. The organic layer was then recovered, the methyl isobutyl ketone was removed under reduced pressure, and 150 g of PGMEA was added to form a homogeneous solution. Water and low-boiling point solvents were distilled off, and the concentration was further adjusted to recover a 20% PGMEA solution of aromatic ring-containing resin compound (A-4). (A-4): Mw = 1760, Mw / Mn = 2.4 [ka]

[0207] [Synthesis Example 5] Synthesis of aromatic ring-containing resin polymer (A-5) Under a nitrogen atmosphere, 20.0 g of 4,4'-dihydroxydiphenyl ether, 0.4 g of p-toluenesulfonic acid, and 60 g of propylene glycol monomethyl ether were added to a flask and stirred at an internal temperature of 90°C. After forming a homogeneous solution, 17.8 g of a 37% aqueous solution of formaldehyde was slowly added dropwise, followed by stirring at an internal temperature of 105°C for 20 hours. After cooling to room temperature, 150 g of hexane was added with stirring to precipitate a mochi-like precipitate. After allowing to stand for a while, the upper layer was decanted. 30 g of PGME was added to the residue and formed a homogeneous solution by stirring. The solution was then diluted with 150 g of MIBK and washed five times with 50 g of ultrapure water. The organic layer was then recovered, methyl isobutyl ketone was removed under reduced pressure, and 150 g of PGMEA was added to form a homogeneous solution. Water and low-boiling point solvents were distilled off, and the concentration was further adjusted to recover a 20% PGMEA solution of aromatic ring-containing resin compound (A-5). (A-5) Mw=6030, Mw / Mn=1.7 [ka]

[0208] [Synthesis Example 6] Synthesis of aromatic ring-containing resin polymer (A-6) Under a nitrogen atmosphere, 10.0 g of polymer (A-5), 6.5 g of potassium carbonate, and 40 g of N,N-dimethylformamide were added to a flask and stirred at an internal temperature of 50°C to form a suspension. 7.0 g of an 80% toluene solution of propargyl bromide was added dropwise to the dispersion, and the reaction was allowed to proceed at an internal temperature of 50°C for 15 hours. After the reaction, 150 g of ultrapure water and 150 g of MIBK were added to form a homogeneous solution and terminated. The mixture was transferred to a separatory funnel, the separated aqueous layer was removed, and the mixture was washed twice with 100 g of 3% aqueous nitric acid solution and five times with 150 g of ultrapure water. The organic layer was recovered, and methyl isobutyl ketone was removed under reduced pressure. 150 g of PGMEA was added to form a homogeneous solution. Water and low-boiling point solvents were distilled off, and the concentration was further adjusted to recover a 20% PGMEA solution of aromatic ring-containing resin compound (A-6). (A-6) Mw=7400, Mw / Mn=1.9 [ka]

[0209] [Synthesis Example 7] Synthesis of aromatic ring-containing resin polymer (A-7) Under a nitrogen atmosphere, 20.0 g of catechol, 0.4 g of p-toluenesulfonic acid, and 60 g of propylene glycol monomethyl ether were added to a flask and stirred at an internal temperature of 90°C. After forming a homogeneous solution, 11.8 g of a 37% aqueous solution of formaldehyde was slowly added dropwise, followed by stirring at an internal temperature of 105°C for 20 hours. After cooling to room temperature, 150 g of ultrapure water was added with stirring to precipitate a mochi-like precipitate. After allowing to stand for a while, the upper layer was decanted. 30 g of PGME was added to the residue and formed a homogeneous solution by stirring. The solution was then diluted with 150 g of MIBK and washed five times with 50 g of ultrapure water. The organic layer was then recovered, methyl isobutyl ketone was removed under reduced pressure, and 150 g of PGMEA was added to form a homogeneous solution. Water and low-boiling point solvents were distilled off, and the concentration was further adjusted to recover a 20% PGMEA solution of aromatic ring-containing resin compound (A-7). (A-7) Mw=3900, Mw / Mn=1.6 [ka]

[0210] [Synthesis Example 8] Synthesis of aromatic ring-containing resin polymer (A-8) Under a nitrogen atmosphere, 10.0 g of polymer (A-7), 11.4 g of potassium carbonate, and 40 g of N,N-dimethylformamide were added to a flask and stirred at an internal temperature of 50°C to form a suspension. 12.2 g of an 80% toluene solution of propargyl bromide was added dropwise to the dispersion, and the reaction was allowed to proceed at an internal temperature of 50°C for 15 hours. After the reaction, 150 g of ultrapure water and 150 g of MIBK were added to form a homogeneous solution and terminated. The mixture was transferred to a separatory funnel, the separated aqueous layer was removed, and the mixture was washed twice with 100 g of 3% aqueous nitric acid solution and five times with 150 g of ultrapure water. The organic layer was recovered, and methyl isobutyl ketone was removed under reduced pressure. 150 g of PGMEA was added to form a homogeneous solution. Water and low-boiling point solvents were distilled off, and the concentration was further adjusted to recover a 20% PGMEA solution of aromatic ring-containing resin compound (A-8). (A-8) Mw=4120, Mw / Mn=1.7 [ka]

[0211] [Synthesis Example 9] Synthesis of aromatic ring-containing resin polymer (A-9) Under a nitrogen atmosphere, 10.0 g of p-cresol, 0.2 g of p-toluenesulfonic acid, and 40 g of propylene glycol monomethyl ether were added to a flask and stirred at an internal temperature of 90°C. After forming a homogeneous solution, 6.0 g of a 37% aqueous solution of formaldehyde was slowly added dropwise, followed by stirring at an internal temperature of 105°C for 20 hours. After cooling to room temperature, 100 g of ultrapure water was added with stirring to precipitate a mochi-like precipitate. After allowing to stand for a while, the upper layer was decanted. 20 g of PGME was added to the residue and formed a homogeneous solution by stirring. The solution was then diluted with 100 g of MIBK and washed five times with 50 g of ultrapure water. The organic layer was then recovered, and methyl isobutyl ketone was removed under reduced pressure. 150 g of PGMEA was added to form a homogeneous solution. Water and low-boiling point solvents were distilled off, and the concentration was further adjusted to recover a 20% PGMEA solution of aromatic ring-containing resin compound (A-9). (A-9) Mw = 3400, Mw / Mn = 1.6 [ka]

[0212] [Synthesis Example 10] Synthesis of aromatic ring-containing resin polymer (A-10) Under a nitrogen atmosphere, 10.0 g of 1,3,5-trihydroxybenzene, 10.0 g of 3,4-dihydroxybenzaldehyde, 0.2 g of p-toluenesulfonic acid, and 40 g of propylene glycol monomethyl ether were added to a flask and stirred at an internal temperature of 90°C. After forming a homogeneous solution, the mixture was reacted at an internal temperature of 105°C for 5 hours. After cooling to room temperature, the mixture was diluted with 100 g of MIBK and washed five times with 50 g of ultrapure water. The organic layer was then recovered, and the methyl isobutyl ketone was removed under reduced pressure. 150 g of PGMEA was added to form a homogeneous solution. Water and low-boiling point solvents were distilled off, and the concentration was further adjusted to recover a 20% PGMEA solution of aromatic ring-containing resin compound (A-10). (A-10) Mw = 1125, Mw / Mn = 1.4 [ka]

[0213] [Synthesis Example 11] Synthesis of aromatic ring-containing resin compound (A-11) Under a nitrogen atmosphere, 1.0 g of catechol, 21.0 g of methanesulfonic acid, and 30 g of 1,2-dichloroethane were added to a flask and stirred at an internal temperature of 60°C. After forming a homogeneous solution, 21.9 g of 3-phenoxybenzyl alcohol was slowly added dropwise, and the reaction was carried out at an internal temperature of 70°C for 5 hours. After cooling to room temperature, the mixture was diluted with 200 g of methyl isobutyl ketone (MIBK) and washed five times with 50 g of ultrapure water. The organic layer was then recovered, the methyl isobutyl ketone was removed under reduced pressure, and 150 g of PGMEA was added to form a homogeneous solution. Water and low-boiling point solvents were distilled off, and the concentration was further adjusted to recover a 20% PGMEA solution of aromatic ring-containing resin compound (A-11). (A-11): Mw = 1680, Mw / Mn = 2.0 [ka]

[0214] [Synthesis Example 12] Synthesis of polymer (B-1) containing β-diketone structure in the repeating unit Under a nitrogen atmosphere, 10.0 g of di-tert-butyl malonate, 3.7 g of 1,4-butanediol, and 50 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 polymer (B-1). (B-1): Mw = 11500, Mw / Mn = 1.7 [ka]

[0215] [Synthesis Example 13] Synthesis of polymer (B-2) containing β-diketone structure in the repeating unit Under a nitrogen atmosphere, 10.0 g of di-tert-butyl malonate, 8.4 g of 1,12-dodecanediol, and 50 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 polymer (B-2). (B-2): Mw = 17500, Mw / Mn = 2.2 [ka]

[0216] [Synthesis Example 14] Synthesis of polymer (B-3) containing β-diketone structure in the repeating unit Under a nitrogen atmosphere, 10.0 g of di-tert-butyl malonate, 11.7 g of hexaethylene glycol, and 50 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 polymer (B-3). (B-3): Mw = 14800, Mw / Mn = 2.1 [ka]

[0217] [Synthesis Example 15] Synthesis of polymer (B-4) containing β-diketone structure in the repeating unit Under a nitrogen atmosphere, 10.0 g of di-tert-butyl malonate, 14.1 g of potassium carbonate, and 50 g of DMF were added to a flask, and 12.5 g of 1-bromopropane was added dropwise. The internal temperature was then raised to 60°C and the reaction proceeded for 15 hours. After cooling to room temperature, 200 g of methyl isobutyl ketone was added, and the mixture was washed twice with 150 g of ultrapure water. The organic layer was recovered and the methyl isobutyl ketone was removed under reduced pressure. After removing the methyl isobutyl ketone, the mixture was dissolved in 50 g of xylene, and 8.4 g of 1,12-dodecanediol was added. The reaction proceeded for 2 hours at an internal temperature of 140°C while removing tert-butyl alcohol produced by transesterification from the system. The temperature was then raised to 160°C while removing tert-butyl alcohol and o-xylene from the system, and the reaction proceeded for 6 hours at 160°C. After cooling to 50°C, 200 g of hexane was added, and a polymer was precipitated as a gum. The mixture was cooled to room temperature and allowed to stand for 1 hour, after which the supernatant was decanted. The residue was dissolved in 150 g of methyl isobutyl ketone, washed with 100 g of 3% nitric acid, and then washed five times with ultrapure water. The methyl isobutyl ketone was removed under reduced pressure, and 150 g of PGMEA (propylene glycol monomethyl ether acetate) was added to form a homogeneous solution. Water and low-boiling point solvents were then distilled off, and the concentration was further adjusted to recover a 50% PGMEA solution of polymer (B-4). (B-4): Mw = 19250, Mw / Mn = 2.2 [ka]

[0218] [Composition for organic film formation UDL-1] A polymer (A-1) containing an aromatic ring and a polymer (B-1) containing a β-diketone structure as a repeating unit were dissolved in propylene glycol monomethyl ether acetate (PGMEA) containing 0.5% by mass of surfactant FC-4430 (manufactured by Sumitomo 3M Limited) in the proportions shown in Table 1, and the resulting solution was filtered through a 0.02 μm membrane filter to prepare an organic film-forming composition (UDL-1).

[0219] [Preparation of organic film-forming compositions (UDL-2 to 21) and organic film-forming compositions for comparative examples (UDL-1 to 12 for comparative examples)] Each chemical solution was prepared in the same manner as UDL-1, except that the type and content of each component were as shown in Table 1. In Table 1, "-" indicates that the corresponding component was not used. The following formula (D-1) was used as the crosslinking agent, 1,6-diacetoxyhexane (boiling point 260°C) was used as the high-boiling point solvent (F-1), the following formula (G-1) was used as the thermally decomposable resin, and further polyethylene glycol methyl ether 10000 (PEGME10000) was used as (P-1), and dimethyl malonate was used as (M-1).

[0220] [Crosslinking agent] The crosslinking agent (D-1) used in the organic film-forming composition is shown below. [ka]

[0221] [Pyrolytic resin] The thermally decomposable resin (G-1) used in the organic film-forming composition is shown below. [ka] Mw=6,400Mw / Mn=2.5

[0222] [Table 1]

[0223] [Solvent resistance evaluation] The organic film-forming compositions (UDL-1 to 21, Comparative Examples UDL-1 to 12) prepared above were applied to silicon substrates, baked at 180°C for 60 seconds, and then baked at 350°C for 60 seconds, after which the film thickness (a [nm]) was measured. The film thickness was also measured from the center to the periphery of the substrate, and the difference between the maximum and minimum film thicknesses, Range (b [nm]), was calculated to determine the in-plane uniformity ((b / a) x 100). Next, PGMEA was dispensed onto the film, left for 30 seconds, spin-dried, and baked at 100°C for 60 seconds to evaporate the PGMEA. The film thickness (c [nm]) was then measured. The difference in film thickness before and after PGMEA treatment (residual film ratio: (c / a) x 100) was calculated. The results are shown in Table 2 below. [Table 2]

[0224] As shown in Table 2, the organic film-forming compositions of the present invention (Examples 1-1 to 1-21) had a post-baking residual film ratio ((c / a) × 100) of 98.5% or more, confirming that they possess the sufficient thermosetting properties required for resist underlayer films. Furthermore, since the in-plane uniformity was also good, it was confirmed that these compositions are less likely to produce sublimates or poor compatibility, and are less likely to cause film formation or coating defects. Similar results were obtained for Comparative Examples 1-1 to 1-3, which were compositions excluding the polymer (B) containing a β-diketone structure in the main chain of the polymer from the present invention. This confirmed that the addition of component (B) did not adversely affect the film curability or film formability. On the other hand, Comparative Examples 1-4 to 1-6, which contained a simple polyethylene glycol (P-1) without a β-diketone structure; Comparative Examples 1-7 to 1-9, which contained a thermally decomposable resin (G-1); and Comparative Examples 1-10 to 1-12, which contained a monomolecular compound (M-1) containing a β-diketone structure, resulted in significantly deteriorated in-plane uniformity. This is thought to be due to unevenness during application caused by poor compatibility with the main resin when (P-1) is included, sublimation of low molecular weight components produced by thermal decomposition when (G-1) is included, and the unevenness of the film caused by sublimation of (M-1) itself due to the low molecular weight of (M-1) itself when (M-1) is included.

[0225] [Evaluation of filling characteristics and planarization] The organic film-forming compositions (UDL-1 to 21 and Comparative Examples UDL-1 to 9) prepared above were each applied to a SiO2 wafer substrate having a dense line and space pattern (line width 60 nm, line depth 100 nm, center-to-center distance between adjacent two lines 120 nm) and heated at 350°C for 60 seconds using a hot plate to form an organic film with a thickness of approximately 150 nm. The substrate used was a base substrate 8 (SiO2 wafer substrate) having a dense line and space pattern as shown in Figure 2. The cross-sectional shape of each wafer substrate was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd. to confirm whether the substrate could be filled into the uneven surface. The results are shown in Table 3. When an organic film-forming composition with poor filling properties was used, the uneven surface could not be filled successfully in this evaluation. When an organic film-forming composition with good filling properties was used, the dense line and space pattern could be filled without gaps, as shown in Figure 2. A indicates that filling was possible without large voids, B indicates that voids were visible, and C indicates that filling was not possible. The cross-sectional shape of each wafer substrate obtained in the above filling property evaluation was also observed using a scanning electron microscope (SEM), and the step (Delta 10 in Figure 2(B)) between the dense line pattern area and the non-line pattern area of ​​the filling film (coating film) 9 was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd. The results are shown in Table 3. In this evaluation, the smaller the step, the better the planarization properties. [Table 3]

[0226] As shown in Table 3, Examples 2-1 to 2-21, which used the organic film-forming compositions of the present invention (UDL-1 to 21), and Comparative Examples 2-1 to 2-3, which used Comparative Examples UDL1 to 3 without any additives, were able to fill dense line and space patterns without generating voids, confirming their excellent filling properties. On the other hand, Comparative Examples 2-4 to 2-6, which contained simple polyethylene glycol (P-1), were unable to fill dense line and space patterns, either because they were unable to fill or because they generated voids. This is thought to be due to poor compatibility, which resulted in poor film-forming properties and insufficient filling of spaces during spin coating. Furthermore, Comparative Examples 2-7 to 2-9, which contained a thermally decomposable resin (G-1), and Comparative Examples 2-10 to 2-12, which contained a β-diketone compound (M-1), were able to fill, but voids were generated. This is thought to be due to the decomposition and sublimation of the thermally decomposable resin, and the sublimation of the β-diketone compound itself, which created gaps in the filled spaces. Furthermore, in terms of flatness, when Examples 2-1 to 2-19, which used organic film-forming compositions (UDL-1 to 21) using a polymer containing a repeating unit having a β-diketone structure (B) of the present invention, were compared with Comparative Examples 2-1 to 2-3, which used Comparative Examples UDL1 to 3 that did not contain the (B) polymer of the present invention, Examples 2-1 to 2-19, which contained the (B) polymer of the present invention, all showed an improvement of 10 nm or more compared to Comparative Examples 2-1 to 2-3. This is thought to be the result of ensuring thermal fluidity by adding a polymer containing a β-diketone structure in the repeating unit, and good results were also obtained for other organic film-forming compositions of the present invention.

[0227] [Etching resistance evaluation] The organic film-forming compositions (UDL-1, 5, 7) of the present invention, which use the same (A) aromatic ring-containing resin (A-1), (A-5), or (A-7) and (B) polymer containing a repeating unit containing a β-diketone structure, and comparative examples UDL1-1 to 1-3, which do not contain the (B) polymer of the present invention, were applied to silicon substrates, heated on a hot plate at 350°C for 60 seconds, and subjected to the plasma treatment conditions described below to form organic films, and their film thicknesses a were measured. Next, etching was performed using CF4 gas under the conditions described below using a Tokyo Electron Telius etching system, and their film thicknesses b were measured. The film thickness etched per minute using CF4 gas was calculated from the film thickness (film thickness a - film thickness b) in a specified time, as the etching rate B (nm / min). A smaller etching rate indicates better etching resistance to CF4 gas.

[0228] Dry etching conditions with CF4 gas Chamber pressure: 100mT RF power (top): 500W RF power (bottom): 400W CF4 gas flow rate: 300sccm Time: 30sec [Table 4]

[0229] As shown in Table 4, Examples 3-1 to 3-3, which used compositions for forming resist underlayer films (UDL-1, 5, 7) of the present invention, and Comparative Examples 3-1 to 3-3, which used comparative UDL1-1 to 1-3, which did not contain the polymer containing a β-diketone structure, showed similar etching resistance to both gas species, confirming that the polymer containing a β-diketone structure did not have an adverse effect on etching resistance.

[0230] From the above, the composition for forming an organic film of the present invention has a high degree of both thermal fluidity and thermosetting properties, and is capable of forming an organic film with high film-forming, embedding, and planarization properties without impairing the etching resistance of the original main resin, and is extremely useful as a resist underlayer film material used in multilayer resist methods and as a reversal agent used in tone reversal etching methods.

[0231] This specification includes the following inventions.

[0232] [1]: A composition for forming an organic film, comprising: (A) an aromatic ring-containing resin; (B) a polymer containing a repeating unit having a β-diketone structure represented by the following formula (1); and (C) a solvent.

[0233] [ka] In the above formula (1), L1 is a saturated or unsaturated, straight-chain or branched divalent hydrocarbon group having 2 to 20 carbon atoms, and the hydrocarbon group may be interrupted one or more times by an atom selected from oxygen, nitrogen, and sulfur. R A and R B may be the same or different and are a hydrogen atom, a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a thiol group, a hydroxyl group, an amino group, a carboxy group, or a halogen group. [2]: The organic film-forming composition according to [1], wherein the aromatic ring-containing resin (A) contains hydrogen at the diarylmethylene position or hydrogen at the trityl position. [3]: The composition for forming an organic film according to [2], wherein the aromatic ring in the aromatic ring-containing resin (A) contains a hydroxyl group as a substituent. [4]: The composition for forming an organic film according to any one of [1] to [3], characterized in that the aromatic ring-containing resin (A) is selected from polymers having repeating units represented by the following formulas (P-1) and (P-2), and compounds represented by formulas (P-3) to (P-6).

[0234] [ka] (In the following formulas (P-1) and (P-2), R is a hydrogen atom or a substituted or unsubstituted benzene ring or naphthalene ring. In (P-1) to (P-6), R1 is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. In (P-1), (P-3), (P-4) and (P-5), m1 is an integer of 0 or 1. In (P-1), (P-3), (P-4) and (P-6), n1 is an integer of 1 to 4. In (P-2) and (P-5), n2 is an integer of 1 or 2. In (P-3) and (P-5), n3 is an integer of 0 to 2. In (P-3) to (P-6), l is an integer of 5 to 20. Here, l represents the feed ratio.) [5]: In the above formula (1), R A and R B is a hydrogen atom, a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds. [6]: In the above formula (1), R A and R B The composition for forming an organic film according to any one of [1] to [5], wherein is a hydrogen atom. [7]: The composition for forming an organic film according to any one of [1] to [6], characterized in that in the above formula (1), L1 is a saturated or unsaturated, linear or branched hydrocarbon group having 2 to 20 carbon atoms and containing no heteroatoms. [8]: The composition for forming an organic film according to any one of [1] to [7], characterized in that the (B) polymer having a β-diketone structure as a repeating unit is contained in an amount of 0.5 to 30 parts by mass per 100 parts by mass of the (A) aromatic ring-containing resin. [9]: The composition for forming an organic film according to any one of [1] to [8], wherein the solvent (C) of the composition for forming an organic film is a mixture of a high-boiling point solvent and a low-boiling point solvent.

[10] : The composition for forming an organic film according to any one of [1] to [9], further comprising one or more of (D) a crosslinking agent and (E) a surfactant.

[11] : A method for forming an organic film that functions as an organic flat film used in the manufacturing process of a semiconductor device, comprising spin-coating the organic film-forming composition according to any one of [1] to

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

[12] : A method for forming an organic film that functions as an organic flat film used in the manufacturing process of a semiconductor device, comprising spin-coating the organic film-forming composition according to any one of [1] to

[10] onto a substrate to be processed, and heat-treating the substrate coated with the organic film-forming composition in an atmosphere with an oxygen concentration of 0.1% or more and 21% or less to form a cured film.

[13] : The organic film forming method according to

[11] or

[12] , wherein the substrate to be processed has a structure or step having a height of 30 nm or more.

[14] : A pattern forming method comprising the steps of forming an organic film on a workpiece using the organic film-forming composition according to any one of [1] to

[10] , forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms, forming a resist upper layer film on the resist intermediate film using a resist upper layer film material consisting of a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the resist intermediate film on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[15] : A pattern forming method comprising the steps of: forming an organic film on a workpiece using the organic film-forming composition according to any one of [1] to

[10] ; forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms; forming an organic antireflective film on the resist intermediate film; forming a resist upper layer film on the organic antireflective film using a resist upper layer film material consisting of a photoresist composition; forming a circuit pattern on the resist upper layer film; transferring the pattern to the organic antireflective film and the resist intermediate film by etching using the resist upper layer film on which the circuit pattern has been formed as a mask; transferring the pattern to the organic film by etching using the resist intermediate film on which the pattern has been transferred as a mask; and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[16] : 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

[10] , forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming a resist upper layer film on the inorganic hard mask using a resist upper layer film material comprising a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the inorganic hard mask by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[17] : 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

[10] , forming an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the organic film, forming an organic antireflective film on the inorganic hard mask, forming a resist upper layer film on the organic antireflective film using a resist upper layer film material comprising a photoresist composition, forming a circuit pattern on the resist upper layer film, transferring the pattern to the organic antireflective film and the inorganic hard mask by etching using the resist upper layer film on which the circuit pattern has been formed as a mask, transferring the pattern to the organic film by etching using the inorganic hard mask on which the pattern has been transferred as a mask, and further transferring the pattern to the workpiece by etching using the organic film on which the pattern has been transferred as a mask.

[18] : The pattern formation method according to either

[16] or

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

[0235] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention. [Explanation of symbols]

[0236] 1...substrate, 2...processed layer, 2a...pattern formed on the processed layer, 3...organic film, 3a...organic film pattern, 4...silicon-containing resist intermediate film, 4a...silicon-containing resist intermediate film pattern, 5...resist upper layer film, 5a...resist upper layer film pattern, 6...exposed portion, 8...patterned substrate, 9...coated film, Delta10: Step difference between the patterned and non-patterned portions of the coating film 9

Claims

1. (A) Aromatic ring-containing resin (B) A polymer containing a repeating unit containing a β-diketone structure represented by the following formula (1): (C) Solvent A composition for forming an organic film, comprising: 【Chemistry 1】 (In the above formula (1), L １ R is a saturated or unsaturated, straight-chain or branched divalent hydrocarbon group having 2 to 20 carbon atoms, and the hydrocarbon group may be interrupted one or more times by an atom selected from oxygen, nitrogen, and sulfur. Ａ and R Ｂ may be the same or different and are a hydrogen atom, a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a thiol group, a hydroxyl group, an amino group, a carboxy group, or a halogen group.

2. 2. The organic film-forming composition according to claim 1, wherein the aromatic ring-containing resin (A) contains hydrogen at the diarylmethylene position or hydrogen at the trityl position.

3. 3. The organic film-forming composition according to claim 2, wherein the aromatic ring in the aromatic ring-containing resin (A) contains a hydroxyl group as a substituent.

4. The composition for forming an organic film according to claim 1, characterized in that the aromatic ring-containing resin (A) contains a polymer having repeating units represented by the following formulas (P-1) and (P-2), and a compound selected from the group consisting of compounds represented by formulas (P-3) to (P-6): 【Chemistry 2】 (In the following formulas (P-1) and (P-2), R is a hydrogen atom or a substituted or unsubstituted benzene ring or naphthalene ring. In (P-1) to (P-6), R １ is a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and in (P-1), (P-3), (P-4) and (P-5), m １ is an integer of 0 or 1, and in (P-1), (P-3), (P-4) and (P-6), n １ is an integer of 1 to 4, and in (P-2) and (P-5), n ２ is an integer of 1 or 2, and in (P-3) and (P-5), n ３ is an integer of 0 to 2, and in (P-3) to (P-6), l is an integer of 5 to 20. Here, l represents the charge ratio.

5. In the above formula (1), R Ａ and R Ｂ is a hydrogen atom, a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds.

6. In the above formula (1), R Ａ and R Ｂ 2. The organic film-forming composition according to claim 1, wherein is a hydrogen atom.

7. In the above formula (1), L １ 2. The organic film-forming composition according to claim 1, wherein is a saturated or unsaturated, straight-chain or branched hydrocarbon group having 2 to 20 carbon atoms and containing no heteroatoms.

8. 2. The organic film-forming composition according to claim 1, wherein the polymer (B) having a β-diketone structure as a repeating unit is contained in an amount of 0.5 to 30 parts by mass per 100 parts by mass of the aromatic ring-containing resin (A).

9. 2. The composition for forming an organic film according to claim 1, wherein the solvent (C) in the composition for forming an organic film is a mixture of a high-boiling point solvent and a low-boiling point solvent.

10. 2. The composition for forming an organic film according to claim 1, further comprising at least one of (D) a crosslinking agent and (E) a surfactant.

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

12. 11. A method for forming an organic film that functions as an organic flat film used in a manufacturing process of a semiconductor device, the method comprising spin-coating the organic film-forming composition according to claim 1 onto a substrate to be processed, and heat-treating the substrate coated with the organic film-forming composition in an atmosphere having an oxygen concentration of 0.1% or more and 21% or less, thereby forming a cured film.

13. 12. The organic film forming method according to claim 11, wherein the substrate to be processed has a structure or step having a height of 30 nm or more.

14. a resist intermediate film material containing silicon atoms formed on the organic film; a resist upper layer film material comprising a photoresist composition formed on the resist intermediate film; a circuit pattern formed on the resist upper layer film; a pattern transferred by etching onto the resist intermediate film using the resist upper layer film on which the circuit pattern has been formed as a mask; a pattern transferred by etching onto the organic film using the resist intermediate film on which the pattern has been transferred as a mask; and a pattern transfer method comprising the steps of: forming an organic film on a workpiece using the organic film-forming composition according to any one of claims 1 to 10; forming a resist intermediate film on the organic film using a resist intermediate film material containing silicon atoms formed on the organic film using a resist upper layer film material comprising a photoresist composition; forming a circuit pattern on the resist upper layer film;

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

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

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

18. 17. The pattern formation method according to claim 16, wherein the inorganic hard mask is formed by a CVD method or an ALD method.

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