Composition for forming metal-containing films and method for forming patterns

Abstract

To provide a composition for a metal-containing film that yields a metal-containing film capable of producing an excellent pattern shape and preventing fine-pattern collapse.SOLUTION: The present invention provides a composition for forming a metal-containing film, containing: (A) a metal compound; (B) a surface modifier; and (C) a solvent, where the metal compound contains at least one metal atom selected from the group consisting of Ti, Zr, and Hf, and the surface modifier (B) is a polymer compound that contains repeating units of a specific structure containing a heterocyclic structure, where the polymer compound is free of repeating units containing hydroxyl groups.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a metal-containing film-forming composition that can be used for fine patterning by a multilayer resist method in the semiconductor device manufacturing process, and a pattern-forming method using the composition. [Background technology]

[0002] With the increasing integration and speed of LSIs, the miniaturization of pattern dimensions is progressing rapidly. Lithography technology has achieved the formation of fine patterns in line with this miniaturization by shortening the wavelength of the light source and appropriately selecting the resist composition. At the heart of this is the single-layer positive photoresist composition. This single-layer positive photoresist composition has a framework in the resist resin that is resistant to dry etching with chlorine-based or fluorine-based gas plasma, and also has a switching mechanism that causes the exposed area to dissolve, thereby forming a pattern by dissolving the exposed area, and the remaining resist pattern is used as an etching mask to dry etch the substrate to be processed.

[0003] However, when miniaturization was performed while keeping the thickness of the photoresist film the same, that is, when the pattern width was reduced, the resolution performance of the photoresist film decreased. Furthermore, when attempting to develop the photoresist film with a developer, the aspect ratio became too large, resulting in pattern collapse. For this reason, the photoresist film has been made thinner as patterns have been miniaturized.

[0004] On the other hand, the processing of substrates typically involves dry etching using a photoresist film with a pattern formed on it as an etching mask. However, in reality, there is no dry etching method that can achieve complete etching selectivity between the photoresist film and the substrate. As a result, the photoresist film is damaged and disintegrates during substrate processing, making it impossible to accurately transfer the resist pattern to the substrate. Therefore, with the miniaturization of patterns, high dry etching resistance has been required for the resist composition. However, at the same time, in order to improve resolution, resins with low light absorption at the exposure wavelength have been required for the resins used in the photoresist composition. Therefore, as the exposure light has become shorter in wavelength, from i-line to KrF and ArF, the resins have also changed to novolac resins, polyhydroxystyrene, and resins with aliphatic polycyclic skeletons. However, in reality, the etching rate under dry etching conditions during substrate processing has become fast, and recent photoresist compositions with high resolution tend to have weaker etching resistance.

[0005] This necessitates dry etching of substrates using thinner photoresist films with weaker etching resistance, making the securing of materials and processes for this manufacturing stage a matter of urgency.

[0006] One way to solve these problems is the multilayer resist method. In this method, a photoresist film (i.e., a resist upper layer) and a resist interlayer with different etching selectivity are interposed between the resist upper layer and the substrate to be processed. After obtaining a pattern on the resist upper layer, the resist upper layer pattern is used as a dry etching mask to transfer the pattern to the resist interlayer by dry etching, and then the resist interlayer is used as a dry etching mask to transfer the pattern to the substrate to be processed by dry etching.

[0007] One multilayer resist method is the three-layer resist method, which can be performed using the same resist compositions as those used in the single-layer resist method. In this three-layer resist method, for example, an organic film made of novolac resin or the like is deposited on the substrate to be processed as the resist underlayer, a silicon-containing resist interlayer is deposited on top of that as the resist interlayer, and a normal organic photoresist film is formed on top of that as the resist upper layer. When dry etching is performed using a fluorine-based gas plasma, the organic resist upper layer has a good etching selectivity ratio compared to the silicon-containing resist interlayer, so the resist upper layer pattern can be transferred to the silicon-containing resist interlayer by dry etching with a fluorine-based gas plasma. With this method, even if a resist composition that does not have sufficient thickness to form a pattern for direct processing of the substrate or a resist composition that does not have sufficient dry etching resistance for substrate processing is used, the pattern can be transferred to the silicon-containing resist interlayer (resist interlayer), and then by performing pattern transfer by dry etching with an oxygen-based or hydrogen-based gas plasma, a pattern of an organic film (resist underlayer) made of novolac resin or the like with sufficient dry etching resistance for substrate processing can be obtained. Many types of resist underlayer films, such as those described in Patent Document 1, are already known.

[0008] As silicon-containing resist interlayers used in the three-layer resist method described above, silicon-containing inorganic films produced by CVD, such as SiO2 films (e.g., Patent Document 2) and SiON films (e.g., Patent Document 3), and films that can be obtained by rotary coating, such as SOG (spin-on glass) films (e.g., Patent Document 4 and Non-Patent Document 1) and crosslinkable silsesquioxane films (e.g., Patent Document 5), are used, and polysilane films (e.g., Patent Document 6) may also be used. Among these, SiO2 films and SiON films have high performance as dry etching masks when dry etching the underlying organic film, but require special equipment for film formation. In contrast, SOG films, crosslinkable silsesquioxane films, and polysilane films can be formed by rotary coating and heating alone, and are considered to have high process efficiency.

[0009] The silicon-containing films conventionally used in such multilayer resist methods have several problems. For example, when attempting to form a resist pattern by photolithography, it is well known that exposure light is reflected by the substrate and interferes with the incident light, causing the so-called standing wave problem. To obtain fine patterns without edge roughness in the resist film under state-of-the-art ArF immersion and high NA exposure conditions, an anti-reflective function is essential for the interlayer. Furthermore, in the state-of-the-art semiconductor processes described above, the thinning of photoresists is progressing even further, so thinning of the interlayer is also required, and in next-generation exposure processes, it is required to impart an anti-reflective effect with a film thickness of 30 nm or less. In addition, the dry etching rate for oxygen gas plasma, which is commonly used when processing the resist underlayer, is preferably lower in order to increase the etching selectivity ratio between the interlayer and the underlayer, and improvement in dry etching resistance is required for the interlayer in line with the trend towards thinner films.

[0010] To meet the requirements for anti-reflective properties and dry etching characteristics, metal-containing films (metal hard mask films) containing Ti or Zr are attracting attention as resist interlayers, replacing conventional silicon-containing films. TiO2 and ZrO2 are known as high refractive index materials, and including them in the film makes it possible to improve the anti-reflective effect under high NA exposure conditions. Furthermore, the inclusion of metal-oxygen bonds is expected to provide excellent dry etching resistance to oxygen gas.

[0011] Furthermore, since the metal-containing film exhibits excellent dry etching resistance not only to oxygen gas but also to fluorine gas, a two-layer resist method is also promising, in which a metal-containing film is deposited on the substrate as a resist underlayer, and a resist upper layer is formed on top of it.

[0012] On the other hand, when such a metal-containing film is used directly beneath the resist upper layer, improving adhesion with the resist pattern becomes a challenge. The cured metal-containing film has a much higher surface energy (or a smaller water contact angle) than the subsequently applied photoresist. This mismatch in surface energy causes poor adhesion between the metal-containing film and the subsequently applied photoresist, leading to pattern collapse.

[0013] To suppress the collapse of photoresist patterns on metal-containing films, surface modification of the metal-containing film is necessary. For example, Patent Document 7 reports a metal hard mask containing a surface-modified organic polymer. It has been reported that by utilizing the difference in free energy between the organic polymer and the metal compound and unevenly distributing the organic polymer on the surface, adhesion to the resist pattern is improved. To suppress pattern collapse, organic polymers containing surface-treated portions selected from hydroxyl, protected hydroxyl, protected carboxyl, and mixtures thereof are used. However, in the current situation where finer pattern formation is required, these materials do not have sufficient pattern collapse suppression performance.

[0014] Recently, it has been recognized that the interaction at the interface between the resist upper layer and the lower layer directly beneath it in fine patterns affects the sensitivity of the resist, the shape of the pattern (rectangularity and space residue), and from these perspectives, there is a need for performance improvement in the lower layer directly beneath the resist upper layer (Non-Patent Literature 2). [Prior art documents] [Patent Documents]

[0015] [Patent Document 1] Japanese Patent Publication No. 2004-205685 [Patent Document 2] Japanese Patent Application Publication No. 7-183194 [Patent Document 3] Japanese Patent Application Publication No. 7-181688 [Patent Document 4] Japanese Patent Application Publication No. 5-291208 [Patent Document 5] Special Publication No. 2005-520354 [Patent Document 6] Japanese Patent Application Publication No. 11-60735 [Patent Document 7] Patent No. 6463600 specification [Non-patent literature]

[0016] [Non-Patent Document 1] J.Appl.Polym. Sci.,Vol.88,636-640(2003) [Non-Patent Document 2] Proc. SPIE Vol. 7273,72731J(2009) [Overview of the project] [Problems that the invention aims to solve]

[0017] The present invention has been made in view of the above circumstances, and provides a metal-containing film that can be obtained in a fine patterning process in the semiconductor device manufacturing process, and which has high adhesion to the resist upper layer film and can suppress the collapse of the fine pattern. film The objective is to provide a pattern-forming composition and a pattern-forming method using the composition. [Means for solving the problem]

[0018] To solve the above problems, the present invention provides: (A) Metal compounds and, (B) Surface modifier and (C) Solvent and It contains, The metal compound comprises at least one metal atom selected from the group consisting of Ti, Zr, and Hf. The present invention provides a metal-containing film-forming composition characterized in that the (B) surface modifier is a polymer compound containing one or both of the repeating units represented by the following general formula (1) and the repeating units represented by the following general formula (2), and the polymer compound does not contain repeating units containing hydroxyl groups. [ka] (In the formula, R1 is a hydrogen atom or a methyl group, R2 is a monovalent organic group having 2 to 20 carbon atoms and containing a heterocyclic structure, and R3 is a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms.)

[0019] Such a metal-containing film-forming composition provides high adhesion to the resist upper layer, prevents distortion of fine patterns, and forms a metal-containing film that gives a good pattern shape. Furthermore, because the resulting metal-containing film exhibits a high refractive index, it can exhibit a high anti-reflective effect under ArF immersion and high NA exposure conditions.

[0020] Furthermore, it is preferable that the heterocyclic structure contains an oxygen atom.

[0021] Having such a structure in the metal-containing film-forming composition provides higher adhesion to the resist upper layer film, making it even more effective in preventing the deformation of fine patterns.

[0022] Furthermore, it is preferable that R2 in the above general formulas (1) and (2) is a monovalent organic group containing a group selected from the following formulas (R2-1) to (R2-3). [ka] (In the formula, R4 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the dashed line indicates a bond.)

[0023] By including a surface modifier (B) having such a structure in the metal-containing film-forming composition, higher adhesion to the resist upper layer film can be obtained, making it even more effective in preventing the deformation of fine patterns.

[0024] Furthermore, it is preferable that the (B) surface modifier is a polymer compound further containing either the repeating unit represented by formula (3a) or formula (3b) below. [ka] (In the above formula, R F1 is a monovalent organic group having 1 to 20 carbon atoms and containing at least one F atom, and R F2 (where R1 is a fluorine atom or a monovalent organic group having 1 to 10 carbon atoms containing one or more fluorine atoms, R1 is a hydrogen atom or a methyl group, and n is 1 to 5.)

[0025] Using such a surface modifier is preferable because it makes it easier for the surface modifier to be unevenly distributed on the surface of the metal-containing film.

[0026] Furthermore, it is preferable that the weight-average molecular weight of the polymer compound used in the (B) surface modifier is 6,000 to 50,000.

[0027] Furthermore, it is preferable that the degree of dispersion of the polymer compound used in the (B) surface modifier, expressed as weight-average molecular weight / number-average molecular weight, is 3.0 or less.

[0028] By setting the weight-average molecular weight and / or degree of dispersion of the polymer compounds contained in the metal-containing film-forming composition to this range, excellent film-forming properties can be obtained, and the generation of sublimation during heat curing can be suppressed, preventing contamination of the equipment.

[0029] Furthermore, it is preferable that the content of the (B) surface modifier contained in the metal-containing film-forming composition is 1 part by mass or more and 50 parts by mass or less per 100 parts by mass of the metal compound.

[0030] By including the surface modifier in this ratio, higher adhesion to the resist upper layer film can be obtained without degrading the dry etching resistance or refractive index of the metal-containing film-forming composition, making it even more effective in preventing the deformation of fine patterns.

[0031] Furthermore, (D) Thermal acid generator, (E) Photoacid generator, (F) Crosslinking agent, and (G) Surfactants It is preferable that it contains at least one of the following.

[0032] The presence and selection of these various additives allows for fine-tuning of performance in terms of film formation, reduction of sublimation, and various characteristics of resist patterning, according to customer requirements, which is practically preferable.

[0033] Furthermore, the (C) solvent includes (C-1) a high-boiling point solvent, The (C-1) high-boiling point solvent is preferably one or more organic solvents with a boiling point of 180 degrees or higher.

[0034] By including such a high-boiling-point solvent, sufficient thermal fluidity can be obtained during film formation. Therefore, when forming a metal-containing film, it is possible to achieve a high degree of compatibility between (A) etching selectivity of the metal compound and (B) pattern adhesion of the surface modifier without forming a sea-island structure.

[0035] Furthermore, it is preferable that the metal compound (A) is derived from a metal compound represented by the following general formula (4). [ka] (In the formula, M is Ti, Zr, or Hf. L is a monodentate ligand having 1 to 30 carbon atoms.) or It is a polydentate ligand, where X is a halogen atom, alkoxy group, carboxylate group, acyloxy group, or -NR a R b It is a hydrolyzable group selected from among the following. a and R b Each of these is independently a hydrogen atom or a monovalent organic group with 1 to 20 carbon atoms. a + b = 4, where a and b are integers between 0 and 4.

[0036] By using such metal compounds, it is possible to form metal-containing films with superior dry etching resistance to oxygen gas.

[0037] In this case, it is more preferable that the (A) metal compound is a reaction product of a compound derived from the metal compound represented by the general formula (4) and an organic compound having 1 to 30 carbon atoms containing at least one crosslinking group represented by any of the following general formulas (a-1) to (a-4), (b-1) to (b-4), and (c-1) to (c-3). [Chemical formula] (In the above general formulas (a-1) to (a-4), R a is hydrogen or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding site.) [Chemical formula] (In the above general formula, R b is a hydrogen atom or a methyl group, and in the same formula, they may be the same or different from each other. R c is hydrogen or a substituted or unsubstituted saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, and * represents a bonding site.) [Chemical formula] (In the above general formulas (c-1) to (c-3), Y1 is a divalent organic group having 1 to 20 carbon atoms, R is a hydrogen atom, a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent 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 group having 7 to 31 carbon atoms. R d is an organic group in which a protecting group is removed by the action of any one or both of an acid and heat to generate one or more hydroxyl groups or carboxyl groups, and * represents a bonding site.) [Chemical formula] (In the above general formula (c-4), R e is an organic group in which a protecting group is removed by the action of any one or both of an acid and heat, and * represents a bonding site with Y1.)

[0038] If a metal compound (A) containing such an organic group is used, sufficient thermal fluidity can be obtained during film formation. Therefore, when forming a metal-containing film, it is possible to achieve an even higher level of compatibility between the etching selectivity of the metal compound (A) and the pattern adhesion of the surface modifier (B) without forming a sea-island structure.

[0039] Furthermore, the present invention provides a method for forming a pattern on a substrate to be processed, (I-1) A step of forming a metal-containing film by applying the metal-containing film-forming composition of the present invention onto a substrate to be processed, and then heat-treating it. (I-2) A step of forming a resist upper layer film on the metal-containing film using a photoresist material, (I-3) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (I-4) A step of transferring the pattern to the metal-containing film by dry etching using the resist upper layer film on which the pattern is formed as a mask, and (I-5) A step of processing the workpiece substrate using the metal-containing film on which the pattern is formed as a mask to form a pattern on the workpiece substrate. The present invention provides a pattern forming method characterized by having the following features.

[0040] Furthermore, the present invention provides a method for forming a pattern on a substrate to be processed, (II-1) A step of forming a resist underlayer film on a substrate to be processed, (II-2) A step of forming a metal-containing film by applying the metal-containing film-forming composition of the present invention onto the resist underlayer film and then heat-treating it, (II-3) A step of forming a resist upper layer film on the metal-containing film using a photoresist material, (II-4) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (II-5) A step of transferring the pattern to the metal-containing film by dry etching, using the resist upper layer film on which the pattern is formed as a mask. (II-6) A step of transferring the pattern to the resist underlayer film by dry etching, using the metal-containing film on which the pattern has been transferred as a mask. (II-7) A step of processing the substrate to be processed using the resist underlayer film on which the pattern is formed as a mask to form a pattern on the substrate to be processed, The present invention provides a pattern forming method characterized by having the following features.

[0041] Thus, the metal-containing film-forming composition of the present invention can be suitably used in various pattern formation methods such as two-layer resist processes and three-layer resist processes. With these pattern formation methods, the metal-containing film provided by the present invention can effectively suppress pattern deformation, making it suitable for photolithography of the resist upper layer film, and enabling high-precision transfer of the resist upper layer film pattern to the workpiece substrate. [Effects of the Invention]

[0042] As described above, the present invention provides a metal-containing film-forming composition that has high adhesion to the resist upper layer film and an effect of suppressing the deformation of fine patterns. Furthermore, this metal-containing film-forming composition has high adhesion and an effect of suppressing the deformation of fine patterns, and imparts a highly rectangular pattern shape to the substrate being processed, making it extremely useful in multilayer resist processes. In addition, the metal-containing film-forming composition of the present invention has excellent resistance to dry etching using oxygen gas and fluorine gas, respectively, so it can form fine patterns on the substrate being processed with high precision in various pattern formation methods such as two-layer resist processes and three-layer resist processes. [Brief explanation of the drawing]

[0043] [Figure 1] Figure 1 is an explanatory diagram of an example of the pattern formation method of the present invention (3-layer resist process). [Figure 2] Figure 2 is an explanatory diagram of an example of the pattern formation method of the present invention (two-layer resist process). [Figure 3] Figure 3 is an explanatory diagram of the reflectance calculation in the pattern formation method. [Modes for carrying out the invention]

[0044] As described above, in the fine patterning process of semiconductor device manufacturing, there has been a need for the development of a metal-containing film formation composition that provides a metal-containing film that yields a good pattern shape, has high adhesion to the resist upper layer film and suppresses the collapse of the fine pattern, and a pattern formation method using this composition.

[0045] As a result of diligent research into the above-mentioned problems, the inventors of this invention have found that a metal-containing film-forming composition containing a polymer compound of a specific structure, and a pattern-forming method using this metal-containing film-forming composition, can solve the above-mentioned problems, and have completed the present invention.

[0046] In other words, the present invention is (A) Metal compounds and, (B) Surface modifier and (C) Solvent and It contains, The metal compound comprises at least one metal atom selected from the group consisting of Ti, Zr, and Hf. The metal-containing film-forming composition is characterized in that the (B) surface modifier is a polymer compound containing one or both of the repeating units represented by the following general formula (1) and the repeating units represented by the following general formula (2), and the polymer compound does not contain repeating units containing hydroxyl groups. [ka] (In the formula, R1 is a hydrogen atom or a methyl group, R2 is a monovalent organic group having 2 to 20 carbon atoms and containing a heterocyclic structure, and R3 is a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms.)

[0047] Furthermore, the present invention relates to a method for forming a pattern on a substrate to be processed, (I-1) A step of forming a metal-containing film by applying the metal-containing film-forming composition of the present invention onto a substrate to be processed, and then heat-treating it. (I-2) A step of forming a resist upper layer film on the metal-containing film using a photoresist material, (I-3) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (I-4) A step of transferring the pattern to the metal-containing film by dry etching using the resist upper layer film on which the pattern is formed as a mask, and (I-5) A step of processing the workpiece substrate using the metal-containing film on which the pattern is formed as a mask to form a pattern on the workpiece substrate. This is a pattern forming method characterized by having [a certain feature].

[0048] Furthermore, the present invention relates to a method for forming a pattern on a substrate to be processed, (II-1) A step of forming a resist underlayer film on a substrate to be processed, (II-2) A step of forming a metal-containing film by applying the metal-containing film-forming composition of the present invention onto the resist underlayer film and then heat-treating it, (II-3) A step of forming a resist upper layer film on the metal-containing film using a photoresist material, (II-4) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (II-5) A step of transferring the pattern to the metal-containing film by dry etching, using the resist upper layer film on which the pattern is formed as a mask. (II-6) A step of transferring the pattern to the resist underlayer film by dry etching, using the metal-containing film on which the pattern has been transferred as a mask. (II-7) A step of processing the substrate to be processed using the resist underlayer film on which the pattern is formed as a mask to form a pattern on the substrate to be processed, This is a pattern forming method characterized by having [a certain feature].

[0049] The present invention will be described in detail below, but the present invention is not limited to these descriptions.

[0050] <Metal-containing film forming composition> The present invention (A) Metal compounds and, (B) Surface modifier and (C) Solvent and It contains, The metal compound comprises at least one metal atom selected from the group consisting of Ti, Zr, and Hf. The metal-containing film-forming composition is characterized in that the (B) surface modifier is a polymer compound containing one or both of the repeating units represented by the following general formula (1) and the repeating units represented by the following general formula (2), and the polymer compound does not contain repeating units containing hydroxyl groups. [ka] (In the formula, R1 is a hydrogen atom or a methyl group, R2 is a monovalent organic group having 2 to 20 carbon atoms and containing a heterocyclic structure, and R3 is a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms.)

[0051] In the metal-containing film-forming composition of the present invention, (A) a metal compound, (B) a surface modifier, and (C) a solvent may each be used individually or in combination of two or more components. Furthermore, the metal-containing film-forming composition may also contain components other than those described above (A), (B), and (C). Each component will be described below.

[0052] <(A) Metal compounds> The metal compound (A) contained in the metal-containing film-forming composition of the present invention comprises at least one metal atom selected from the group consisting of Ti, Zr, and Hf.

[0053] By including such metals, the refractive index of the metal-containing film after heat treatment can be increased, and a metal-containing film with excellent dry etching resistance using oxygen gas and fluorine gas can be formed.

[0054] (A) The lower limit of the content of metal element atoms in the metal compound is preferably 10% by mass, more preferably 20% by mass, and even more preferably 30% by mass. The upper limit of the above content is preferably 50% by mass. The content of metal element atoms can be determined by measurement using a differential thermal balance (TG / DTA).

[0055] With such a proportion of metal elements, the refractive index of the metal-containing film-forming composition, as well as its dry etching resistance to oxygen and fluorine gases, can be further improved.

[0056] The metal atoms contained in the above metal compound may consist of atoms of one element or of two or more elements. However, it is preferable that the metal atoms consist of atoms of one element, given the desire for the etching rate during inorganic film etching transfer processing after fine pattern formation to be uniform in-plane at the nanometer level.

[0057] (A) The metal compound is preferably a compound having a metal-oxygen covalent bond.

[0058] The presence of metal-oxygen atoms in the above-mentioned metal compound results in a metal-containing film formed from the metal-containing film-forming composition exhibiting superior etching selectivity. The oxygen atoms may be bonded one to one metal atom or multiple oxygen atoms, but it is preferable that the structure mainly consists of two oxygen atoms bonded to a metal atom. By mainly including a structure in which two oxygen atoms are bonded to a metal atom, the metal compound can be made into a more linear structure, such as -MOMO- (where M is at least one metal atom selected from the group consisting of Ti, Zr, and Hf), thereby improving its solvent solubility.

[0059] To mix two substances with different properties and form a two-layer structure in a single application, the difference in free energy between (A) the metal compound and (B) the surface modifier must be appropriate. If the difference in free energy is not appropriate, a so-called sea-island structure often occurs, where domains from one layer are scattered within the matrix of the other layer. Therefore, the combination of (A) the metal compound and (B) the surface modifier is crucial.

[0060] As the (A) metal compound of the present invention, commercially available metal compounds can be used, but for example, a metal-containing compound having a hydrolyzable group (hereinafter referred to as (a) metal-containing compound) can be used. Alternatively, it can be synthesized by a method such as carrying out a hydrolysis condensation reaction of the (a) metal-containing compound. That is, the (A) metal compound can be derived from the (a) metal-containing compound. Here, "hydrolysis condensation reaction" refers to a reaction in which the hydrolyzable group of the (a) metal-containing compound is hydrolyzed and converted to -OH, and the two resulting -OH groups undergo dehydration condensation to form -O-.

[0061] The (A) metal compound of the present invention includes the (a) metal-containing compound, the hydrolysis condensation product of the (a) metal-containing compound, or a monodentate ligand or Many It is preferable to use a compound obtained by reacting with a substance that can act as a dentate ligand, and (a) a hydrolysis condensation product of a metal-containing compound or (a) a monodentate ligand or Many It is more preferable to use a compound obtained by reacting a substance that can act as a acetagnic ligand.

[0062] With such (A) metal compounds, the surface energy is higher than that of (B) surface modifiers. Therefore, when forming a resist underlayer film, it is possible to achieve a high degree of balance between the etching selectivity of (A) metal compounds and the pattern adhesion of (B) surface modifiers without forming a sea-island structure.

[0063] [(a) Metal-containing compounds] The metal-containing compound described in (a) above is a metal compound (I) having a hydrolyzable group, a hydrolyzate of metal compound (I), a hydrolyzed condensate of metal compound (I), or a combination thereof. In other words, the metal-containing compound described in (a) above is derived from metal compound (I). Metal compound (I) can be used alone or in combination of two or more types.

[0064] Examples of the metal compound (I) include compound (I-1) represented by the following formula (4). By using such a metal compound (I-1), a stable compound (A) can be formed, and the dry etching resistance can be improved. [ka] (In the formula, M is Ti, Zr, or Hf. L is a monodentate ligand having 1 to 30 carbon atoms.) or It is a polydentate ligand, where X is a halogen atom, alkoxy group, carboxylate group, acyloxy group, or -NR a R b It is a hydrolyzable group selected from among the following. a and R b Each of these is independently a hydrogen atom or a monovalent organic group with 1 to 20 carbon atoms. a + b = 4, where a and b are integers between 0 and 4.

[0065] [Hydrolyzable group] Examples of the hydrolyzable group X include halogen atoms, alkoxy groups, carboxylate groups, acyloxy groups, and -NR groups. a R b R is one example. a and R b Each of these is preferably a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

[0066] Examples of the halogen atoms mentioned above include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0067] Examples of the alkoxy groups mentioned above include methoxy groups, ethoxy groups, and n-p groups. BExamples include the poxy group, i-propoxy group, n-butoxy group, and t-butoxy group.

[0068] Examples of the carboxylate groups mentioned above include acetate groups, propionate groups, butyrate groups, n-hexanecarboxylate groups, and n-octanecarboxylate groups.

[0069] Examples of the above-mentioned acyloxy groups include acetoxy group, ethylyloxy group, propionyloxy group, butyryloxy group, t-butyryloxy group, t-amiryloxy group, n-hexanecarbonyloxy group, and n-octanecarbonyloxy group.

[0070] The above -NR a R b Examples of such groups include unsubstituted amino groups, methylamino groups, dimethylamino groups, diethylamino groups, and dipropylamino groups.

[0071] The hydrolyzable group X is preferably an alkoxy group, and more preferably an i-propoxy group, an n-butoxy group, or a t-butoxy group.

[0072] [Monodentate ligand] Examples of the monodentate ligands mentioned above include hydroxo ligands, carboxyl ligands, amide ligands, amine ligands, ammonia ligands, and olefin ligands.

[0073] Examples of the above-mentioned amide ligands include unsubstituted amide ligands (NH2), methylamide ligands (NHMe), dimethylamide ligands (NMe2), diethylamide ligands (NEt2), and dipropylamide ligands (NPr2).

[0074] Examples of the amine ligands mentioned above include pyridine, trimethylamine ligand, and piperidine ligand.

[0075] Examples of olefin ligands include chain olefins such as ethylene and propylene, and cyclic olefins such as cyclopentene, cyclohexene, and norbornene.

[0076] [Polydentate ligand] Examples of the polydentate ligands mentioned above include ligands derived from hydroxy acid esters, ligands derived from β-diketones, ligands derived from β-ketoesters, ligands derived from α,α-dicarboxylic acid esters, hydrocarbons having π bonds, and diphosphines.

[0077] Examples of the hydroxy acid esters mentioned above include glycolic acid esters, lactate esters, 2-hydroxycyclohexane-1-carboxylic acid esters, salicylic acid esters, and the like.

[0078] Examples of the above-mentioned β-diketones include acetoacetate esters, α-alkyl-substituted acetoacetate esters, β-ketopentanoate esters, benzoyl acetate esters, and 1,3-acetonedicarboxylic acid esters.

[0079] Examples of the α,α-dicarboxylic acid esters mentioned above include malonic acid diesters, α-alkyl-substituted malonic acid diesters, α-cycloalkyl-substituted malonic acid diesters, and α-aryl-substituted malonic acid diesters.

[0080] Examples of hydrocarbons having the π bond mentioned above include linear dienes such as butadiene and isoprene, cyclic dienes such as cyclopentadiene, methylcyclopentadiene, pentamethylcyclopentadiene, cyclohexadiene, and norbornadiene, and aromatic hydrocarbons such as benzene, toluene, xylene, hexamethylbenzene, naphthalene, and indene.

[0081] Examples of the above-mentioned diphosphines include 1,1-bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, and 1,1'-bis(diphenylphosphino)ferrocene.

[0082] In the general formula (4) above, a + b = 4, and a and b are integers from 0 to 4. For a, 0 to 3 is preferred, 0 to 2 is more preferred, 1 to 2 is even more preferred, and 2 is particularly preferred. For b, 2 to 4 is preferred, 2 or 3 is more preferred, and 2 is even more preferred. By setting a and b within the above ranges, the stability of the (A) metal compound can be increased.

[0083] (a) As the metal-containing compound, metal alkoxides that have not undergone hydrolysis or hydrolysis condensation, or metal alkoxides that have a ligand and have not undergone hydrolysis condensation are preferred.

[0084] (a) Examples of metal-containing compounds include titanium-containing compounds such as diisopropoxybis(2,4-pentanedione)titanium(IV), tetra-n-butoxytitanium(IV), tetra-n-propoxytitanium(IV), tri-n-butoxymonostearatetitanium(IV), titanium(IV) butoxide oligomer, aminopropyltrimethoxytitanium(IV), triethoxymono(2,4-pentanedione)titanium(IV), tri-n-propoxymono(2,4-pentanedione)titanium(IV), triisopropoxymono(2,4-pentanedione)titanium, di-n-butoxybis(2,4-pentanedione)titanium(IV), etc., and zirconium-containing compounds such as dibutoxybis(ethylacetate) Tate) Zirconium(IV), di-n-butoxybis(2,4-pentanedione)zirconium(IV), tetra-n-butoxyzirconium(IV), tetra-n-propoxyzirconium(IV), tetraisopropoxyzirconium(IV), aminopropyltriethoxyzirconium(IV), 2-(3,4-epoxycyclohexyl)ethyltrimethoxyzirconium(IV), γ-glycidoxypropyltrimethoxyzirconium(IV), 3-isocyanopropyltrimethoxyzirconium(IV), triethoxymono(2,4-pentanedione)zirconium(IV), tri-n-propoxymono(2,4-pentanedione)zirconium(IV), triisopropoxymono(2,4-pentanedione) Examples include zirconium(IV), tri(3-methacryloxypropyl)methoxyzirconium(IV), and tri(3-acryloxypropyl)methoxyzirconium(IV). Compounds containing hafnium include diisopropoxybis(2,4-pentanedione)hafnium(IV), tetrabutoxyhafnium(IV), tetraisopropoxyhafnium(IV), tetraethoxyhafnium(IV), and dichlorobis(cyclopentadienyl)hafnium(IV).

[0085] (A) In the synthesis reaction of metal compounds, (a) in addition to metal-containing compounds, (A) monodentate ligands or ManyCompounds that can act as receptor ligands (hereinafter referred to as (b) ligand-forming compounds) may be added.

[0086] Examples of ligand-forming compounds in (b) above include organic compounds derived from hydroxo ligands, carboxyl ligands, amide ligands, amine ligands, ammonia ligands, olefin ligands, etc., listed as L in formula (4) above, organic compounds derived from hydroxy acid esters, ligands derived from β-diketones, ligands derived from β-ketoesters, ligands derived from α,α-dicarboxylic acid esters, etc., as well as compounds having multiple hydroxyl groups.

[0087] Furthermore, (b) the ligand-forming compound may be an organic compound having 1 to 30 carbon atoms that contains at least one bridging group represented by any of the following general formulas (a-1) to (a-4), (b-1) to (b-4), and (c-1) to (c-3).

[0088] [ka] (In the above general formulas (a-1) to (a-4), R a (where is a hydrogen atom or a monovalent organic group with 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.) [ka] (In the above general formula, R b R is a hydrogen atom or a methyl group, and in the same formula they may be the same or different from each other. c (where * represents hydrogen, a substituted or unsubstituted saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, and * represents a bond.) [ka] (In the above general formulas (c-1) to (c-3), Y1 is a divalent organic group having 1 to 20 carbon atoms, R is a hydrogen atom, a substituted or unsubstituted saturated or unsaturated divalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, R d This refers to an organic group represented by the following general formula (c-4) in which a protecting group is removed by the action of either an acid, heat, or both, generating one or more hydroxyl groups or carboxyl groups, where * represents a bond. [ka] (In the above general formula (c-4), R e (* represents an organic group whose protecting group is removed by either acid, heat, or both, and * indicates the bond with Y1.)

[0089] (b) The ligand-forming compound contains at least one crosslinking group as indicated in (a-1) to (a-4), (b-1) to (b-4), and (c-1) to (c-3) above, which allows for sufficient thermal fluidity during film formation. Therefore, when forming a metal-containing film, it is possible to achieve a higher degree of compatibility between (A) etching selectivity of the metal compound and (B) pattern adhesion of the surface modifier without forming a sea-island structure.

[0090] (A) From the viewpoint of productivity and stability of metal compounds, the ligand-forming compounds (b) described above are more preferably compounds derived from carboxyl ligands, compounds derived from β-diketone ligands, and compounds having multiple hydroxyl groups. These can be used individually or in combination of two or more.

[0091] Examples of compounds derived from carboxyl ligands include the compound shown in formula (5) below. [ka] (In the above general formula (5), p is either 0 or 1. If p is 1, X 1is a divalent organic group having 2 to 20 carbon atoms, and W is an alkoxy group having 1 to 10 carbon atoms, one of the following general formulas (5-A) or (b-1) to (b-4). When p is 0, X 1 This is a monovalent organic group having 8 to 30 carbon atoms that contains a bridging group and an aromatic ring, both of the structures represented by the general formulas (a-2) and (a-3) above. [ka] (In the above general formula (5-A), Y is a divalent organic group having 1 to 20 carbon atoms and saturated or 2 to 20 carbon atoms and unsaturated, R A (This represents one of the structures shown in the general formulas (a-1) to (a-4) above, where h represents 1 to 6, and * represents the bond with the carbonyl atom.)

[0092] If the compound is derived from a carboxyl ligand with such a structure, (A) the thermosetting properties of the metal compound will be improved, and a metal-containing film with excellent mixing resistance with the resist upper layer can be formed.

[0093] In the above general formula (5), it is preferable that p is 1 and W has the structure shown in the following general formula (5-B). [ka] (In the above general formula (5-B), R A1 This is the structure shown by the general formula (a-1) above, and R A2 is one of the structures represented by the above general formula (a-2) or (a-3), Z is either an oxygen atom or a secondary amine, L is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R A3 (where is a divalent organic group with 1 to 20 carbon atoms, saturated or unsaturated with 2 to 20 carbon atoms, t is 1 to 6, s is 0 to 5, t+s is 1 to 6, r is 1 to 10, u is 0 or 1, m is 0 or 1, and * represents the bond with the carbon atom of the carbonyl group.)

[0094] If the compound is derived from a carboxyl ligand with such a structure, (A) the heat resistance of the metal compound is improved, so the formed metal-containing film exhibits excellent film-forming properties, and the generation of sublimation products during heat curing is suppressed, preventing contamination of the equipment.

[0095] In the above general formula (5), p is 1, W is an alkoxy group having 1 to 10 carbon atoms, and X 1 It is preferable that the structure is one of those represented by the following general formula (5-C). [ka]

[0096] If the compound is derived from a carboxyl ligand with such a structure, (A) the heat resistance of the metal compound is improved, so the formed metal-containing film exhibits excellent film-forming properties, and the generation of sublimation products during heat curing is suppressed, preventing contamination of the equipment.

[0097] Alternatively, in the general formula (5) above, p is 0 and X 1 It is preferable that the structure is one of those represented by the following general formula (5-D). [ka] (In the above general formula (5-D), R f This is the same as the general formula (a-2) or (a-3) above, and * represents the bond between the carbonyl atom and the carbon atom.

[0098] Examples of compounds derived from carboxyl ligands include the compound shown in formula (6) below. [ka] (In the above general formula (6), X 2 R is a divalent organic group having 1 to 31 carbon atoms. 6A (This is one of the general formulas (c-1) to (c-3) above.)

[0099] In the above general formula (6), X 2The group is a divalent organic group having 1 to 31 carbon atoms, and from the viewpoint of thermosetting properties, it is more preferable to be a saturated hydrocarbon having 1 to 20 carbon atoms or an unsaturated hydrocarbon having 2 to 20 carbon atoms.

[0100] In the above general formulas (c-1) to (c-3), Y1 is preferably a substituted or unsubstituted saturated or unsaturated divalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, and preferably Y1 is a saturated or unsaturated hydrocarbon having 1 to 20 carbon atoms or 2 to 20 carbon atoms.

[0101] In the general formulas (c-1) to (c-3) above, if Y1 is a saturated hydrocarbon having 1 to 20 carbon atoms or an unsaturated hydrocarbon having 2 to 20 carbon atoms, the thermosetting properties of the metal compound (A) can be further improved. This is also preferable from the viewpoint of raw material availability.

[0102] As an example of Y1, the following structures can be specifically illustrated, but are not limited to these. [ka] (*1 is a bond with an oxygen atom or nitrogen atom, and *2 is R d (This represents the connection point.)

[0103] In the above general formula (c-4), R e The group is an organic group whose thermally acid-unstable group is eliminated by the action of acid, heat, or both. Preferably, it is a tertiary hydrocarbyl group or a group that forms an acetal structure with an adjacent oxygen atom, with a tertiary hydrocarbyl group being particularly preferred. The tertiary hydrocarbyl group is preferably one having 4 to 20 carbon atoms, and among these, one with fewer carbon atoms is more preferred.

[0104] Examples of compounds derived from β-diketone ligands include the compound shown in formula (7). [ka] (In the above general formula, R 7A~R 7c This may contain a hydrogen atom or a bridging group represented by any of the above general formulas (a-1) to (a-4) and (b-1) to (b-4), and has 1 to 20 carbon atoms. Monovalent It is an organic group.

[0105] The compound of general formula (7) above preferably contains at least one crosslinking group represented by any of the general formulas (a-1) to (a-4) and (b-1) to (b-4). Such a compound is preferable because it can further improve the thermosetting properties of the (A) metal compound.

[0106] Examples of compounds having multiple hydroxyl groups include dihydric alcohols represented by any of the formulas (7-A) to (7-C). [ka] (In the above general formula, R 7a ~R 7b This may contain a hydrogen atom or a bridging group represented by any of the above general formulas (a-1) to (a-4), and has 1 to 20 carbon atoms. Monovalent It is an organic group, R 7c ~R 7f This may contain a hydrogen atom or a bridging group represented by any of the following general formulas (a-1) to (a-4) and (b-1) to (b-4), and has 1 to 20 carbon atoms. Monovalent It is an organic group, Y 2 R is a divalent organic group having 1 to 10 carbon atoms. In the general formula (7-A) above, adjacent R 7a and R 7b These elements may bond to each other, forming unsaturated or saturated ring structures.

[0107] The compounds of the above general formulas (7-A) to (7-C) preferably contain at least one crosslinking group represented by any of the above general formulas (a-1) to (a-4) and (b-1) to (b-4). Such compounds are preferable because they can further improve the thermosetting properties of the (A) metal compound.

[0108] (A) In the metal compound, the content of ligands derived from (b) the ligand-forming compound is preferably 10 mol% to 90 mol%, and more preferably 20 mol% to 80 mol%, of the total amount of ligands coordinating to the metal atom. (b) Ligands other than the ligand-forming compound, for example, ligands derived from alkoxy groups having 1 to 10 carbon atoms, are preferably contained in an amount of 0 mol% to 50 mol%, and more preferably 0 mol% to 20 mol%, of the total amount of ligands coordinating to the metal atom.

[0109] Furthermore, in addition to (a) the metal-containing compound and (b) the ligand-forming compound, (c) the silicon-containing compound may be added during the synthesis reaction of the metal compound.

[0110] (a) By substituting the hydrolyzable groups of the metal-containing compound with (c) the silicon-containing compound, the stability of the (A) metal compound in the metal-containing film-forming composition can be improved.

[0111] (c) Examples of silicon-containing compounds include the structure shown in formula (s) below. [ka] (Among the above (s), R s1 , R s2 and R s3 This is one of the following organic groups selected from: an organic group having 1 to 30 carbon atoms having a bridging group in any of the structures shown by the general formulas (s-1) to (s-3) below; a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; and an aryl group having 1 to 20 carbon atoms. [ka] (In the above general formulas (s-1) to (s-3), R s4 (where is a hydrogen atom or a monovalent organic group with 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.)

[0112] (c) The silicon-containing compound is more preferably a compound represented by any of the following formulas, and trimethylsilanol is more preferred from the viewpoint of productivity. [ka]

[0113] (A) When the metal compound contains ligands derived from (b) a ligand-forming compound and ligands derived from (c) a silicon-containing compound, the content of ligands derived from (b) the ligand-forming compound in (A) the metal compound is preferably 10 mol% to 90 mol%, and more preferably 20 mol% to 80 mol%, of the total amount of ligands coordinating to the metal atom. (c) Silicon-containing compound thing Ligands derived from (b) are preferably present in an amount of 10 mol% to 90 mol%, and more preferably 20 mol% to 80 mol%, of the total amount of ligands coordinating to the metal atom. Ligands other than (b) ligand-forming compounds and (c) silicon-containing compounds, such as ligands derived from alkoxy groups having 1 to 10 carbon atoms, are preferably present in an amount of 0 mol% to 50 mol%, and more preferably 0 mol% to 20 mol%, of the total amount of ligands coordinating to the metal atom.

[0114] (b) When synthesizing a metal compound (A) containing a ligand derived from a ligand-forming compound, the synthesis method is not particularly limited as long as the metal compound (A) contains a ligand derived from the ligand-forming compound (b). For example, a metal alkoxide or metal acetylacetonate (acac) can be used for the metal-containing compound (a), and the compound (b) is obtained by reacting the alkoxide or acac metal with compound (b). The metal-containing compound (a) may be hydrolyzed and condensed before being reacted with the ligand-forming compound (b), or the metal-containing compound (a) may be reacted with compound (b) before hydrolyzed and condensed. If it is difficult to control the hydrolysis and condensation, the reaction with compound (b) may be carried out in a non-aqueous environment. These are preferably adjusted as appropriate according to the properties required for the metal compound (A) and the metal-containing film. (c) When a silicon-containing compound and (b) a ligand-forming compound are to be used as ligands, it is preferable to react (a) a metal-containing compound with (c) a silicon-containing compound first, and then with (b) a ligand-forming compound.

[0115] (a) A method for carrying out a hydrolysis condensation reaction using a metal-containing compound is, for example, to carry out a hydrolysis condensation reaction of the metal-containing compound in a solvent containing water. In this case, other compounds having hydrolyzable groups may be added as needed. Also, an acid such as acetic acid may be added as a catalyst for the hydrolysis condensation reaction. The lower limit of the amount of water used in this hydrolysis condensation reaction is preferably 0.2 moles, more preferably 1 mole, and even more preferably 3 moles, relative to the hydrolyzable groups of the metal-containing compound, etc. The upper limit of the amount of water is preferably 20 moles, more preferably 15 moles, and even more preferably 10 moles.

[0116] (A) The solvent used in the synthesis reaction of metal compounds is not particularly limited, and for example, solvents similar to those exemplified as solvents in (C) below can be used. Typical solvents and solvent mixtures include those containing ester, ether, or alcohol functional groups, for example, a mixture of 70 / 30 by volume of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME). Examples of other solvents that can be used include butanediol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, 1-butanol, 2-butanol, 2-methyl-1-propanol, 4-methyl-2- PeExamples include ethanol, acetone, tetrahydrofuran, toluene, hexane, ethyl acetate, cyclohexanone, methyl amyl ketone, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, diamyl ether, isoamyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, γ-butyrolactone, methyl isobutyl ketone, and cyclopentyl methyl ether.

[0117] [(B) Surface modifiers] The surface modifier contained in the metal-containing film-forming composition of the present invention is a polymer compound containing one or both of the repeating units represented by the following general formula (1) and the repeating units represented by the following general formula (2). Furthermore, the polymer compound does not contain repeating units containing hydroxyl groups. [ka] (In the formula, R1 is a hydrogen atom or a methyl group, R2 is a monovalent organic group having 2 to 20 carbon atoms and containing a heterocyclic structure, and R3 is a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms.)

[0118] With such a surface modifier (B), the surface energy is lower compared to the metal compound (A), so when a metal-containing film is formed, it is possible to achieve a high degree of compatibility between the etching selectivity of the metal compound (A) and the pattern adhesion of the surface modifier (B) without forming a sea-island structure.

[0119] The above R3 is preferably a hydrogen atom.

[0120] It is preferable that the heterocyclic structure of R2 in a polymer compound containing either the repeating unit shown in the general formula (1) or formula (2) above is a heterocyclic structure containing an oxygen atom.

[0121] The inclusion of such a heterocyclic structure provides higher adhesion to the resist pattern, making it even more effective in preventing the deformation of fine resist patterns.

[0122] It is preferable that R2 is a monovalent organic group containing a group selected from the following formulas (R2-1) to (R2-3). [ka] (In the formula, R4 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the dashed line indicates a bond.)

[0123] The inclusion of such a heterocyclic structure causes the epoxy or oxetane structure to undergo a ring-opening reaction during heat deposition, leading to film hardening. Furthermore, the hydroxyl groups generated by this ring-opening reaction also contribute to improved adhesion to the resist upper layer.

[0124] In the above (R2-3), R4 is preferably a hydrogen atom, a methyl group, or an ethyl group, with an ethyl group being more preferred.

[0125] The following structures are preferred examples of the repeating units shown in equations (1) and (2) above. [ka] (R1 and R4 are the same as above.)

[0126] Furthermore, the repeating unit represented by the above general formula (1) or the above general formula (2) may be present as only one type or as two or more types in the polymer compound of the surface modifier (B).

[0127] The polymer compound contained in the surface modifier (B) above preferably has a content of 30 mol% or more of either the repeating unit represented by general formula (1) or general formula (2) above, and more preferably 50 mol% or more, relative to the total repeating units.

[0128] Furthermore, the polymer compound contained in the surface modifier (B) above preferably has a content of either the repeating unit represented by the general formula (1) or formula (2) above of 95 mol% or less, and more preferably 90 mol% or less, relative to the total repeating units.

[0129] By adjusting the content ratio of either the repeating unit shown in general formula (1) or general formula (2) above, the polarity of the polymer compound is adjusted, resulting in good adhesion to the resist pattern. Furthermore, since the epoxy or oxetane structure of general formulas (1) and (2) undergoes a ring-opening reaction during heat deposition and the film hardens, a dense, adhesive film can be formed, preventing intermixing between the adhesive film and the resist upper layer film. This prevents the generation of residue in the spaced areas of the pattern, and a highly rectangular pattern can be obtained. Therefore, in the surface modifier (B) above, it is preferable that the content of either the repeating unit shown in general formula (1) or general formula (2) above is 30 mol% or more and 95 mol% or less, particularly 50 mol% or more and 90 mol or less, relative to the total number of repeating units.

[0130] Preferably, the surface modifier is a polymer compound further comprising either a repeating unit represented by formula (3a) or formula (3b) below. [ka] (In the above formula, R F1 is a monovalent organic group having 1 to 20 carbon atoms and containing at least one F atom, and R F2 (where R1 is a fluorine atom or a monovalent organic group having 1 to 10 carbon atoms containing one or more fluorine atoms, R1 is a hydrogen atom or a methyl group, and n is 1 to 5.)

[0131] The polymer compound is more preferable if it contains either the repeating unit shown in formula (3a) or formula (3b), as this makes it easier for the (B) surface modifier to be unevenly distributed on the surface of the metal-containing film.

[0132] The following structures are preferred examples of the repeating units shown in formulas (3a) and (3b). [ka] (R1 is the same as above.)

[0133] Furthermore, the repeating units represented by the above general formulas (3a) and (3b) may be present in (B) the polymer compound as either one type or two or more types.

[0134] The polymer compound that is the surface modifier described in (B) above is more preferably such that the content of repeating units represented by the above general formula (1) or general formula (2) is 30 mol% to 95 mol% or 50 mol% to 90 mol% relative to the total number of repeating units. The content of repeating units represented by the above general formulas (3a) and (3b) is more preferably such that it is 5 mol% to 70 mol% or 10 mol% to 50 mol%.

[0135] Furthermore, the surface modifier (B) described above preferably has repeating units represented by the following general formula (B-1).

[0136] [ka] (In the formula, R1 ’ R5 is a hydrogen atom or a methyl group, R5 is a divalent linking group with 2 to 10 carbon atoms containing a single bond or an ester group, and R6 is a saturated or unsaturated tertiary alkyl group with 4 to 20 carbon atoms.

[0137] In the above general formula (B-1), R5 is a single bond or a divalent linking group having 2 to 10 carbon atoms containing an ester group. Specifically, examples of R5 include a single bond, -CO2CH2-, -CO2CH2CH2-, -CO2CH2CH2CH2-, -CO2CH(CH3)-, -CO2CH2CH2CH2CH2-, -CO2CH2CH2CH2CH2CH2CH2-, -CO2CH2CH2O-, -CO2CH2CH2OCH2CH2O-, -CO2CH2CH2OCH2CH2OCH2CH2O-, etc. Among these, -CO2CH2-, -CO2CH2CH2-, -CO2CH2CH2CH2-, -CO2CH2CH2CH2CH2CH2-, and -CO2CH2CH2CH2CH2CH2- are particularly preferred.

[0138] The following structures are examples of R6 in the repeating unit shown in the general formula (B-1) above, but are not limited to these. Dashed lines indicate bonding.

[0139] [ka]

[0140] [ka]

[0141] [ka]

[0142] When forming a metal-containing film from a metal-containing film-forming composition containing a polymer compound with repeating units represented by the general formula (B-1) above, the elimination decomposition reaction of the tertiary alkyl group R6 proceeds due to the action of heat and / or the acid generated by the acid generator described later, generating a carboxylic acid. The polarity of this carboxylic acid improves adhesion to the resist pattern, improves the rectangularity of the pattern, and prevents the generation of residue in the gaps of the pattern.

[0143] Furthermore, the generated carboxylic acid may undergo a ring-opening addition reaction with the repeating units shown in the general formulas (1) and (2) above, forming a hydroxyester crosslinked structure. A typical example of the reaction is shown below. In the following formula, (B-2) is the state in which R6 in the repeating unit (B-1) is eliminated to form a carboxylic acid, and (B-3) is the state in which a ring-opening addition reaction occurs with (1"), which is an example of the general formulas (1) and (2) above, to form a hydroxyester crosslinked structure. The area enclosed by the dotted line is the hydroxyester crosslinked structure formed by this reaction.

[0144] [ka] (In the formula, R1, R5, R6, and R1' are the same as above.)

[0145] The formation of this hydroxyester crosslinked structure is a crosslinking reaction, which promotes the hardening of the adhesion film. Sufficient hardening forms a dense film, preventing intermixing between the adhesion film and the resist upper layer film. This prevents residue in the gaps of the pattern, resulting in a highly rectangular pattern.

[0146] Furthermore, the hydroxyester crosslinking structure described above is a polar group and interacts with the resist pattern; therefore, the presence of repeating units (B-1) also contributes to preventing the resist pattern from collapsing.

[0147] Furthermore, the repeating unit represented by the general formula (B-1) above may be present in only one type or in two or more types within the polymer compound (B).

[0148] When the polymer compound (B) above contains repeating units represented by formula (B-1), the content of the repeating units represented by formula (B-1) relative to the total repeating units of the polymer compound (B) above is preferably 1 mol% to 30 mol%, and 5 mol% to 15 mol%. % The following are preferable.

[0149] Furthermore, in the present invention, the above-mentioned (B) polymer compound does not contain any constituent units that include hydroxyl groups.

[0150] When a polymer compound contains hydroxyl groups, it is undesirable because it risks impairing the stability of the metal compound.

[0151] The weight-average molecular weight of the above (B) polymer compound is preferably 6,000 to 50,000, and the degree of dispersion expressed as weight-average molecular weight / number-average molecular weight is preferably 3.0 or less.

[0152] The "weight-average molecular weight" referred to here is the value measured by gel permeation chromatography (GPC) using tetrahydrofuran as the solvent and polystyrene as the standard substance. By having the weight-average molecular weight and dispersion of the polymer compound used in the (B) surface modifier contained in the metal-containing film-forming composition within this range, excellent film formation is obtained during spin coating, and the generation of sublimation during heat curing is suppressed, thus preventing contamination of the equipment. In particular, when forming a metal-containing film as a resist interlayer, if the composition contains low-molecular-weight, volatile components, the film thickness distribution within the processed substrate surface tends to vary. However, by setting the molecular weight and dispersion of the polymer compound used as described above and controlling the amount of low-molecular-weight components in the composition, the film thickness distribution within the processed substrate surface can be kept small. Therefore, the weight-average molecular weight of the polymer compound contained in the (B) surface modifier used in the metal-containing film-forming composition of the present invention is preferably 6,000 to 50,000, and particularly preferably 8,000 to 40,000. The dispersion is preferably 3.0 or less.

[0153] The content of (B) surface modifier in the metal-containing film-forming composition is preferably 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass, per 100 parts by mass of (A) metal compound.

[0154] With such a concentration, it is possible to achieve an even higher level of compatibility between (A) etching selectivity of the metal compound and (B) pattern adhesion of the surface modifier.

[0155] (B) As a method for synthesizing polymer compounds for surface modifiers, for example, monomers having polymerizable unsaturated bonds corresponding to each repeating unit are mixed, and a radical polymerization initiator is added in a solvent and heated polymerization is carried out. Polymerization conditions can be selected in various ways depending on the monomers used, the target molecular weight, etc., and are not particularly limited, but specific examples of solvents used during polymerization include toluene, benzene, tetrahydrofuran, diethyl ether, dioxane, 2-butanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, cyclohexanone, γ-butyrolactone, ethyl acetate, butyl acetate, diacetone alcohol, etc. Examples of radical polymerization initiators include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2-azobis(2-methylpropionate), benzoyl peroxide, and lauroyl peroxide. Additionally, thiols such as octanthiol and 2-mercaptoethanol may be added as chain transfer agents during polymerization. The polymerization reaction can preferably be carried out by heating to 40°C or the boiling point of the reaction solvent. The reaction time is preferably 0.5 to 100 hours, more preferably 1 to 48 hours.

[0156] For example, by using polymerizable double bond compounds represented by the following general formulas (1'), (2'), and (B-1') as monomers and performing the polymerization described above, polymer compounds containing repeating units represented by the above general formulas (1), (2), and (B-1) can be synthesized. [ka] (In the formula, R1~R3, R5~R6, R1 ’ (This is the same as above.)

[0157] During polymerization, heating may be carried out after mixing all the raw materials, or the remaining raw materials may be added all at once or gradually, either individually or mixed, to some of the raw materials that have been preheated. For example, a polymerization method in which only the polymerization solvent is heated and then the monomer solution and polymerization initiator solution are added separately and gradually is particularly preferred because it yields a relatively homogeneous polymer compound and prevents abnormal reactions such as runaway reactions.

[0158] The polymer compound solution obtained as described above may be directly incorporated into the metal-containing film-forming composition, or, if necessary, it may be purified using conventional methods such as crystallization, liquid-liquid separation, filtration, and concentration to remove residual monomers, residual solvents, reaction by-products, and other impurities. When purifying the polymer compound, a crystallization method in which a poor solvent such as water, aqueous alcohol, or saturated hydrocarbon is added to the polymer compound solution and the resulting precipitate is filtered off, or a liquid-liquid separation method in which the poor solvent layer is separated and removed is preferred, with the liquid-liquid separation method being particularly preferred. Purifying the polymer compound by the liquid-liquid separation method allows for efficient removal of low molecular weight components from the polymer compound solution, thus reducing the generation of sublimes when forming a metal-containing film from the metal-containing film-forming composition containing this polymer compound, and consequently preventing contamination of the film-forming equipment.

[0159] <(C) Solvent> The (C) solvent that can be used in the metal-containing film-forming composition of the present invention is not particularly limited as long as it dissolves the above-mentioned (A) metal compound and (B) surface modifier, as well as the (D) thermal acid generator, (E) photoacid generator, (F) crosslinking agent, (G) surfactant, and other additives, if included therein.

[0160] Specifically, for example, an organic solvent described in paragraphs

[0091] to

[0092] of JP-A-2007-199653 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, and γ-butyrolactone, or a mixture containing one or more of these is preferably used.

[0161] The blending amount of the organic solvent is preferably 200 to 10,000 parts, more preferably 250 to 5,000 parts, per 100 parts by mass of the (A) metal compound.

[0162] <(C-1) High-boiling solvent> In the composition for forming a metal-containing film of the present invention, the (C) solvent may contain a (C-1) high-boiling organic solvent.

[0163] The (C-1) high-boiling organic solvent can be one or more organic solvents having a boiling point of 180 degrees (°C) or higher.

[0164] For example, as the (C) solvent, a mixture of one or more organic solvents having a boiling point of less than 180 °C and one or more organic solvents having a boiling point of 180 °C or higher ((C-1) high-boiling solvent) may be used.

[0165] (C-1) As for the high boiling point solvent, there are no particular restrictions on hydrocarbons, alcohols, ketones, esters, ethers, chlorinated solvents, etc., as long as it can dissolve each component of the metal-containing film-forming composition of the present invention, 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 Dibutyl 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 thereof 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, dibutyl adipate, etc., and these may be used alone or in combination.

[0166] (C - 1) The high - boiling solvent may be appropriately selected from, for example, the above - mentioned ones according to the temperature for heat - treating the metal - containing film - forming composition of the present invention. The boiling point of the high - boiling solvent is preferably 180°C to 300°C, and more preferably 200°C to 300°C. With such a boiling point, there is no risk that the volatilization during baking (heat - treatment) becomes too fast, so sufficient heat fluidity can be obtained during film formation. When forming a resist underlayer film, it is considered that (A) the etching selectivity of the metal compound and (B) the pattern adhesion of the surface modifier can be more highly compatible without forming a sea - island structure. Also, with such a boiling point, it will not remain in the film without volatilizing even after baking, so there is no risk of adversely affecting the film physical properties such as etching resistance.

[0167] Also, when using (C - 1) the high - boiling solvent, the blending amount is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the organic solvent having a boiling point of less than 180°C. With such a blending amount, sufficient heat fluidity can be imparted during baking, and it does not remain in the film and does not lead to deterioration of film physical properties such as etching resistance, so it is preferable.

[0168] <Other components> When the metal - containing film - forming composition is a metal - containing film - forming composition that can be used as a resist underlayer film in the multilayer resist method, it may contain one or more of the above (A) metal compounds, (B) surface modifiers, and (C) solvents, and may optionally contain at least one or more of (D) thermal acid generators, (E) photoacid generators, (F) cross - linking agents, and (G) surfactants.

[0169] The following describes components other than (A) metal compounds, (B) surface modifiers, and (C) organic solvents that may be included in the resist underlayer film forming composition of the present invention.

[0170] [(D) Thermal acid generator] In the metal-containing film-forming composition of the present invention, it is preferable to add (D) a thermal acid generator to promote the crosslinking reaction by heat.

[0171] Examples of thermal acid generators (D) that can be used in the metal-containing film-forming composition of the present invention include the following general formula (7).

[0172] [ka] (In the formula, X A - R represents a non-nucleophilic counterion. 70 , R 71 , R 72 , and R 73 Each represents a hydrogen atom or a linear, branched, or cyclic alkyl, alkenyl, oxoalkyl, or oxoalkenyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl or aryloxoalkyl group having 7 to 12 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with alkoxy groups, etc. Also, R 70 and R 71 , or R 70 , R 71 and R 72 It may form a ring, and if a ring is formed, R 70 and R 71 , or R 70 , R 71 and R 72 This represents an alkylene group having 3 to 10 carbon atoms, or a heteroaromatic ring containing the nitrogen atom in the formula within the ring.

[0173] The above, R 70 , R 71 , R 72 , and R 73These groups may be the same or different from each other. Specifically, examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl groups.

[0174] Examples of alkenyl groups include vinyl, allyl, propenyl, butenyl, hexenyl, and cyclohexenyl groups.

[0175] Examples of oxoalkyl groups include 2-oxocyclopentyl group, 2-oxocyclohexyl group, 2-oxopropyl group, 2-cyclopentyl-2-oxoethyl group, 2-cyclohexyl-2-oxoethyl group, and 2-(4-methylcyclohexyl)-2-oxoethyl group.

[0176] Examples of oxoalkenyl groups include the 2-oxo-4-cyclohexenyl group and the 2-oxo-4-propenyl group.

[0177] Examples of aryl groups include phenyl groups, naphthyl groups, alkoxyphenyl groups such as p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-tert-butoxyphenyl, and m-tert-butoxyphenyl, alkylphenyl groups such as 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, ethylphenyl, 4-tert-butylphenyl, 4-butylphenyl, and dimethylphenyl, alkylnaphthyl groups such as methylnaphthyl and ethylnaphthyl, alkoxynaphthyl groups such as methoxynaphthyl and ethoxynaphthyl, dialkylnaphthyl groups such as dimethylnaphthyl and diethylnaphthyl, and dialkoxynaphthyl groups such as dimethoxynaphthyl and diethoxynaphthyl.

[0178] Examples of aralkyl groups include benzyl groups, phenylethyl groups, and phenethyl groups.

[0179] Examples of aryloxoalkyl groups include 2-phenyl-2-oxoethyl group, 2-(1-naphthyl)-2-oxoethyl group, 2-(2-naphthyl)-2-oxoethyl group, and other 2-aryl-2-oxoethyl groups.

[0180] Also, R 70 and R 71 , or R 70 , R 71 and R 72When the nitrogen atom in the formula forms a heteroaromatic ring within the ring, the derivatives include imidazole derivatives (e.g., imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazan derivatives, pyrroline derivatives (e.g., pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, and pyridine derivatives (e.g., pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-phenyl Examples include lidone, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, dimethylaminopyridine, etc., pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (e.g., quinoline, 3-quinoline carbonitride, etc.), isoquinoline derivatives, sinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives, etc.

[0181] The above, X A -Examples of the non-nucleophilic counter ions include halide ions such as chloride ions and bromide ions, fluoroalkyl sulfonates such as triflate, 1,1,1-trifluoroethanesulfonate, and nonafluorobutanesulfonate, aryl sulfonates such as tosylate, benzenesulfonate, 4-fluorobenzenesulfonate, and 1,2,3,4,5-pentafluorobenzenesulfonate, alkyl sulfonates such as mesylate and butanesulfonate, imide acids such as bis(trifluoromethylsulfonyl)imide, bis(perfluoroethylsulfonyl)imide, and bis(perfluorobutylsulfonyl)imide, methide acids such as tris(trifluoromethylsulfonyl)methide and tris(perfluoroethylsulfonyl)methide, and further sulfonates substituted with fluorine at the α-position represented by the following general formula (8) and sulfonates substituted with fluorine at the α- and β-positions represented by the following general formula (9).

[0182]

Chemical formula

[0183] In the above general formula (8), R 81 is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 23 carbon atoms, an acyl group, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group. In the above general formula (9), R 91 is a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0184] Specific examples of the above thermal acid generator can be illustrated as follows, but are not limited thereto.

[0185]

Chemical formula

[0186] The metal-containing of the present invention filmThe (D) thermal acid generator contained in the forming composition can be used individually or in combination of two or more types. The amount of thermal acid generator added is preferably 0.05 to 30 parts, more preferably 0.1 to 10 parts, per 100 parts of the (B) surface modifier. If the amount is 0.05 parts or more, the amount of acid generated and the crosslinking reaction will be sufficient, and if it is 30 parts or less, there is little risk of mixing occurring due to the migration of acid to the upper resist layer.

[0187] [(E) Photoacid Generator] The metal-containing film-forming composition of the present invention may contain (E) a photoacid generator to appropriately adjust the pattern shape, exposure sensitivity, etc., of the resist upper layer film. One type of photoacid generator may be used alone or in combination of two or more types. As an example of a photoacid generator, those described in paragraphs

[0160] to

[0179] of Japanese Patent Application Publication No. 2009-126940 may be used. The amount of photoacid generator to be added is preferably 0.05 to 30 parts, more preferably 0.1 to 10 parts, per 100 parts of the (B) surface modifier. If the amount of photoacid generator added is within the above range, the resolution is good and there is no risk of foreign matter problems occurring after resist development or during peeling.

[0188] [(F) Crosslinking agent] Furthermore, the metal-containing film-forming composition of the present invention may also contain a (F) crosslinking agent to enhance curability and further suppress intermixing with the resist upper layer film. The crosslinking agent is not particularly limited, and various known crosslinking agents of different types can be widely used. Examples include melamine-based crosslinking agents, glycoluryl-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, epoxy-based crosslinking agents, and phenol-based crosslinking agents. The above (F) crosslinking agents can be used individually or in combination of two or more types. When a crosslinking agent is added, the amount added is preferably 5 to 50 parts, more preferably 10 to 40 parts, per 100 parts of the above (B) surface modifier. If the amount added is 5 parts or more, sufficient curability can be achieved and intermixing with the resist upper layer film can be suppressed. On the other hand, if the amount added is 50 parts or less, there is no risk of deterioration in adhesion due to a lower ratio of (B) surface modifier in the composition, nor a decrease in dry etching resistance due to a lower ratio of (A) metal compound.

[0189] Examples of melamine-based crosslinking agents include hexamethoxymethylated melamine, hexasubtoxicmethylated melamine, alkoxy and / or hydroxy-substituted derivatives thereof, and partially self-condensed derivatives thereof.

[0190] Examples of glycoluryl crosslinking agents include tetramethoxymethylated glycoluryl, tetrabutoxymethylated glycoluryl, their alkoxy and / or hydroxy substituted derivatives, and their partial self-condensates.

[0191] Examples of benzoguanamine-based crosslinking agents include tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, their alkoxy and / or hydroxy-substituted derivatives, and their partial self-condensed derivatives.

[0192] Examples of urea-based crosslinking agents include dimethoxymethylated dimethoxyethyleneurea, its alkoxy and / or hydroxy-substituted derivatives, and partially self-condensed derivatives thereof.

[0193] A specific example of a β-hydroxyalkylamide crosslinking agent is N,N,N',N'-tetra(2-hydroxyethyl)adipamide.

[0194] Examples of isocyanurate-based crosslinking agents include triglycidyl isocyanurate and triallyl isocyanurate.

[0195] Examples of aziridine-based crosslinking agents include 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate].

[0196] Examples of oxazoline-based crosslinking agents 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 copolymers.

[0197] Examples of epoxy crosslinking agents include diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, poly(glycidyl methacrylate), trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, and pentaerythritol tetraglycidyl ether.

[0198] As the phenolic crosslinking agent, specifically, the compounds represented by the following general formula (10) can be exemplified.

Chemical formula

[0199] Q is a single bond or a q-valent hydrocarbon group having 1 to 20 carbon atoms. q 1 is an integer of 1 to 5, and more preferably 2 or 3. Specifically, examples of Q include methane, ethane, propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, methylpentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylisopropylbenzene, diisopropylbenzene, methylnaphthalene, ethylnaphthalene, eicosane. R 16 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specifically, examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, octyl group, ethylhexyl group, decyl group, eicosanyl group, and a hydrogen atom or a methyl group is preferred.

[0200] As examples of the compounds represented by the above general formula (10), specifically, the following compounds can be exemplified. Among these, from the viewpoints of improving the curability of the adhesion film and the film thickness uniformity, hexamethoxymethylated products of triphenolmethane, triphenolethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene are preferred.

[0201]

Chemical formula

[0202] [ka]

[0203] The above (F) crosslinking agent can be used individually or in combination of two or more types. The amount of (F) crosslinking agent to be added is preferably 10% to 50% by mass, and more preferably 15% to 30% by mass, per 100 parts of the above (B) surface modifier. If the amount added is 10% by mass or more, sufficient curability is achieved and intermixing with the resist upper layer film can be suppressed. On the other hand, if the amount added is 50% by mass or less, there is no risk of deterioration of adhesion due to a lower ratio of (B) surface modifier in the metal-containing film-forming composition, and no risk of deterioration of dry etching resistance due to a lower ratio of (A) metal compound.

[0204] [(G) Surfactants] The metal-containing film-forming composition of the present invention may contain (G) a surfactant to improve the coatability in spin coating. One surfactant may be used alone or in combination of two or more. As a surfactant, for example, those described in paragraphs

[0142] to

[0147] of Japanese Patent Application Publication No. 2009-269953 can be used. When adding a surfactant, the amount to be added is preferably 0.001 to 20 parts, more preferably 0.01 to 10 parts, per 100 parts of the above (A) metal compound. Within this range, the coatability is reliably improved and a thin, uniform, and adhesive film can be formed.

[0205] [Plasticizer] Furthermore, a plasticizer may be added to the metal-containing film-forming composition of the present invention. The plasticizer is not particularly limited, and various known types of plasticizers can be widely used. Examples include low molecular weight compounds such as phthalates, adipicates, phosphates, trimelliticates, and citrates, as well as polymers such as polyethers, polyesters, and polyacetal polymers described in Japanese Patent Application Publication No. 2013-253227. The amount of plasticizer to be added is preferably 1% to 500% by mass per 100 parts of the metal compound (A). When the amount added is within this range, excellent pattern embedding and averaging are achieved.

[0206] <Metal-containing film formation method> In the present invention, by using the above-described metal-containing film-forming composition, a metal-containing film can be formed, for example, as a resist underlayer for a multilayer resist film used in lithography.

[0207] In the resist underlayer film formation method using the metal-containing film-forming composition of the present invention, the above-mentioned metal-containing film-forming composition is coated onto a substrate to be processed by a spin coating method or the like. After spin coating, the solvent is evaporated, and baking (heat treatment) is performed to promote the crosslinking reaction in order to prevent mixing with the resist upper layer film. Baking is preferably performed at a temperature of 100°C to 450°C for 10 to 600 seconds, and more preferably at a temperature of 200°C to 300°C for 10 to 300 seconds. Considering the impact on device damage and wafer deformation, the upper limit of the heating temperature in the lithography wafer process is preferably 450°C or lower, and more preferably 300°C or lower.

[0208] Furthermore, in the resist underlayer film formation method using the metal-containing film-forming composition of the present invention, the metal-containing film-forming composition of the present invention can be coated onto a workpiece substrate by a spin coating method or the like, as described above, and the metal-containing film-forming composition can be cured by firing in an atmosphere with an oxygen concentration of 0.1% to 21% by volume to form a metal-containing film.

[0209] By firing the metal-containing film-forming composition of the present invention in such an oxygen atmosphere, a sufficiently hardened film can be obtained. While air may be used as the atmosphere during baking, it is preferable to seal in an inert gas such as N2, Ar, or He to reduce oxygen levels and prevent oxidation of the metal-containing film. To prevent oxidation, it is necessary to control the oxygen concentration, preferably 1000 ppm or less, more preferably 100 ppm or less (by volume). Preventing oxidation of the metal-containing film during baking is preferable because it prevents increased absorption and reduced etching resistance.

[0210] Alternatively, the above-mentioned metal-containing film-forming composition can be used to form a metal-containing film, for example, as an interlayer in a multilayer resist film used in lithography.

[0211] <Method for forming patterns using a composition for forming a resist underlayer film> Furthermore, the present invention provides a method for forming a pattern on a workpiece substrate using a two-layer resist process with the metal-containing film-forming composition of the present invention, (I-1) A step of forming a metal-containing film by applying the metal-containing film-forming composition of the present invention onto a substrate to be processed, and then heat-treating it. (I-2) A step of forming a resist upper layer film on the metal-containing film using a photoresist material, (I-3) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (I-4) A step of transferring the pattern to the metal-containing film by dry etching using the resist upper layer film on which the pattern is formed as a mask, and (I-5) A step of processing the workpiece substrate using the metal-containing film on which the pattern is formed as a mask to form a pattern on the workpiece substrate. The present invention provides a pattern forming method characterized by having the following features.

[0212] Since the resist upper layer of the above two-layer resist process exhibits etching resistance to chlorine-based gases, it is preferable to perform dry etching of the metal-containing film using the resist upper layer as a mask in the above two-layer resist process using an etching gas mainly composed of chlorine-based gases. Since the metal-containing film exhibits etching resistance to fluorine-based gases, it is preferable to perform dry etching of the substrate to be processed using the metal-containing film as a mask using an etching gas mainly composed of fluorine-based gases.

[0213] Furthermore, the present invention provides a method for forming a pattern on a workpiece substrate using a three-layer resist process with the metal-containing film-forming composition of the present invention, (II-1) A step of forming a resist underlayer film on a substrate to be processed, (II-2) A step of forming a metal-containing film by applying the metal-containing film-forming composition of the present invention onto the resist underlayer film and then heat-treating it, (II-3) A step of forming a resist upper layer film on the metal-containing film using a photoresist material, (II-4) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (II-5) A step of transferring the pattern to the metal-containing film by dry etching, using the resist upper layer film on which the pattern is formed as a mask. (II-6) A step of transferring the pattern to the resist underlayer film by dry etching, using the metal-containing film on which the pattern has been transferred as a mask. (II-7) A step of processing the substrate to be processed using the resist underlayer film on which the pattern is formed as a mask to form a pattern on the substrate to be processed, The present invention provides a pattern forming method characterized by having the following features.

[0214] Since the metal-containing film formed by the metal-containing film-forming composition of the present invention and used as an intermediate film in the above three-layer resist process exhibits etching resistance to oxygen-based gases, it is preferable to perform dry etching of the organic resist underlayer film, which is carried out using the metal-containing film as a mask, with an etching gas mainly composed of oxygen-based gases in the above three-layer resist process. Since the organic underlayer film exhibits etching resistance to fluorine-based gases, it is preferable to perform dry etching of the substrate to be processed, which is carried out using the organic underlayer film as a mask, with an etching gas mainly composed of fluorine-based gases.

[0215] In the pattern formation method described above, the resist upper layer film can be either positive or negative, and the same photoresist composition as commonly used can be used. When forming the resist upper layer film with the above photoresist composition, a spin coating method is preferred.

[0216] When forming a resist upper layer film using a photoresist composition by spin coating, pre-baking is performed after resist coating, preferably at 60-180°C for 10-300 seconds. Subsequently, exposure is performed according to a conventional method, followed by post-exposure baking (PEB) and development to obtain the resist pattern. The thickness of the resist upper layer film is not particularly limited, but 10-500 nm, and especially 20-400 nm, is preferred.

[0217] Examples of exposure light include high-energy rays with wavelengths 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 (126 nm), soft X-rays (EUV) in the 3-20 nm range, electron beams (EB), ion beams, and X-rays.

[0218] As a method for forming the pattern of the resist upper layer film described above, it is preferable to use photolithography with a wavelength of 5 nm to 300 nm, direct writing with an electron beam, nanoimprinting, or a combination thereof to form the pattern.

[0219] Furthermore, it is preferable that the development method in the pattern formation method be alkaline development or development with an organic solvent.

[0220] Next, etching is performed using the obtained resist pattern as a mask. For example, in a two-layer resist process, etching of the metal-containing film is performed using a chlorine-based gas with the upper resist pattern as a mask. This forms the metal-containing film pattern. Then, etching of the substrate to be processed is performed using the obtained metal-containing film pattern as a mask. Etching of the workpiece can be performed by conventional methods; for example, if the workpiece is SiO2, SiN, or a silica-based low-dielectric-constant insulating film, etching is performed mainly using a fluorocarbon-based gas.

[0221] The metal-containing films obtained using the metal-containing film-forming composition of the present invention have excellent etching resistance when these workpieces are etched.

[0222] Examples of organic resist underlayer materials that can be used for the above-mentioned resist underlayer include those already known as underlayers for the 3-layer resist method or the 2-layer resist method using a silicon resist composition. For example, see Japanese Patent Publication No. 2012-1687, Japanese Patent Publication No. 2012-77295, Japanese Patent Publication No. 2004-264710, Japanese Patent Publication No. 2005-043471, Japanese Patent Publication No. 2005-250434, Japanese Patent Publication No. 2007-293294, Japanese Patent Publication No. 2008-65303, and Japanese Patent Publication No. 2004-205 Japanese Patent Publication No. 685, Japanese Patent Publication No. 2007-171895, Japanese Patent Publication No. 2009-14816, Japanese Patent Publication No. 2007-199653, Japanese Patent Publication No. 2008-274250, Japanese Patent Publication No. 2010-122656, Japanese Patent Publication No. 2012-214720, Japanese Patent Publication No. 2014-29435, International Publication WO Examples of resins and compositions can be found in Japanese Patent Publication No. 2012 / 077640, International Publication No. WO2010 / 147155, International Publication No. WO2012 / 077640, International Publication No. WO2010 / 147155, International Publication No. WO2012 / 176767, Japanese Patent Publication No. 2005-128509, Japanese Patent Publication No. 2006-259249, Japanese Patent Publication No. 2006-259482, Japanese Patent Publication No. 2006-293298, Japanese Patent Publication No. 2007-316282, Japanese Patent Publication No. 2012-145897, Japanese Patent Publication No. 2017-119671, Japanese Patent Publication No. 2019-44022, and others.

[0223] The above-mentioned resist underlayer film can be formed on a substrate by a spin coating method or the like, similar to the photoresist composition, using, for example, a composition solution containing the above-mentioned organic resist underlayer film material. After forming the organic resist underlayer film by a spin coating method or the like, it is desirable to bake the film to evaporate the organic solvent. The bake temperature is preferably in the range of 100 to 600°C, and the bake time is preferably in the range of 10 to 300 seconds.

[0224] Instead of the above-mentioned organic resist underlayer material, it is also possible to apply an organic hard mask formed by CVD or ALD.

[0225] In a three-layer resist process, dry etching of the metal-containing film is performed, for example, using a chlorine-based gas to mask the upper resist pattern. This forms the metal-containing film pattern. Next, using the obtained metal-containing film pattern as a mask, the resist underlayer film is etched using an oxygen-based gas. This forms the resist underlayer film pattern. Finally, using the obtained organic resist underlayer film pattern as a mask, the substrate to be processed is etched.

[0226] The metal-containing films obtained using the metal-containing film-forming composition of the present invention have excellent etching resistance when etching the underlying resist layer.

[0227] The workpiece (workpiece substrate) is not particularly limited and can be any substrate such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, Al, or a substrate on which the workpiece layer has been deposited. Various low-k films and their stopper films can be used as the workpiece layer, typically with a thickness of 50 to 10,000 nm, and especially 100 to 5,000 nm. When depositing the workpiece layer, the substrate and the workpiece layer are made of different materials.

[0228] Here, an example of a pattern formation method using the above three-layer resist process will be explained with reference to Figure 1. In this example, first, as shown in Figure 1(A), a resist underlayer film 3 is formed on the workpiece layer 2 of a workpiece substrate 10 consisting of a substrate 1 and a workpiece layer 2 thereon using an organic resist underlayer film material. A metal-containing film 4 is then formed on the resist underlayer film 3 using the metal-containing film forming composition of the present invention, and a resist upper layer film 5 is formed on the metal-containing film 4 using a photoresist material. Next, as shown in Figure 1(B), the exposed portion 6 of the resist upper layer film is pattern-exposed. Then, as shown in Figure 1(C), the resist upper layer film is developed with a developer to form a resist upper layer film pattern 5a on the resist upper layer film. Next, as shown in Figure 1(D), the resist upper layer film on which pattern 5a is formed is used as a mask to transfer the pattern to the metal-containing film 4 by dry etching to obtain a metal-containing film pattern 4a. Next, as shown in Figure 1(E), the metal-containing film on which pattern 4a has been transferred is used as a mask to transfer the pattern to the resist underlayer film by dry etching to obtain a resist underlayer film pattern 3a. Then, as shown in Figure 1(F), the resist underlayer film on which the pattern 3a is formed is used as a mask to process the workpiece layer 2 on the substrate 1, thereby forming the pattern 2a on the workpiece substrate 10.

[0229] Furthermore, an example of a pattern formation method using the above two-layer resist process will be explained with reference to Figure 2. In this example, first, as shown in Figure 2(G), a metal-containing film 4 is formed on the workpiece layer 2 of a workpiece substrate 10 consisting of a substrate 1 and a workpiece layer 2 thereon using the metal-containing film forming composition of the present invention, and a resist upper layer film 5 is formed on the metal-containing film 4 using a photoresist material. Next, as shown in Figure 2(H), the exposed portion 6 of the resist upper layer film is pattern-exposed. Then, as shown in Figure 2(I), the resist upper layer film is developed with a developer to form a resist upper layer film pattern 5a on the resist upper layer film. Next, as shown in Figure 2(J), the resist upper layer film on which pattern 5a is formed is used as a mask to transfer the pattern to the metal-containing film 4 by dry etching to obtain a metal-containing film pattern 4a. Then, as shown in Figure 2(K), the workpiece layer 2 on the substrate 1 is processed using the metal-containing film on which pattern 4a is formed as a mask to form a pattern 2a on the workpiece substrate 10. [Examples]

[0230] The present invention will be described in more detail below with reference to synthesis examples, comparative synthesis examples, examples, and comparative examples, but the present invention is not limited thereto.

[0231] [(A) Examples of metal compound synthesis] In the following synthesis examples, the organic group raw materials G: (G1) to (G10) and the silicon-containing organic group raw materials H: (H1) to (H2) shown below were used.

[0232] The raw material groups G: (G1) to (G10) and H: (H1) to (H2) are shown below.

[0233] [ka]

[0234] [ka]

[0235] The following metal compounds were used as the metal source M. (M1): Diisopropoxybis(2,4-pentanedione)titanium(IV) (75% by mass solution in 2-propanol (IPA)) (M2): Titanium tetraisopropoxide (Sigma-Aldrich Corp, 377996) (M3):Zr(OBu)4:Zirconium(IV) tetrabutoxide (80% by mass 1-butanol solution) (Tokyo Chemical Industries, Ltd., Z0016) (M4):Hf(OBu)4:Hafnium(IV)n-butoxide (Sigma-Aldrich Corp, 667943) (M5):Ti(OBu)4:Tetrabutyl orthotitanate (Tokyo Chemical Industries, Ltd., B0742) (M6): Titanium butoxide tetramer (Fujifilm Wako Pure Chemical Corporation)

[0236] [Synthesis Example A1] Synthesis of Metal Compound (A-1) Under a nitrogen atmosphere, 50.9 g of diisopropoxybis(2,4-pentane dionate)titanium(IV)(M1) (mass of metal compound: 38.2 g) was dissolved in 180.0 g of propylene glycol monoethyl ether (hereinafter referred to as PGEE), and 20.2 g of deionized water was added dropwise over 10 minutes at room temperature while stirring. The reaction was then carried out at 60°C for 2 hours, after which it was cooled to room temperature. After adding 250 g of propylene glycol monoethyl ether, the mixture was concentrated under reduced pressure using a rotary evaporator to obtain a PGEE solution of metal compound (A-1).

[0237] [Synthesis Example A2] Synthesis of Metal Compound (A-2) Under a nitrogen atmosphere, 28.4 g of titanium tetraisopropoxide (M2) was dissolved in 50.0 g of 2-propanol, and while stirring, a 50.0 g solution of IPA in 2.7 g of deionized water was added dropwise over 2 hours at room temperature. 12.4 g of organic raw material group (G1) was added to the resulting solution and stirred at room temperature for 30 minutes. This solution was concentrated under reduced pressure at 30°C, then heated to 60°C, and continued under reduced pressure until no more distillate was observed. Once no distillate was observed, 120.0 g of PGMEA / PGME (weight ratio 70 / 30) solution was added, and the mixture was heated at 40°C under reduced pressure until no more IPA distilled, yielding a PGMEA / PGME solution of metal compound (A-2).

[0238] [Synthesis Examples A3-A8] Synthesis of metal compounds (A-3)-(A-8) Except for using the above-mentioned metal source M and compound group G in the amounts shown in Table 1, the metal compounds (A-3) to (A-8) shown in Table 1 were obtained under the same reaction conditions as in Synthesis Example A1. [Table 1]

[0239] [Synthesis Example A9] Synthesis of Metal Compound (A-9) Under a nitrogen atmosphere, 11.8 g of tetrabutyl orthotitanate (M5) was dissolved in 20.6 g of PGMEA / PGME (weight ratio 70 / 30) solution, and the reaction temperature was raised to 50°C while stirring. 6.5 g of compound H1 was then added dropwise to the solution. After addition, the reaction temperature was increased to 60°C and stirring was continued for 2 hours. Next, a mixture of 6.4 g of compound G3 suspended in 8.6 g of PGMEA / PGME (weight ratio 70 / 30) solution was added to the reaction system, and stirring was continued at a reaction temperature of 60°C for 1 hour. After cooling to room temperature, the resulting reaction solution was filtered through a 0.45 μm PTFE filter to obtain a PGMEA / PGME solution of metal compound (A-9).

[0240] [Synthesis Examples A10-A16] Synthesis of metal compounds (A-10)-(A-16)] Except for using the above-mentioned metal source M, compound group G, and compound group H in the amounts shown in Table 2, the metal compounds (A-10) to (A-16) shown in Table 2 were obtained under the same reaction conditions as in Synthesis Example A9.

[0241] [Table 2]

[0242] [(B) Synthesis of surface modifiers] (B) Polymer compounds (B-1) to (B-14) for surface modifiers and comparative polymer compounds (B-15) to (B-16) were synthesized. Monomers (J1) to (J13) shown below were used to prepare these polymer compounds.

[0243] [ka]

[0244] [Synthesis Example B1] Synthesis of polymer compound (B-1) 100 g of monomer 1 (raw material J1) and 290.0 g of propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") were weighed into a 500 ml flask, and the mixture was degassed while stirring to prepare a monomer solution. In another 500 ml flask, 2.9 g of dimethyl 2,2-azobis(2-methylpropionate) (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) and 50.0 g of PGMEA were weighed and the mixture was degassed while stirring to prepare a polymerization initiator solution. Furthermore, 60 g of PGMEA was weighed into a 1 L flask under a nitrogen atmosphere, and after degassing while stirring, the flask was heated until the internal temperature reached 80°C. The monomer solution and the polymerization initiator solution were added simultaneously and separately over 4 hours. After heating and stirring for 16 hours, the mixture was cooled to room temperature. The resulting polymerization solution was added dropwise to 1,500 g of stirred hexane, and the precipitated polymer was filtered off. Furthermore, the obtained polymer was washed twice with 600 g of hexane and then vacuum-dried at 50°C for 20 hours to obtain polymer compound (B-1), which is a white powdery polymer. GPC analysis revealed that polymer compound (B-1) had a weight-average molecular weight (Mw) of 10,000 and a dispersion degree (Mw / Mn) of 2.0.

[0245] [Synthesis Examples B2-B14 and Comparative Synthesis Examples B15-B16] Synthesis of polymer compounds (B-2)-(B-16) The polymer compounds (B-2) to (B-16) shown in Table 3 were obtained under the same reaction conditions as in Synthesis Example B1, except that monomer 1, monomer 1 and monomer 2, or monomer 1, monomer 2 and monomer 3 were used with the amounts shown in Table 3. Table 3 below also shows the weight-average molecular weight (Mw) and dispersion (Mw / Mn) of each polymer compound.

[0246] [Table 3]

[0247] Preparation of metal-containing film-forming compositions (MUL1-16, comparative MUL1-5) For the preparation of the metal-containing film-forming compositions, one of the above metal compounds (A-1) to (A-16), one of the polymer compounds (B-1) to (B-16) as a surface modifier, the following compounds (AG1) to (AG3) as a thermal acid generator, the following compound (AG4) or (AG5) as a photoacid generator, the following compound (XL1) or (XL2) as a crosslinking agent, and a solvent (C1: ethylene glycol dibenzyl ether: boiling point 364°C) as a high-boiling point solvent were used. These were dissolved in an organic solvent containing 0.001% by mass of PF636 (manufactured by OMNOVA) in the proportions shown in Table 4, and then filtered through a 0.1 μm fluororesin filter to prepare the metal-containing film-forming compositions (MUL1 to 16, comparative MUL1 to 5). As the organic solvent, a mixed solvent of PGMEA and PGEE was used, as shown in Table 4.

[0248] [ka]

[0249] [Table 4]

[0250] [Solvent resistance evaluation and contact angle evaluation] In Examples 1-1 to 1-16 and Comparative Examples 1-1 to 1-4, each of the metal-containing film-forming compositions (MUL-1 to 16, Comparative Examples MUL-1 to 4) prepared above was applied to a silicon substrate. The coating was then baked at 250°C for 60 seconds, and the film thickness from the center to the outer edge of the substrate was measured to calculate the average film thickness (a [nm]). Subsequently, PGMEA solvent was dispensed onto the coating, left for 30 seconds, then spin-dried, and then baked at 100°C for 60 seconds to evaporate the PGMEA, and the film thickness (b [nm]) was measured. The difference in film thickness before and after PGMEA treatment (residual film percentage: (b / a) × 100) was calculated. The results are shown in Table 5 below.

[0251] Furthermore, the contact angle (CA1) with pure water was measured for films that had been fired at 250°C for 60 seconds. The results are shown in Table 5 below.

[0252] In Comparative Examples 1-5, which used the metal-containing film-forming composition (Comparative Example MUL-5), the evaluation was discontinued because precipitates formed after the sample preparation described above. It is presumed that the precipitates formed in the metal-containing film-forming composition (Comparative Example MUL-5) because the polymer compound (B-16) used as the surface modifier (B) contains constituent units with hydroxyl groups, and reacted with the metal compound.

[0253] [Table 5]

[0254] As shown in Table 5, the metal-containing film materials of the present invention (MUL-1 to 16) all exhibit good film formation properties, minimal film loss due to solvent treatment, and good solvent resistance. Furthermore, by using a surface modifier, films with a contact angle of over 60° with respect to pure water are obtained, indicating good adhesion to the resist pattern. In particular, Examples 1-5 to 1-16, which use metal compounds containing crosslinking groups represented by any of the general formulas (a-1) to (a-4), (b-1) to (b-4), and (c-1) to (c-3), showed high contact angles. Among these, Examples 1-5 to 1-8, which use hydrolysis condensates of metal compounds (metal compounds A-5 to A-8), Examples 1-10 to 1-14, which use polymer compounds containing F atom-containing structural units as surface modifiers, and Example 1-16, which uses a high-boiling point solvent as an additive, showed particularly high contact angles.

[0255] [Etching resistance evaluation] In Examples 2-1 to 2-16 and Comparative Examples 2-1 to 2-4, each of the metal-containing film-forming compositions (MUL-1 to 16, and Comparative Examples MUL-1 to 4) was applied to a silicon substrate, and the coating was heated at 250°C for 60 seconds using a hot plate. death, A metal-containing film with a thickness of 50 nm was formed (film thickness a).

[0256] In Comparative Example 2-5, the silicon atom-containing resist interlayer material (SOG-1) described below was applied, and the coating was baked at 220°C for 60 seconds to form a resist interlayer with a thickness of 50 nm.

[0257] The silicon atom-containing resist interlayer material (SOG-1) was prepared by dissolving an ArF silicon-containing interlayer polymer (SiP1) and a thermal crosslinking catalyst (CAT1) in a solvent (a mixed solvent of solvent 1 and solvent 2 below) containing 0.1% by mass of FC-4430 (manufactured by Sumitomo 3M) in the proportions shown in Table 6, and filtering the mixture through a fluororesin filter with a pore size of 0.1 μm.

[0258] [Table 6]

[0259] The structural formulas of the ArF silicon-containing interlayer polymer (SiP1) and thermal crosslinking catalyst (CAT1) used are shown below.

[0260] [ka]

[0261] Next, etching was performed using CF4 gas and O2 gas under the following conditions with a ULVAC CE-300I etching system, and the film thickness b was measured. The etching rate (nm / min) was calculated from the film thickness etched per minute (film thickness b - film thickness a) over a specified time using each gas. The results are shown in Table 7.

[0262] Dry etching conditions with CF4 gas Pressure: 1 Pa Antenna RF power: 100W Bias RF Power: 15W CF4 gas flow rate: 15 sccm Time: 30sec

[0263] Dry etching conditions using O2 gas Pressure: 1 Pa Antenna RF power: 300W Bias RF Power: 10W O2 gas flow rate: 25 sccm Time: 30sec

[0264] [Table 7]

[0265] As shown in Table 7, the metal-containing film-forming compositions (MUL-1 to MUL-16) of the present invention were found to exhibit excellent etching resistance to CF4 gas and O2 gas. Due to their excellent etching resistance to CF4 gas, they are suitable for a two-layer resist process in which a resist pattern is transferred to a substrate in combination with a photoresist upper layer film.

[0266] Furthermore, the metal-containing film compositions (MUL-1 to MUL-16) of the present invention exhibit superior resistance to etching using O2 gas compared to SOG-1 used in Comparative Example 2-5, making them suitable for a three-layer resist process in which a resist pattern is transferred to a substrate in combination with an organic resist underlayer film.

[0267] [Pattern formation method] In Examples 3-1 to 3-3 and Comparative Examples 3-1 to 3-4, ODL-306 manufactured by Shin-Etsu Chemical Co., Ltd. was used as an organic underlayer film on a substrate and applied to a Si wafer by spin coating. The coating was baked at 350°C for 60 seconds to produce a carbon film with a thickness of 45 nm. The carbon ratio of the carbon film was 88%. On top of this, compositions prepared by diluting each of the metal-containing film-forming compositions (MDL-3, 8, 12 and Comparative Examples MDL-2 to 4) with an organic solvent (PGMEA / PGME = 700 / 300 parts by mass) were applied and heated at 250°C for 60 seconds using a hot plate. death,A 10 nm thick resist interlayer was formed. An ArF single-layer resist, a resist top layer material, was applied on top of it, and the coating was baked at 105°C for 60 seconds to form a 100 nm thick photoresist film. An immersion protective film material (TC-1) was applied on top of the photoresist film, and the coating was baked at 90°C for 60 seconds to form a 50 nm thick protective film.

[0268] In Comparative Example 3-4, a composition obtained by diluting the silicon atom-containing resist interlayer material (SOG-1) used in Comparative Example 2-5 with an organic solvent (PGEE / pure water = 5000 / 600 parts by mass) was applied, and the coating was baked at 220°C for 60 seconds to form a resist interlayer with a thickness of 10 nm.

[0269] The resist upper layer material (single-layer resist for ArF) was prepared by dissolving a polymer (RP1), an acid generator (PAG1), and a basic compound (Amine1) in the proportions shown in Table 8 in a solvent containing 0.1% by mass of the surfactant FC-4430 (manufactured by Sumitomo 3M Co., Ltd.), and filtering the mixture through a 0.1 μm fluororesin filter.

[0270] [Table 8]

[0271] The polymer (RP1), acid generator (PAG1), and basic compound (Amine1) used in the resist upper layer material (single-layer resist for ArF) are shown below. [ka]

[0272] The immersion protective film material (TC-1) was prepared by dissolving the protective film polymer (PP1) in an organic solvent in the proportions shown in Table 9 and filtering the solution through a 0.1 μm fluororesin filter.

[0273] [Table 9]

[0274] The protective film polymer (PP1) used in the immersion protective film material (TC-1) is shown below.

[0275] [ka]

[0276] Next, the sample was exposed using an ArF immersion lithography system (Nikon Corporation; NSR-S610C, NA 1.30, σ 0.98 / 0.78, 35-degree dipole s polarized illumination, 6% halftone phase shift mask), baked (PEB) at 100°C for 60 seconds, and developed with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds to obtain a 50 nm 1:1 positive-type line-and-space pattern (resist upper layer pattern).

[0277] The reflectance was calculated using PROLITH 2020a (Lithotech Japan Co., Ltd.). Figure 3 shows the results of calculating the reflectance for a metal-containing film with a fixed thickness of 10 nm, where the refractive index n of the metal-containing film at a wavelength of 193 nm is 1.80 to 2.30 and the extinction coefficient k is 0.19 to 0.50. Optical constants (n / k) that can significantly reduce the reflectance from the underlying substrate during pattern exposure are preferred.

[0278] The optical constants of the metal-containing film-forming composition were determined by coating the metal-containing film-forming composition onto a silicon substrate, baking the coating at 250°C for 60 seconds, and then using a variable-angle spectroscopic ellipsometer (VASE) manufactured by JA Woolam.

[0279] The LWR of the pattern was observed using a CG5000 (Hitachi High-Technologies Corporation), and the pattern cross-section was observed using an S-4700 (Hitachi, Ltd. electron microscope).

[0280] The results are shown in Table 10.

[0281] Next, a hard mask pattern was formed by dry etching, using the resist upper layer pattern as a mask to etch the resist interlayer. The resulting hard mask pattern was then used as a mask to etch the organic underlayer to form a pattern. Finally, the resulting resist underlayer pattern was used as a mask to etch the SiO2 film. The etching conditions are as follows.

[0282] (Examples 3-1 to 3-3 and Comparative Examples 3-1 to 3-3) Transfer conditions for hard mask patterns to metal-containing films (resist interlayers). Dry etching conditions with Cl2 gas Pressure: 1 Pa Antenna RF power: 320W Bias RF Power: 30W Cl2 gas flow rate: 25 sccm Time: 10sec

[0283] (Comparative Example 3-4) Transfer conditions for hard mask patterns onto SOG-1 films (resist interlayers). Dry etching conditions with CF4 gas Pressure: 1 Pa Antenna RF power: 100W Bias RF Power: 15W CF4 gas flow rate: 15 sccm Time: 15sec

[0284] Transfer conditions for resist interlayer patterns to organic underlayers. Dry etching conditions using O2 gas Pressure: 1 Pa Antenna RF power: 300W Bias RF Power: 10W O2 gas flow rate: 25 sccm Time: 20sec

[0285] Transfer conditions for resist underlayer film patterns onto SiO2 film. Dry etching conditions with CF4 gas Pressure: 1 Pa Antenna RF power: 100W Bias RF Power: 15W CF4 gas flow rate: 15 sccm Time: 60sec

[0286] [Table 10]

[0287] As shown in Table 10, in Examples 3-1 to 3-3 using the metal-containing film-forming compositions (MUL-3, 8, 12) of the present invention, it was confirmed that the pattern shape after development was good in all cases. It is presumed that the addition of a surface modifier improved adhesion to the resist upper layer film pattern, and that the high refractive index n at a wavelength of 193 nm, which allowed for the suppression of reflected light from the substrate to less than 1% even with a thin film thickness of 10 nm, was the reason for obtaining a good resist pattern. The metal-containing film-forming compositions of the present invention can improve adhesion to the resist pattern without degrading the characteristics of the high refractive index material, and are particularly effective when using a metal-containing film-forming composition containing zirconium, which exhibits a high refractive index at a wavelength of 193 nm, as the resist underlayer film.

[0288] Furthermore, after etching following substrate transfer, the resist upper layer film pattern was successfully transferred to the substrate, confirming its suitability for microfabrication using the multilayer resist method.

[0289] In Comparative Examples 3-1 to 3-2, which did not use a surface modifier, and in Comparative Example 3-3, which used a polymer compound different from the present invention as a surface modifier, collapse of the resist upper layer film pattern was observed after development.

[0290] In Comparative Example 3-4, which used SOG-1 as the resist interlayer material, the LWR after development was found to be inferior to that of Examples 3-1 to 3-3, which used the metal-containing film-forming compositions (MUL-3, 8, 12) of the present invention, possibly due to the high reflectivity of 4.4% during pattern exposure. Furthermore, in Comparative Example 3-4, the pattern shape after substrate transfer etching was found to be undercut. This is presumed to be due to insufficient resistance to oxygen gas used when processing the resist underlayer film by dry etching.

[0291] From the above, it can be seen that the metal-containing film-forming composition and pattern-forming method of the present invention have high adhesion to the resist upper layer film pattern and have an effect of suppressing the collapse of fine patterns, and also provide a highly rectangular pattern shape for the resist upper layer film, and are therefore particularly suitable for use in multilayer resist processes and are extremely useful in fine patterning for semiconductor device manufacturing.

[0292] This specification includes the following embodiments: [1](A) Metal compounds, (B) Surface modifier and (C) Solvent and It contains, The metal compound comprises at least one metal atom selected from the group consisting of Ti, Zr, and Hf. A metal-containing film-forming composition characterized in that the (B) surface modifier is a polymer compound containing one or both of the repeating units represented by the following general formula (1) and the repeating units represented by the following general formula (2), wherein the polymer compound does not contain repeating units containing hydroxyl groups. [ka] (In the formula, R1 is a hydrogen atom or a methyl group, R2 is a monovalent organic group having 2 to 20 carbon atoms and containing a heterocyclic structure, and R3 is a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms.) [2] The metal-containing film-forming composition according to [1], characterized in that the heterocyclic structure is a heterocyclic structure containing an oxygen atom. [3] The metal-containing film-forming composition according to [1] or [2], characterized in that R2 in the general formulas (1) and (2) is a monovalent organic group containing a group selected from the following formulas (R2-1) to (R2-3). [ka] (In the formula, R4 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the dashed line indicates a bond.) [4] The metal-containing film-forming composition according to any one of [1] to [3], characterized in that the (B) surface modifier is a polymer compound further comprising either a repeating unit represented by the following formula (3a) or formula (3b). [ka] (In the above formula, R F1 is a monovalent organic group having 1 to 20 carbon atoms and containing at least one F atom, and R F2 (where R1 is a fluorine atom or a monovalent organic group having 1 to 10 carbon atoms containing one or more fluorine atoms, R1 is a hydrogen atom or a methyl group, and n is 1 to 5.) [5] The metal-containing film-forming composition according to any one of [1] to [4], characterized in that the weight-average molecular weight of the polymer compound used in the (B) surface modifier is 6,000 to 50,000. [6] The metal-containing film-forming composition according to any one of [1] to [5], characterized in that the degree of dispersion of the polymer compound used in (B) the surface modifier, expressed as weight-average molecular weight / number-average molecular weight, is 3.0 or less. [7] The metal-containing film-forming composition according to any one of [1] to [6], characterized in that the content of the (B) surface modifier contained in the metal-containing film-forming composition is 1 part by mass or more and 50 parts by mass or less per 100 parts by mass of the metal compound. [8] Furthermore, (D) Thermal acid generator, (E) Photoacid generator, (F) Crosslinking agent, and (G) Surfactants A metal-containing film-forming composition according to any one of [1] to [7], characterized by containing at least one of them. [9] The solvent (C) contains a high-boiling solvent (C-1), The high-boiling solvent (C-1) is one or more organic solvents having a boiling point of 180 degrees or more, and the metal-containing film-forming composition according to any one of [1] to [8] is characterized by this.

[10] The metal compound (A) is derived from a metal compound represented by the following general formula (4), and the metal-containing film-forming composition according to any one of [1] to [9] is characterized by this. [Chemical formula] (In the formula, M is any one of Ti, Zr, or Hf. L is a monodentate ligand having 1 to 30 carbon atoms or a polydentate ligand, and X is a hydrolyzable group selected from a halogen atom, an alkoxy group, a carboxylate group, an acyloxy group, -NR a R b and the like. R a and R b are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. a + b = 4, and a and b are integers from 0 to 4.)

[11] The metal compound (A) is a reaction product of a compound derived from the metal compound represented by the general formula (4) and an organic compound having 1 to 30 carbon atoms containing at least one crosslinking group represented by any of the following general formulas (a-1) to (a-4), (b-1) to (b-4), and (c-1) to (c-3), and the metal-containing film-forming composition according to

[10] is characterized by this. [Chemical formula] (In the above general formulas (a-1) to (a-4), R a is hydrogen or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding portion.) [Chemical formula] (In the above general formula, R bR is a hydrogen atom or a methyl group, and in the same formula they may be the same or different from each other. c (where * represents hydrogen, a substituted or unsubstituted saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, and * represents a bond.) [ka] (In the above general formulas (c-1) to (c-3), Y1 is a divalent organic group having 1 to 20 carbon atoms, R is a hydrogen atom, a substituted or unsubstituted saturated or unsaturated divalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, R d This refers to an organic group represented by the following general formula (c-4) in which a protecting group is removed by the action of either an acid, heat, or both, generating one or more hydroxyl groups or carboxyl groups, where * represents a bond. [ka] (In the above general formula (c-4), R e (* represents an organic group whose protecting group is removed by either acid, heat, or both, and * indicates the bond with Y1.)

[12] A method for forming a pattern on a substrate to be processed, (I-1) A step of forming a metal-containing film by applying a metal-containing film-forming composition described in any of [1] to

[11] onto a substrate to be processed, and then heat-treating it, (I-2) A step of forming a resist upper layer film on the metal-containing film using a photoresist material, (I-3) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (I-4) A step of transferring the pattern to the metal-containing film by dry etching using the resist upper layer film on which the pattern is formed as a mask, and (I-5) A step of processing the workpiece substrate using the metal-containing film on which the pattern is formed as a mask to form a pattern on the workpiece substrate. A pattern forming method characterized by having the following features.

[13] A method for forming a pattern on a substrate to be processed, (II-1) A step of forming a resist underlayer film on a substrate to be processed, (II-2) A step of forming a metal-containing film by applying a metal-containing film-forming composition according to any one of [1] to

[11] onto the resist underlayer film and then heat-treating it, (II-3) A step of forming a resist upper layer film on the metal-containing film using a photoresist material, (II-4) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (II-5) A step of transferring the pattern to the metal-containing film by dry etching, using the resist upper layer film on which the pattern is formed as a mask. (II-6) A step of transferring the pattern to the resist underlayer film by dry etching, using the metal-containing film on which the pattern has been transferred as a mask. (II-7) A step of processing the substrate to be processed using the resist underlayer film on which the pattern is formed as a mask to form a pattern on the substrate to be processed, A pattern forming method characterized by having the following features.

[0293] It should be noted that the present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention. [Explanation of Symbols]

[0294] 1...Substrate, 2...Layer to be processed, 2a...Pattern (pattern formed on the layer to be processed), 3...Resist underlayer film, 3a...Resist underlayer film pattern, 4...Metal-containing film, 4a...Metal-containing film pattern, 5...Resist top layer film, 5a...Resist top layer film pattern, 6...Exposed area, 10...Substrate to be processed.

Claims

1. (A) Metal compounds and (B) Surface modifier and (C) Solvent and It contains, The metal compound comprises at least one metal atom selected from the group consisting of Ti, Zr, and Hf. The (B) surface modifier is a polymer compound containing one or both of the repeating units represented by the following general formula (1) and the repeating units represented by the following general formula (2), wherein the polymer compound does not contain repeating units containing hydroxyl groups. A metal-containing film-forming composition characterized in that the (B) surface modifier is further a polymer compound containing either the repeating unit shown in formula (3a) or formula (3b) below. 【Chemistry 1】 (In the formula, R １ R is a hydrogen atom or a methyl group, ２ R is a monovalent organic group having 2 to 20 carbon atoms and containing a heterocyclic structure. ３ (This is a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms.) 【Chemistry 2】 (In the above formula, R F1 is a monovalent organic group having 1 to 20 carbon atoms containing at least one fluorine atom, R F2 is a monovalent organic group having 1 to 10 carbon atoms containing a fluorine atom or one or more fluorine atoms, R 1 is a hydrogen atom or a methyl group, and n represents 1 to 5.)

2. The metal-containing film-forming composition according to claim 1, characterized in that the heterocyclic structure is a heterocyclic structure containing an oxygen atom.

3. In the above general formulas (1) and (2), R ２ However, the following formula (R ２ -1) to (R ２ The metal-containing film-forming composition according to claim 1, characterized in that it is a monovalent organic group containing a group selected from (-3). 【Transformation 3】 (In the formula, R ４ (The atoms are hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, and the dashed lines indicate bonding.)

4. The metal-containing film-forming composition according to claim 1, characterized in that the weight-average molecular weight of the polymer compound used in the (B) surface modifier is 6,000 to 50,000.

5. The metal-containing film-forming composition according to claim 1, characterized in that the degree of dispersion of the polymer compound used in the (B) surface modifier, expressed as weight-average molecular weight / number-average molecular weight, is 3.0 or less.

6. The metal-containing film-forming composition according to claim 1, characterized in that the content of the (B) surface modifier contained in the metal-containing film-forming composition is 1 part by mass or more and 50 parts by mass or less per 100 parts by mass of the metal compound.

7. moreover, (D) Thermal acid generator, (E) Photoacid generator, (F) Crosslinking agent, and (G) Surfactants The metal-containing film-forming composition according to claim 1, characterized in that it contains at least one of the following.

8. The (C) solvent includes (C-1) a high-boiling point solvent, The metal-containing film-forming composition according to claim 1, characterized in that the (C-1) high-boiling point solvent is one or more organic solvents having a boiling point of 180 degrees or higher.

9. The metal-containing film-forming composition according to claim 1, characterized in that the metal compound (A) is derived from a metal compound represented by the following general formula (4). 【Chemistry 4】 (In the formula, M is any one of Ti, Zr or Hf. L is a monodentate ligand or a polydentate ligand having 1 to 30 carbon atoms, and X is a halogen atom, an alkoxy group, a carboxylate group, an acyloxy group, -NR ａ R ｂ is a hydrolyzable group selected from. R ａ and R ｂ are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. a + b = 4, and a and b are integers from 0 to 4.)

10. The metal-containing film-forming composition according to claim 9, characterized in that the (A) metal compound is a reaction product of a compound derived from a metal compound represented by the general formula (4) and an organic compound having 1 to 30 carbon atoms that contains at least one crosslinking group represented by any of the following general formulas (a-1) to (a-4), (b-1) to (b-4), and (c-1) to (c-3). 【Transformation 5】 (In the above general formulas (a-1) to (a-4), R ａ (where is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.) 【Transformation 6】 (In the above general formula, R ｂ R is a hydrogen atom or a methyl group, and in the same formula they may be the same or different from each other. ｃ (where * represents hydrogen, a substituted or unsubstituted saturated or unsaturated monovalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, and * represents a bond.) 【Transformation 7】 (In the above general formulas (c-1) to (c-3), Y １ R is a divalent organic group having 1 to 20 carbon atoms, R is a hydrogen atom, a substituted or unsubstituted saturated or unsaturated divalent organic group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, R ｄ This refers to an organic group represented by the following general formula (c-4) in which a protecting group is removed by the action of either an acid, heat, or both, generating one or more hydroxyl groups or carboxyl groups, where * represents a bond. 【Transformation 8】 (In the above general formula (c-4), R ｅ * is an organic group whose protecting group is removed by the action of acid, heat, or both, and * is Y １ (This represents the connection point.)

11. A method for forming a pattern on a substrate to be processed, (I-1) A step of forming a metal-containing film by applying a metal-containing film-forming composition according to any one of claims 1 to 10 onto a substrate to be processed, and then heat-treating it. (I-2) A step of forming a resist upper layer film on the metal-containing film using a photoresist material, (I-3) A step of forming a pattern on the resist upper layer film by pattern exposure followed by development with a developer solution. (I-4) A step of transferring the pattern to the metal-containing film by dry etching using the resist upper layer film on which the pattern is formed as a mask, and (I-5) A step of processing the workpiece substrate using the metal-containing film on which the pattern is formed as a mask to form a pattern on the workpiece substrate. A pattern forming method characterized by having the following features.

12. A method for forming a pattern on a substrate to be processed, (II-1) A step of forming a resist underlayer film on the substrate to be processed, (II-2) A step of forming a metal-containing film by applying a metal-containing film-forming composition according to any one of claims 1 to 10 onto the resist underlayer film and then heat-treating it, (II-3) A step of forming a resist upper layer film on the metal-containing film using a photoresist material, (II-4) After pattern exposure of the resist upper layer film, develop it with a developer to form a pattern on the resist upper layer film. (II-5) A step of transferring the pattern to the metal-containing film by dry etching, using the resist upper layer film on which the pattern is formed as a mask. (II-6) A step of transferring the pattern to the resist underlayer film by dry etching, using the metal-containing film on which the pattern has been transferred as a mask. (II-7) A step of processing the substrate to be processed using the resist underlayer film on which the pattern is formed as a mask to form a pattern on the substrate to be processed, A pattern forming method characterized by having the following features.

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