Composition for forming metal-containing film and pattern forming method

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

[0002] As LSIs become more highly integrated and faster, pattern dimensions are becoming finer. Lithography technology has achieved the formation of finer patterns by shortening the wavelength of light sources and selecting appropriate resist compositions to match them, in line with this trend. The core of this technology is a positive photoresist composition used in a single layer. This single-layer positive photoresist composition has a skeleton in the resist resin that is resistant to dry etching using chlorine- or fluorine-based gas plasma, and also has a switching mechanism that dissolves the exposed areas, forming a pattern by dissolving the exposed areas, and then dry etching the substrate using the remaining resist pattern as an etching mask.

[0003] However, when the thickness of the photoresist film used is kept the same and miniaturization is performed, i.e., when the pattern width is made smaller, the resolution performance of the photoresist film decreases, and when an attempt is made to develop the photoresist film into a pattern using a developer, the so-called aspect ratio becomes too large, resulting in problems such as pattern collapse. For this reason, photoresist films have been made thinner as patterns become finer.

[0004] On the other hand, in the processing of a substrate to be processed, a method is usually used in which a photoresist film on which a pattern is formed is used as an etching mask to process the substrate by dry etching, but in reality, there is no dry etching method that can obtain perfect etching selectivity between the photoresist film and the substrate to be processed. Therefore, there is a problem that the photoresist film is also damaged and collapsed during processing of the substrate, and the resist pattern cannot be accurately transferred to the substrate to be processed. Therefore, with the miniaturization of patterns, a higher dry etching resistance has been required for the resist composition. However, on the other hand, in order to increase the resolution, a resin with low light absorption at the exposure wavelength has been required for the resin used in the photoresist composition. Therefore, as the exposure light has become shorter in wavelength from i-line to KrF and ArF, the resin has also changed to novolac resin, polyhydroxystyrene, and resin with an aliphatic polycyclic skeleton, but in reality, the etching speed under dry etching conditions during substrate processing has become faster, and recent photoresist compositions with high resolution tend to have weaker etching resistance.

[0005] For this reason, it has become necessary to dry etch the substrate to be processed using a thinner photoresist film with a weaker etching resistance, and securing the materials and processes for this processing step has become an urgent need.

[0006] One method for solving such problems is the multi-layer resist method, in which a resist intermediate film having etching selectivity different from that of a photoresist film (i.e., a resist upper layer film) is interposed between the resist upper layer film and a substrate to be processed, a pattern is obtained in the resist upper layer film, and then the pattern is transferred to the resist intermediate film by dry etching using the resist upper layer film pattern as a dry etching mask, and the pattern is further transferred to the substrate to be processed by dry etching using the resist intermediate film as a dry etching mask.

[0007] One of the multilayer resist methods is a three-layer resist method that can be performed using a general resist composition used in a single-layer resist method. In this three-layer resist method, for example, an organic film made of novolac resin or the like is formed on a substrate to be processed as a resist underlayer film, a silicon-containing resist intermediate film is formed on the organic film as a resist intermediate film, and a normal organic photoresist film is formed on the organic film as a resist upper layer film. When dry etching is performed using fluorine-based gas plasma, the organic resist upper layer film has a good etching selectivity to the silicon-containing resist intermediate film, so that the resist upper layer film pattern can be transferred to the silicon-containing resist intermediate film by dry etching using fluorine-based gas plasma. According to this method, even if a resist composition that is difficult to form a pattern with a sufficient film thickness for directly processing a substrate to be processed or a resist composition that does not have sufficient dry etching resistance for processing a substrate is used, a pattern can be transferred to the silicon-containing resist intermediate film (resist intermediate film), and then, by performing pattern transfer by dry etching using oxygen-based or hydrogen-based gas plasma, a pattern of an organic film (resist underlayer film) made of novolac resin or the like that has sufficient dry etching resistance for processing a substrate can be obtained. As the above-mentioned resist underlayer film, many films are already known, for example, the one described in Patent Document 1.

[0008] The silicon-containing resist intermediate film used in the above three-layer resist method is a silicon-containing inorganic film by CVD, such as SiO 2 Films that can be obtained by spin coating include SOG (spin-on-glass) films (e.g., Patent Document 4 and Non-Patent Document 1) and cross-linked silsesquioxane films (e.g., Patent Document 5), and polysilane films (e.g., Patent Document 6) may also be used. 2Although silicon oxide and SiON films have high performance as dry etching masks when dry etching the underlying organic film, they require special equipment for deposition. In contrast, SOG films, cross-linked silsesquioxane films, and polysilane films can be deposited simply by spin coating and heating, and are considered to have high process efficiency.

[0009] The silicon-containing films that have been used conventionally in such multilayer resist methods have some problems. For example, when a resist pattern is formed by photolithography, it is well known that the exposure light is reflected by the substrate and interferes with the incident light, causing the so-called standing wave problem. In order to obtain a fine pattern without edge roughness of the resist film under the state-of-the-art ArF immersion and high NA exposure conditions, an anti-reflection function is essential as an intermediate film. Furthermore, in the state-of-the-art semiconductor processes such as those mentioned above, the photoresist is becoming thinner, so the intermediate film is also required to be thinner, and in the next-generation exposure process, it is required to impart an anti-reflection effect with a film thickness of 30 nm or less. In addition, it is preferable that the dry etching rate for oxygen gas plasma, which is generally used when processing the resist underlayer film, is smaller in order to increase the etching selectivity between the intermediate film and the underlayer film, and the trend toward thinner films requires the intermediate film to have improved dry etching resistance.

[0010] Metal-containing films (metal hard mask films) containing Ti or Zr have been attracting attention as a resist intermediate film that satisfies the requirements for anti-reflection effect and dry etching properties, instead of conventional silicon-containing films. TiO 2 or ZrO 2 are known as high refractive index materials, and by including these in the film, it is possible to improve the anti-reflection effect under high NA exposure conditions. In addition, by including metal-oxygen bonds, excellent dry etching resistance against oxygen gas can be expected.

[0011] In addition, since metal-containing films have excellent dry etching resistance not only to oxygen gas but also to fluorine gas, they are also promising for use in a two-layer resist method in which a metal-containing film is formed on the workpiece substrate as a resist underlayer film, and then a resist toplayer film is formed on top of that.

[0012] On the other hand, when such a metal-containing film is used directly under a resist top layer, improving adhesion with the resist pattern becomes an issue. The hardened metal-containing film has a much higher surface energy (or a smaller water contact angle) than the subsequently applied photoresist. Such a mismatch in surface energy causes poor adhesion between the metal-containing film and the subsequently applied photoresist, resulting in pattern collapse.

[0013] In order to suppress the collapse of the photoresist pattern on the metal-containing film, the 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 the adhesion with the resist pattern is improved by utilizing the difference in free energy between the organic polymer and the metal compound and distributing the organic polymer unevenly on the surface layer. In order to suppress the pattern collapse, an organic polymer containing a surface treatment portion selected from hydroxyl, protected hydroxyl, protected carboxyl, and a mixture thereof is used. However, in the current situation where finer pattern formation is required, it cannot be said that the pattern collapse suppression performance of these materials is sufficient.

[0014] Recently, it is said that the interaction at the interface between the resist top layer film and the underlayer film directly below the resist top layer film in a fine pattern affects the sensitivity of the resist, the shape of the pattern (rectangularity and space residues), etc., and from these perspectives as well, there is a demand for improvement in the performance of the underlayer film directly below the resist top layer film (Non-Patent Document 2). [Prior art documents] [Patent documents]

[0015] [Patent Document 1] JP 2004-205685 A [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) Summary of the Invention [Problem to be solved by the invention]

[0017] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a metal-containing forming composition that can obtain a good pattern shape in a fine patterning process in a semiconductor device manufacturing process, and that can provide a metal-containing film that has high adhesion to a resist overlying film and can prevent collapse of the fine pattern, and a pattern forming method using the composition. [Means for solving the problem]

[0018] In order to solve the above problems, the present invention provides (A) a metal compound; (B) a surface modifier; and (C) Solvent and Contains the metal compound contains at least one metal atom selected from the group consisting of Ti, Zr, and Hf, The present invention provides a composition for forming a metal-containing film, wherein the (B) surface modifier is a polymeric compound containing one or both of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), and the polymeric compound does not contain a repeating unit containing a hydroxyl group. [ka] (In the formula, R 1 is a hydrogen atom or a methyl group, and R 2 is a monovalent organic group having 2 to 20 carbon atoms and containing a heterocyclic structure, R 3 is a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms.

[0019] Such a composition for forming a metal-containing film can form a metal-containing film that has high adhesion to a resist top layer film, has the effect of preventing collapse of a fine pattern, and gives a good pattern shape. Furthermore, the obtained metal-containing film exhibits a high refractive index, and therefore can exhibit a high anti-reflection effect under ArF immersion and high NA exposure conditions.

[0020] The heterocyclic structure is preferably a heterocyclic structure containing an oxygen atom.

[0021] When the metal-containing film-forming composition has such a structure, higher adhesion to the resist upper layer film can be obtained, which is more effective in preventing collapse of the fine pattern.

[0022] In addition, R in the general formulas (1) and (2) 2 is expressed by the following formula (R 2 -1)~(R 2 -3) is preferably a monovalent organic group containing a group selected from the following: [ka] (In the formula, R 4 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the dashed line represents a bond.

[0023] By including the 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, which is more effective in preventing collapse of the fine pattern.

[0024] Moreover, the surface modifier (B) is preferably a polymer compound further containing 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 is an F atom or a monovalent organic group having 1 to 10 carbon atoms containing one or more F atoms, and R 1 is a hydrogen atom or a methyl group, and n is 1 to 5.

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

[0026] The polymer compound used in the surface modifier (B) preferably has a weight average molecular weight of 6,000 to 50,000.

[0027] The polymer compound used in the surface modifier (B) preferably has a polydispersity of 3.0 or less, the polydispersity being expressed by weight average molecular weight / number average molecular weight.

[0028] By setting the weight average molecular weight and / or dispersity of the polymer compound contained in the metal-containing film-forming composition within such ranges, excellent film-forming properties can be obtained, and the generation of sublimates during heat curing can be suppressed, thereby preventing contamination of the equipment.

[0029] The content of the surface modifier (B) contained in the metal-containing film-forming composition is preferably 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the metal compound.

[0030] By containing the surface modifier in such a ratio, higher adhesion to the resist overcoat film can be obtained without deteriorating the dry etching resistance and refractive index of the metal-containing film-forming composition, making it even more effective in preventing the collapse of fine patterns.

[0031] Furthermore, (D) a thermal acid generator, (E) a photoacid generator, (F) a crosslinker, and (G) Surfactants It is preferable that the composition contains at least one of the above.

[0032] The presence or absence and selection of these various additives makes it possible to finely adjust the performance in accordance with customer requirements in terms of film formability, reduction of sublimation products, and various resist patterning properties, which is preferable from a practical standpoint.

[0033] The (C) solvent contains a (C-1) high boiling point solvent, The (C-1) high boiling point solvent is preferably one or more organic solvents having a boiling point of 180° C. or higher.

[0034] By including such a high boiling point solvent, sufficient thermal fluidity can be obtained during film formation, and therefore, when a metal-containing film is formed, a sea-island structure is not formed, and a high degree of compatibility can be achieved between (A) the etching selectivity of the metal compound and (B) the pattern adhesion of the surface modifier.

[0035] The (A) metal compound is preferably derived from a metal compound represented by the following general formula (4). [ka] (In the formula, M is any one of Ti, Zr, and Hf. L is a monodentate or polydentate ligand having 1 to 30 carbon atoms. X is a halogen atom, an alkoxy group, a carboxylate group, an acyloxy group, -NR a R b R is a hydrolyzable group selected from the group consisting of a and R bare 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 of 0 to 4.

[0036] By using such a metal compound, a metal-containing film having superior resistance to dry etching with oxygen gas can be formed.

[0037] In this case, the (A) metal compound is more preferably a reaction product between a compound derived from the metal compound represented by the general formula (4) and an organic compound having 1 to 30 carbon atoms and containing at least one crosslinking group represented by any one of the following general formulae (a-1) to (a-4), (b-1) to (b-4), and (c-1) to (c-3). [ka] (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 is 0 or 1, and * is a bond. [ka] (In the above general formula, R b is a hydrogen atom or a methyl group, which may be the same or different in the same formula, 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. [ka] (In the above general formulas (c-1) to (c-3), Y 1 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 dis an organic group that generates one or more hydroxyl groups or carboxyl groups by the action of either or both of an acid and heat represented by the following general formula (c-4), and * represents a bond. [ka] (In the above general formula (c-4), R e is an organic group whose protecting group is removed by the action of either acid or heat, or both, and * is Y 1 )

[0038] The (A) metal compound containing such an organic group can obtain sufficient thermal fluidity during film formation, and therefore, when a metal-containing film is formed, a sea-island structure is not formed, and it is possible to achieve an even higher compatibility between the etching selectivity of the (A) metal compound and the pattern adhesion of the (B) surface modifier.

[0039] The present invention also provides a method for forming a pattern on a workpiece substrate, comprising the steps of: (I-1) a step of applying the composition for forming a metal-containing film of the present invention onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (I-2) forming a resist top 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-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (I-4) a step of transferring the pattern to the metal-containing film by dry etching using the resist top layer film on which the pattern is formed as a mask; and (I-5) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. The present invention provides a pattern forming method comprising the steps of:

[0040] The present invention also provides a method for forming a pattern on a workpiece substrate, comprising the steps of: (II-1) forming a resist underlayer film on a substrate to be processed; (II-2) a step of applying a composition for forming a metal-containing film of the present invention onto the resist underlayer film, followed by heat treatment to form a metal-containing film; (II-3) forming a resist top layer film on the metal-containing film using a photoresist material; (II-4) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (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 a pattern to the resist underlayer film by dry etching using the metal-containing film to which the pattern has been transferred as a mask; (II-7) a step of processing the substrate using the resist underlayer film on which the pattern is formed as a mask to form a pattern on the substrate; The present invention provides a pattern forming method comprising the steps of:

[0041] Thus, the metal-containing film-forming composition of the present invention can be suitably used in various pattern formation methods such as a two-layer resist process, a three-layer resist process, etc. In these pattern formation methods, the metal-containing film provided by the present invention can effectively suppress pattern collapse, is suitable for photolithography of a resist upper layer film, and enables the resist upper layer film pattern to be transferred to a substrate to be processed with high accuracy. Effect of the Invention

[0042] As described above, the present invention provides a composition for forming a metal-containing film that has high adhesion to a resist top layer film and has a fine pattern collapse prevention effect. In addition, this composition for forming a metal-containing film has high adhesion and has a fine pattern collapse prevention effect, and also imparts a highly rectangular pattern shape of the resist top layer film to the substrate to be processed, so it is extremely useful in a multi-layer resist process. In addition, the composition for forming a metal-containing film of the present invention has excellent resistance to dry etching using oxygen gas and fluorine gas, respectively, so that a fine pattern can be formed with high precision on the substrate to be processed in various pattern formation methods such as a two-layer resist process and a three-layer resist process. [Brief description of the drawings]

[0043] [Figure 1] FIG. 1 is an explanatory diagram of an example of the pattern forming method of the present invention (three-layer resist process). [Diagram 2] FIG. 2 is an explanatory diagram of an example of the pattern forming method of the present invention (two-layer resist process). [Diagram 3] FIG. 3 is an explanatory diagram of reflectance calculation in the pattern formation method. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0044] As described above, there has been a demand for the development of a metal-containing film-forming composition that can provide a metal-containing film that can obtain a good pattern shape in a fine patterning process in a semiconductor device manufacturing process and that has high adhesion to a resist overlying film and prevents collapse of the fine pattern, and a pattern formation method using the composition.

[0045] As a result of extensive research into the above-mentioned problems, the inventors have found that the above-mentioned problems can be solved by a composition for forming a metal-containing film, which contains a polymer compound having a specific structure, and a pattern formation method using this composition for forming a metal-containing film, and have thus completed the present invention.

[0046] That is, the present invention provides: (A) a metal compound; (B) a surface modifier; and (C) Solvent and Contains the metal compound contains 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 polymeric compound containing one or both of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), and the polymeric compound does not contain a repeating unit containing a hydroxyl group. [ka] (In the formula, R 1 is a hydrogen atom or a methyl group, and R 2 is a monovalent organic group having 2 to 20 carbon atoms and containing a heterocyclic structure, R 3 is a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms.

[0047] The present invention also provides a method for forming a pattern on a workpiece substrate, comprising the steps of: (I-1) a step of applying the composition for forming a metal-containing film of the present invention onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (I-2) forming a resist top 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-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (I-4) a step of transferring the pattern to the metal-containing film by dry etching using the resist top layer film on which the pattern is formed as a mask; and (I-5) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. The pattern forming method is characterized by comprising the steps of:

[0048] The present invention also provides a method for forming a pattern on a workpiece substrate, comprising the steps of: (II-1) forming a resist underlayer film on a substrate to be processed; (II-2) a step of applying a composition for forming a metal-containing film of the present invention onto the resist underlayer film, followed by heat treatment to form a metal-containing film; (II-3) forming a resist top layer film on the metal-containing film using a photoresist material; (II-4) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (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 a pattern to the resist underlayer film by dry etching using the metal-containing film to which the pattern has been transferred as a mask; (II-7) a step of processing the substrate using the resist underlayer film on which the pattern is formed as a mask to form a pattern on the substrate; The pattern forming method is characterized by comprising the steps of:

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

[0050] <Metal-containing film forming composition> The present invention relates to (A) a metal compound; (B) a surface modifier; and (C) Solvent and Contains the metal compound contains 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 polymeric compound containing one or both of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), and the polymeric compound does not contain a repeating unit containing a hydroxyl group. [ka] (In the formula, R1 is a hydrogen atom or a methyl group, and R 2 is a monovalent organic group having 2 to 20 carbon atoms and containing a heterocyclic structure, R 3 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, each of the (A) metal compound, (B) surface modifier, and (C) solvent may be used alone or in combination of two or more components. Furthermore, the metal-containing film-forming composition may contain components other than the (A), (B), and (C) components. Each component will be described below.

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

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

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

[0055] Such a ratio of metal elements can further improve the refractive index of the metal-containing film-forming composition and the dry etching resistance to oxygen gas and fluorine gas.

[0056] The metal atoms contained in the above metal compound may be composed of atoms of one type of element or two or more types of elements, but it is preferable that they are composed of atoms of one type of element, since it is desirable for the etching rate during inorganic film etching transfer processing after fine pattern formation to be uniform within the surface at the nanometer order level.

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

[0058] When the metal compound contains a metal-oxygen atom, the metal-containing film formed from the metal-containing film-forming composition has better etching selectivity. The oxygen atom may be bonded to one metal atom or may be bonded to multiple metal atoms, but it is preferable that the metal compound mainly contains a structure in which two oxygen atoms are bonded to a metal atom. When the metal compound mainly contains a structure in which two oxygen atoms are bonded to a metal atom, the metal compound has a more linear structure such as -MOMO- (M is at least one metal atom selected from the group consisting of Ti, Zr, and Hf), which can improve the solvent solubility.

[0059] To mix two substances with different properties and form a two-layer structure with a single coating, 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, in which domains of one layer are scattered in the matrix of the other layer, often occurs, making the combination of (A) the metal compound and (B) the surface modifier important.

[0060] As the (A) metal compound of the present invention, a commercially available metal compound 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. Also, the (A) metal compound can be synthesized by a method of 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, the "hydrolysis condensation reaction" refers to a reaction in which a hydrolyzable group of the (a) metal-containing compound is hydrolyzed and converted to -OH, and the two resulting -OH are dehydration condensed to form -O-.

[0061] As the (A) metal compound of the present invention, it is preferable to use the above-mentioned (a) metal-containing compound, a hydrolysis and condensation reaction product of the (a) metal-containing compound, or a compound obtained by reacting these compounds with something that can become a monodentate ligand or a multidentate ligand, and it is more preferable to use the hydrolysis and condensation reaction product of the (a) metal-containing compound or a compound obtained by reacting the hydrolysis and condensation reaction product of the (a) metal-containing compound with something that can become a monodentate ligand or a multidentate ligand.

[0062] Such a metal compound (A) has a higher surface energy than the surface modifier (B), and therefore when a resist underlayer film is formed, a sea-island structure is not formed, and it is possible to highly achieve both the etching selectivity of the metal compound (A) and the pattern adhesion of the surface modifier (B).

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

[0064] The metal compound (I) may be, for example, a 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 any one of Ti, Zr, and Hf. L is a monodentate or polydentate ligand having 1 to 30 carbon atoms. X is a halogen atom, an alkoxy group, a carboxylate group, an acyloxy group, -NR a R b R is a hydrolyzable group selected from the group consisting of 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 of 0 to 4.

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

[0066] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0067] Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, and a t-butoxy group.

[0068] Examples of the carboxylate group include an acetate group, a propionate group, a butyrate group, an n-hexanecarboxylate group, and an n-octanecarboxylate group.

[0069] Examples of the acyloxy group include an acetoxy group, an ethyloxy group, a propionyloxy group, a butyryloxy group, a t-butyryloxy group, a t-amylyloxy group, an n-hexanecarbonyloxy group, and an n-octanecarbonyloxy group.

[0070] Above -NR a R b Examples of the amino group include an unsubstituted amino group, a methylamino group, a dimethylamino group, a diethylamino group, and a dipropylamino group.

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

[0072] [Monodentate ligand] Examples of the monodentate ligand include a hydroxo ligand, a carboxy ligand, an amide ligand, an amine ligand, an ammonia ligand, and an olefin ligand.

[0073] The amide ligand may be, for example, an unsubstituted amide ligand (NH 2 ), methylamide ligand (NHMe), dimethylamide ligand (NMe 2 ), diethylamide ligand (NEt 2 ), dipropylamide ligand (NPr 2 ) etc.

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

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

[0076] [Polydentate ligand] Examples of the polydentate ligand include a ligand derived from a hydroxy acid ester, a ligand derived from a β-diketone, a ligand derived from a β-ketoester, a ligand derived from an α,α-dicarboxylate, a hydrocarbon having a π bond, and a diphosphine.

[0077] Examples of the hydroxy acid ester include glycolic acid ester, lactic acid ester, 2-hydroxycyclohexane-1-carboxylic acid ester, and salicylic acid ester.

[0078] Examples of the β-diketone include acetoacetate, α-alkyl-substituted acetoacetate, β-ketopentanoate, benzoylacetate, and 1,3-acetonedicarboxylate.

[0079] Examples of the α,α-dicarboxylic acid ester 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 the hydrocarbon having a π bond include chain 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 diphosphine 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 above general formula (4), a+b=4, and a and b are integers of 0 to 4. a is preferably 0 to 3, more preferably 0 to 2, even more preferably 1 or 2, and particularly preferably 2. b is preferably 2 to 4, more preferably 2 or 3, and even more preferably 2. By setting a and b within the above ranges, the stability of the (A) metal compound can be increased.

[0083] (a) The metal-containing compound is preferably a metal alkoxide which has not been hydrolyzed or hydrolytically condensed, or a metal alkoxide which has a ligand and has not been hydrolytically condensed.

[0084] (a) Examples of the metal-containing compound include compounds containing titanium, such as diisopropoxybis(2,4-pentanedionato)titanium(IV), tetra-n-butoxytitanium(IV), tetra-n-propoxytitanium(IV), tri-n-butoxymonostearate titanium(IV), titanium(IV) butoxide oligomer, aminopropyltrimethoxytitanium(IV), triethoxymono(2,4-pentanedionato)titanium(IV), tri-n-propoxymono(2,4-pentanedionato)titanium(IV), triisopropoxymono(2,4-pentanedionato)titanium, and di-n-butoxybis(2,4-pentanedionato)titanium(IV). Examples of the compound containing zirconium include dibutoxybis(ethylacetoacetate). bis(2,4-pentanedionato)zirconium(IV), di-n-butoxybis(2,4-pentanedionato)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-pentanedionato)zirconium(IV), tri-n-propoxymono(2,4-pentanedionato)zirconium(IV), triisopropoxymono(2,4-pentanedionato) Examples of compounds containing hafnium include diisopropoxybis(2,4-pentanedionato)hafnium(IV), tetrabutoxyhafnium(IV), tetraisopropoxyhafnium(IV), tetraethoxyhafnium(IV), and dichlorobis(cyclopentadienyl)hafnium(IV).

[0085] During the synthesis reaction of the (A) metal compound, in addition to the (a) metal-containing compound, a compound that can become a monodentate ligand or a polydentate ligand in the (A) metal compound (hereinafter referred to as (b) ligand-forming compound) may be added.

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

[0087] Furthermore, the (b) ligand-forming compound may be an organic compound having 1 to 30 carbon atoms and containing at least one crosslinking group represented by any one 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 is hydrogen or a monovalent organic group having 1 to 10 carbon atoms, q is 0 or 1, and * is a bond. [ka] (In the above general formula, R b is a hydrogen atom or a methyl group, which may be the same or different in the same formula; 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. [ka] (In the above general formulas (c-1) to (c-3), Y 1 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 that generates one or more hydroxyl groups or carboxyl groups by the action of either or both of an acid and heat represented by the following general formula (c-4), and * represents a bond. [ka] (In the above general formula (c-4), R e is an organic group whose protecting group is removed by the action of either acid or heat, or both, and * is Y 1 )

[0089] By including at least one of the bridging groups represented by any one of (a-1) to (a-4), (b-1) to (b-4), and (c-1) to (c-3) above in the (b) ligand-forming compound, sufficient thermal fluidity can be obtained during film formation. As a result, it is believed that when a metal-containing film is formed, a sea-island structure is not formed, and both the etching selectivity of the (A) metal compound and the pattern adhesion of the (B) surface modifier can be more highly achieved.

[0090] From the viewpoint of productivity and stability of the (A) metal compound, the (b) ligand-forming compound is preferably a compound derived from a carboxy ligand, a compound derived from a β-diketone ligand, or a compound having a plurality of hydroxyl groups. These can be used alone or in combination of two or more.

[0091] An example of the compound derived from a carboxy ligand is a compound represented by the following formula (5). [ka] (In the above general formula (5), p is 0 or 1. When p is 1, X 1 is a divalent organic group having 2 to 20 carbon atoms, and W is an alkoxy group having 1 to 10 carbon atoms, or any one of the following general formula (5-A) and the above general formulas (b-1) to (b-4). 1 is a monovalent organic group having 8 to 30 carbon atoms, containing a bridging group having any of the structures represented by the above general formulas (a-2) and (a-3) and an aromatic ring. [ka] (In the above general formula (5-A), Y is a saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, and R A is any of the structures represented by the above general formulas (a-1) to (a-4), h represents 1 to 6, and * represents the bond to the carbon atom of the carbonyl.

[0092] A compound derived from a carboxy ligand having such a structure can improve the thermosetting property of the metal compound (A) and form a metal-containing film that has excellent resistance to mixing with the resist top layer film.

[0093] In the above general formula (5), it is preferable that p is 1 and W is a structure represented by the following general formula (5-B). [ka] (In the above general formula (5-B), R A1 is the structure represented by the above general formula (a-1), and R A2 is either 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 is a saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, t is 1 to 6, s is 0 to 5, t+s is 1 or more and 6 or less, r is 1 to 10, u is 0 or 1, m is 0 or 1, and * represents a bond to the carbon atom of the carbonyl.

[0094] Compounds derived from carboxy ligands having such a structure have improved heat resistance properties of the (A) metal compound, so that the formed metal-containing film exhibits excellent film-forming properties and can also suppress the generation of sublimates during heat curing, thereby preventing contamination of the device.

[0095] In the general formula (5), p is 1, W is an alkoxy group having 1 to 10 carbon atoms, and X 1 is preferably any of the structures represented by the following general formula (5-C). [ka]

[0096] Compounds derived from carboxy ligands having such a structure have improved heat resistance properties of the (A) metal compound, so that the formed metal-containing film exhibits excellent film-forming properties and can also suppress the generation of sublimates during heat curing, thereby preventing contamination of the device.

[0097] Alternatively, in the general formula (5), p is 0, and X 1 is preferably any of the structures represented by the following general formula (5-D). [ka] (In the above general formula (5-D), R f is the same as in the above general formula (a-2) or (a-3), and * represents the bond to the carbon atom of the carbonyl.)

[0098] An example of the compound derived from a carboxy ligand is a compound represented by the following formula (6). [ka] (In the above general formula (6), X 2 is a divalent organic group having 1 to 31 carbon atoms, R 6A is any one of the above general formulas (c-1) to (c-3).

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

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

[0102] Y 1 Specific examples of the structure include, but are not limited to, the following structures. [ka] (* 1 is a bond to an oxygen or nitrogen atom, * 2 is R d )

[0103] In the above general formula (c-4), R e is an organic group from which a thermoacid labile group is eliminated by the action of either or both of an acid and heat, and is preferably a tertiary hydrocarbyl group or a group that forms an acetal structure together with an adjacent oxygen atom, and is particularly preferably a tertiary hydrocarbyl group. The tertiary hydrocarbyl group is preferably one having 4 to 20 carbon atoms, and among these, one having a smaller number of carbon atoms is more preferred.

[0104] An example of a compound derived from a ligand derived from a β-diketone is a compound represented by the formula (7). [ka] (In the above general formula, R 7A ~R 7c is a divalent organic group having 1 to 20 carbon atoms which may contain a hydrogen atom or a crosslinking group represented by any one of the above general formulas (a-1) to (a-4) and (b-1) to (b-4).

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

[0106] Examples of compounds having a plurality of hydroxy groups include dihydric alcohols represented by any one of the formulas (7-A) to (7-C). [ka] (In the above general formula, R 7a ~R 7b is a hydrogen atom or a divalent organic group having 1 to 20 carbon atoms which may contain a crosslinking group represented by any one of the above general formulas (a-1) to (a-4), R 7c ~R 7f represents a hydrogen atom or a divalent organic group having 1 to 20 carbon atoms which may contain a crosslinking group represented by any one of the following general formulas (a-1) to (a-4) and (b-1) to (b-4), and Y 2 is a divalent organic group having 1 to 10 carbon atoms. In the above general formula (7-A), adjacent R 7a and R 7b may be bonded to each other to form an unsaturated or saturated ring structure.

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

[0108] In the (A) metal compound, the content of the ligand derived from the (b) ligand-forming compound is preferably 10 mol % to 90 mol %, more preferably 20 mol % to 80 mol %, of the total ligands coordinated to the metal atom. The content of the ligand other than the (b) ligand-forming compound, for example, a ligand derived from an alkoxy group having 1 to 10 carbon atoms, is preferably 0 mol % to 50 mol %, more preferably 0 mol % to 20 mol %, of the total ligands coordinated to the metal atom.

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

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

[0111] Examples of the silicon-containing compound (c) include a structure represented by the following formula (s): [ka] (In (s) above, R s1 , R s2 and R s3 is any organic group selected from an organic group having 1 to 30 carbon atoms and a bridging group having any of the structures represented by the following general formulas (s-1) to (s-3), 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 is hydrogen or a monovalent organic group having 1 to 10 carbon atoms, q is 0 or 1, and * is a bond.

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

[0113] When the (A) metal compound contains a ligand derived from the (b) ligand-forming compound and a ligand derived from the (c) silicon-containing compound, the content of the ligand derived from the (b) ligand-forming compound in the (A) metal compound is preferably 10 mol% to 90 mol% of the total of the ligands coordinated to the metal atom, more preferably 20 mol% to 80 mol%. The content of the ligand derived from the (c) silicon-containing compound is preferably 10 mol% to 90 mol% of the total of the ligands coordinated to the metal atom, more preferably 20 mol% to 80 mol%. The content of the ligand other than the (b) ligand-forming compound and the (c) silicon-containing compound, for example, the ligand derived from an alkoxy group having 1 to 10 carbon atoms, is preferably 0 mol% to 50 mol%, more preferably 0 mol% to 20 mol% of the total of the ligands coordinated to the metal atom.

[0114] When synthesizing the (A) metal compound containing a ligand derived from the (b) ligand-forming compound, the synthesis method is not particularly limited as long as the (A) metal compound contains a ligand derived from the (b) ligand-forming compound. For example, a metal alkoxide or metal acetylacetonate (acac) can be used for the (a) metal-containing compound, and the alkoxy or acac metal can be reacted with the compound (b). The (a) metal-containing compound may be hydrolyzed and condensed, and then reacted with the (b) ligand-forming compound, or the (a) metal-containing compound may be reacted with the compound (b) and then hydrolyzed and condensed. If it is difficult to control the hydrolysis and condensation, the compound may be reacted with the compound (b) in a non-water-containing environment. It is preferable to adjust these appropriately according to the properties required for the (A) metal compound and the metal-containing film. When (c) the silicon-containing compound and (b) the ligand-forming compound are used as ligands, it is preferable to react (a) the metal-containing compound with (c) the silicon-containing compound and then react (b) the ligand-forming compound.

[0115] As a method for carrying out a hydrolysis condensation reaction using (a) a metal-containing compound, for example, a method of carrying out a hydrolysis condensation reaction of (a) a metal-containing compound in a solvent containing water can be mentioned. In this case, other compounds having a hydrolyzable group may be added as necessary. In addition, 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 times by mole, more preferably 1 times by mole, and even more preferably 3 times by mole, relative to the hydrolyzable group of (a) a metal-containing compound or the like. The upper limit of the amount of water is preferably 20 times by mole, more preferably 15 times by mole, and even more preferably 10 times by mole.

[0116] The solvent used in the synthesis reaction of (A) the metal compound is not particularly limited, and for example, the same solvents as those exemplified as (C) solvents described later can be used. Typical solvents and solvent mixtures include ester, ether or alcohol functional groups, for example, a 70 / 30 by volume mixture 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- Examples of the alkoxysilane include propanol, 4-methyl-2-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 modifier] The surface modifier contained in the metal-containing film-forming composition of the present invention is a polymeric compound containing one or both of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2). In addition, the polymeric compound does not contain a repeating unit containing a hydroxyl group. [ka] (In the formula, R 1 is a hydrogen atom or a methyl group, and R 2 is a monovalent organic group having 2 to 20 carbon atoms and containing a heterocyclic structure, R 3 is a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms.

[0118] Such a surface modifier (B) has a lower surface energy than the metal compound (A), and therefore when a metal-containing film is formed, a sea-island structure is not formed, and it is possible to highly achieve both the etching selectivity of the metal compound (A) and the pattern adhesion of the surface modifier (B).

[0119] Above R 3 is preferably a hydrogen atom.

[0120] R of a polymer compound containing a repeating unit represented by the above general formula (1) or formula (2) 2 The heterocyclic structure contained in is preferably a heterocyclic structure containing an oxygen atom.

[0121] By including such a heterocyclic structure, higher adhesion to the resist pattern can be obtained, which is further effective in preventing collapse of the fine resist pattern.

[0122] R 2 is expressed by the following formula (R 2 ―1)~(R 2 -3) is preferably a monovalent organic group containing a group selected from the following: [ka] (In the formula, R 4is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the dashed line represents a bond.

[0123] By including such a heterocyclic structure, the epoxy or oxetane structure undergoes a ring-opening reaction during heating to harden the film, and the hydroxyl group generated by this ring-opening reaction also contributes to improving adhesion to the upper layer of the resist.

[0124] Above (R 2 -3)R in 4 is preferably a hydrogen atom, a methyl group or an ethyl group, and more preferably an ethyl group.

[0125] As specific examples of the repeating units represented by the above formulae (1) and (2), the following structures can be preferably exemplified. [ka] (R 1 and R 4 is the same as above.)

[0126] The repeating unit represented by the above general formula (1) or (2) may be contained in the polymer compound of the surface modifier (B) either alone or in combination of two or more kinds.

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

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

[0129] By adjusting the content ratio of any of the repeating units represented by the general formula (1) and the general formula (2), the polarity of the polymer compound is adjusted, and the adhesion to the resist pattern is improved. In addition, the epoxy or oxetane structure of the general formulas (1) and (2) undergoes a ring-opening reaction during heating and film formation, and the film is hardened, so that a dense adhesive film can be formed, and it is possible to prevent intermixing between the adhesive film and the resist upper layer film. This makes it possible to prevent the generation of residues in the space portion of the pattern, and to obtain a pattern with high rectangularity. Therefore, in the surface modifier (B), it is preferable that the content of any of the repeating units represented by the general formula (1) and the general formula (2) relative to the total repeating units is 30 mol% or more and 95 mol% or less, particularly 50 mol% or more and 90 mol% or less.

[0130] The surface modifier is preferably a polymer compound further comprising a repeating unit represented by the following formula (3a) or (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 is an F atom or a monovalent organic group having 1 to 10 carbon atoms containing one or more F atoms, and R 1 is a hydrogen atom or a methyl group, and n is 1 to 5.

[0131] It is more preferable that the polymer compound contains a repeating unit represented by either formula (3a) or formula (3b), since this makes it easier for the surface modifier (B) to be unevenly distributed in the surface layer of the metal-containing film.

[0132] As specific examples of the repeating units represented by formula (3a) and formula (3b), the following structures can be preferably exemplified. [ka] (R 1 is the same as above.)

[0133] The repeating units represented by the above general formula (3a) and general formula (3b) may be contained in the polymer compound (B) either alone or in combination of two or more kinds.

[0134] The polymer compound which is the surface modifier (B) preferably has a content of the repeating units represented by the general formula (1) or (2) of 30 mol % to 95 mol %, more preferably 50 mol % to 90 mol %, based on all repeating units, and more preferably has a content of the repeating units represented by the general formula (3a) or (3b) of 5 mol % to 70 mol %, more preferably 10 mol % to 50 mol %.

[0135] Moreover, the surface modifier (B) preferably further has a repeating unit represented by the following general formula (B-1).

[0136] [ka] (In the formula, R 1 ’ is a hydrogen atom or a methyl group, and R 5 is a divalent linking group having 2 to 10 carbon atoms and containing a single bond or an ester group, and R 6 is a saturated or unsaturated tertiary alkyl group having 4 to 20 carbon atoms.

[0137] In the above general formula (B-1), R 5 R is a divalent linking group having 2 to 10 carbon atoms and containing a single bond or an ester group. 5 Specifically, a single bond, -CO 2 CH 2 -, -CO 2 CH 2 CH 2 -, -CO 2 CH 2 CH 2 CH 2 -, -CO 2 CH(CH 3 )-, -CO 2 CH 2 CH 2 CH 2 CH2 -, -CO 2 CH 2 CH 2 CH 2 CH 2 CH 2 -, -CO 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -, -CO 2 CH 2 CH 2 O-, -CO 2 CH 2 CH 2 OCH 2 CH 2 O-, -CO 2 CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 Examples of the aryl group include -CO-, -O-, etc. 2 CH 2 -, -CO 2 CH 2 CH 2 -, -CO 2 CH 2 CH 2 CH 2 -, -CO 2 CH 2 CH 2 CH 2 CH 2 -, -CO 2 CH 2 CH 2 CH 2 CH 2 CH 2 - is preferred.

[0138] R in the repeating unit represented by the above general formula (B-1) 6 Specific examples of the structure include, but are not limited to, the following structures: The dashed lines indicate bonds.

[0139] [ka]

[0140] [ka]

[0141] [ka]

[0142] When a metal-containing film is formed from a composition for forming a metal-containing film, which contains a polymer compound containing a repeating unit represented by the above general formula (B-1), a tertiary alkyl group R 6 The elimination and decomposition reaction of the above proceeds to generate 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 residues in the spaces of the pattern.

[0143] In addition, the generated carboxylic acid may undergo a ring-opening addition reaction with the repeating units represented by the general formulas (1) and (2) to form a hydroxy ester crosslinked structure. A typical example of the reaction is shown below. In the following formula, R 6 The state in which the alkyl group is eliminated to form a carboxylic acid is represented by (B-2), and the state in which the alkyl group is subjected to a ring-opening addition reaction with (1"), which is an example of the general formulae (1) and (2), to form a hydroxy ester cross-linked structure is represented by (B-3). The area surrounded by the dotted line is the hydroxy ester cross-linked structure formed by this reaction.

[0144] [ka] (In the formula, R 1 , R 5 , R 6 , R 1 ' is the same as above.)

[0145] The formation of this hydroxyester crosslinking structure is a crosslinking reaction that promotes the hardening of the adhesive film. Sufficient hardening leads to the formation of a dense film, which prevents intermixing between the adhesive film and the resist top layer, thereby preventing residues in the spaces of the pattern and allowing the formation of a highly rectangular pattern.

[0146] Furthermore, the above hydroxy ester crosslinked structure is a polar group and has an interaction with the resist pattern, so the presence of the repeating unit (B-1) also contributes to preventing the resist pattern from collapsing.

[0147] The repeating unit represented by the above general formula (B-1) may be contained in the polymer compound (B) either alone or in combination of two or more kinds.

[0148] When the (B) polymer compound contains a repeating unit represented by the above formula (B-1), the content of the repeating unit represented by the formula (B-1) relative to the total repeating units of the (B) polymer compound is preferably 1 mol % or more and 30 mol % or less, and more preferably 5 mol % or more and 15 mol % or less.

[0149] In the present invention, the polymer compound (B) does not contain a structural unit containing a hydroxyl group.

[0150] If the polymer compound contains a hydroxyl group, this is not preferred since there is a risk of impairing the stability of the metal compound.

[0151] The weight average molecular weight of the polymer compound (B) is preferably 6,000 to 50,000, and the dispersity, 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 a value measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and polystyrene as a standard. When the weight average molecular weight and dispersity of the polymer compound used in the (B) surface modifier contained in the metal-containing film-forming composition are within such ranges, excellent film-forming properties can be obtained during spin coating, and the generation of sublimates during heat curing can be suppressed, preventing contamination of the device. In particular, when forming a metal-containing film as a resist intermediate film, if the composition contains a low molecular weight and volatile component, the film thickness distribution in the surface of the substrate to be processed is likely to vary, but if the molecular weight and dispersity of the polymer compound used are set as described above and the amount of the low molecular weight component in the composition is controlled, the film thickness distribution in the surface of the substrate to be processed 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 dispersity is preferably 3.0 or less.

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

[0154] If the content is within this range, it is possible to achieve a higher compatibility between the etching selectivity of the (A) metal compound and the pattern adhesion of the (B) surface modifier.

[0155] (B) As a method for synthesizing a polymeric compound for surface modifier, for example, a method is to mix monomers having polymerizable unsaturated bonds corresponding to each repeating unit, add a radical polymerization initiator in a solvent, and perform thermal polymerization. Polymerization conditions can be selected in various ways depending on the monomers used, the target molecular weight, etc., and are not particularly limited. Specific examples of the solvent 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, and diacetone alcohol. Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2-azobis(2-methylpropionate), benzoyl peroxide, lauroyl peroxide, and the like. In addition, thiols such as octanethiol and 2-mercaptoethanol may be added as chain transfer agents during polymerization. The polymerization reaction can be carried out by heating preferably to 40°C to 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 compounds having polymerizable double bonds represented by the following general formulas (1'), (2'), and (B-1') as monomers and carrying out the polymerization as described above, it is possible to synthesize polymer compounds containing repeating units represented by the above general formulas (1), (2), and (B-1). [ka] (In the formula, R 1 ~R 3 , R 5 ~R 6 , R 1 ’ is the same as above.)

[0157] In the polymerization, all the raw materials may be mixed and then heated, or the remaining raw materials may be added individually or mixed into a portion of the raw materials that has been heated in advance, all at once or gradually. For example, a polymerization method in which only the polymerization solvent is heated and the monomer solution and the polymerization initiator solution are added separately and gradually thereto is particularly preferred, since it can provide a relatively homogeneous polymer compound and can prevent abnormal reactions such as runaway reactions.

[0158] The polymer compound solution obtained as described above may be directly blended into the metal-containing film-forming composition, or may be purified by using a conventional method such as crystallization, separation, filtration, or concentration, as necessary, to remove residual monomers, residual solvents, reaction by-products, and other impurities. When purifying a polymer compound, a crystallization method in which a poor solvent such as water, water-containing alcohol, or saturated hydrocarbon is added to a solution of the polymer compound and the resulting precipitate is filtered, or a separation method in which a poor solvent layer is separated and removed, is preferable, and among these, the separation method is particularly preferable. When a polymer compound is purified by a separation method, low molecular weight components in the polymer compound solution can be efficiently removed, so that the generation of sublimates is reduced when a metal-containing film is formed from a metal-containing film-forming composition containing this polymer compound, and as a result, contamination of the film-forming device can be prevented.

[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 contained therein.

[0160] Specifically, for example, the organic solvents described in paragraphs

[0091] to

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

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

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

[0163] The (C-1) high boiling point 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 point solvent) may be used.

[0165] The (C-1) high boiling point solvent is not particularly limited as long as it can dissolve each component of the metal-containing film forming composition of the present invention, and may be any of hydrocarbons, alcohols, ketones, esters, ethers, chlorine-based solvents, etc., but specific examples include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-Hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, n-nonyl acetate, monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol-n-butyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, propylene glycol diacetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,Examples of the diethyl ester include 6-hexanediol diacetate, triethylene glycol diacetate, γ-butyrolactone, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, and dibutyl adipate. These may be used alone or in combination.

[0166] The (C-1) high boiling point solvent may be appropriately selected from the above-mentioned solvents according to the temperature at which the metal-containing film-forming composition of the present invention is heat-treated. The boiling point of the high boiling point solvent is preferably 180°C to 300°C, more preferably 200°C to 300°C. If the solvent has such a boiling point, there is no risk of the solvent volatilizing too quickly during baking (heat treatment), so that sufficient thermal fluidity can be obtained during film formation, and it is considered that when a resist underlayer film is formed, the etching selectivity of the (A) metal compound and the pattern adhesion of the (B) surface modifier can be more highly compatible without forming a sea-island structure. In addition, if the solvent has such a boiling point, there is no risk of the solvent remaining in the film without volatilizing after baking, so there is no risk of adversely affecting the film properties such as etching resistance.

[0167] When the (C-1) high boiling point solvent is used, the blending amount is preferably 1 to 30 parts by mass per 100 parts by mass of the organic solvent having a boiling point of less than 180° C. Such a blending amount is preferable because it can impart sufficient thermal fluidity during baking and does not remain in the film, leading to deterioration of the film properties such as etching resistance.

[0168] <Other ingredients> When the metal-containing film-forming composition is a metal-containing film-forming composition that can be used as a resist underlayer film used in a multilayer resist method, it is sufficient that the composition contains one or more of the above-mentioned (A) metal compound, (B) surface modifier, and (C) solvent, and may contain at least one or more of (D) thermal acid generator, (E) photoacid generator, (F) crosslinking agent, and (G) surfactant, as necessary.

[0169] Hereinafter, components that may be contained in the composition for forming a resist underlayer film of the present invention other than the above (A) metal compound, (B) surface modifier, and (C) organic solvent will be described.

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

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

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

[0173] Above, R 70 , R 71 , R 72 , and R 73may be the same or different, and specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclopropylmethyl group, a 4-methylcyclohexyl group, a cyclohexylmethyl group, a norbornyl group, and an adamantyl group.

[0174] Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, and a cyclohexenyl group.

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

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

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

[0178] Examples of the aralkyl group include a benzyl group, a phenylethyl group, and a phenethyl group.

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

[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 in the ring, 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, 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-pyridine, Examples of the pyridine derivative include pyridine, 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-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline 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, and the like.

[0181] Above, X A -Examples of the non-nucleophilic counter ion include halide ions such as chloride ion and bromide ion; 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 sulfonates substituted with fluoro at the α-position as shown in the following general formula (8) and sulfonates substituted with fluoro at the α- and β-positions as shown in the following general formula (9).

[0182] [ka]

[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. 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 thermal acid generator include, but are not limited to, the following.

[0185] [ka]

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

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

[0160] to

[0179] of JP-A-2009-126940 can be used. The amount of the photoacid generator added is preferably 0.05 to 30 parts, more preferably 0.1 to 10 parts, based on 100 parts of the surface modifier (B). If the amount of the 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] In addition, in order to enhance the curability and further suppress intermixing with the resist upper layer film, a crosslinking agent (F) may be added to the metal-containing film-forming composition of the present invention. The crosslinking agent is not particularly limited, and various known crosslinking agents can be widely used. Examples include melamine-based crosslinking agents, glycoluril-based crosslinking agents, benzoguanamine-based crosslinking agents, urea-based crosslinking agents, β-hydroxyalkylamide-based crosslinking agents, isocyanurate-based crosslinking agents, aziridine-based crosslinking agents, oxazoline-based crosslinking agents, epoxy-based crosslinking agents, and phenol-based crosslinking agents. The above (F) crosslinking agent can be used alone or in combination of two or more. When the crosslinking agent is added, the amount of the crosslinking agent is preferably 5 to 50 parts, more preferably 10 to 40 parts, based on 100 parts of the above (B) surface modifier. If the amount of the crosslinking agent added is 5 parts or more, sufficient curability is exhibited 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 low ratio of the (B) surface modifier in the composition, and no risk of deterioration in dry etching resistance due to a low ratio of the (A) metal compound.

[0189] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylated melamine, hexabutoxymethylated melamine, alkoxy- and / or hydroxy-substituted products thereof, and partial self-condensates thereof.

[0190] Specific examples of glycoluril crosslinking agents include tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, alkoxy and / or hydroxy substituted products thereof, and partial self-condensates thereof.

[0191] Specific examples of benzoguanamine-based crosslinking agents include tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, alkoxy- and / or hydroxy-substituted products thereof, and partial self-condensates thereof.

[0192] Specific examples of the urea-based crosslinking agent include dimethoxymethylated dimethoxyethyleneurea, its alkoxy and / or hydroxyl substituted derivatives, and partial self-condensates thereof.

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

[0194] Specific examples of the isocyanurate crosslinking agent include triglycidyl isocyanurate and triallyl isocyanurate.

[0195] Specific examples of the aziridine crosslinking agent include 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate].

[0196] Specific examples of the oxazoline crosslinking agent include 2,2'-isopropylidenebis(4-benzyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), 2,2'-methylenebis4,5-diphenyl-2-oxazoline, 2,2'-methylenebis-4-phenyl-2-oxazoline, 2,2'-methylenebis-4-tertbutyl-2-oxazoline, 2,2'-bis(2-oxazoline), 1,3-phenylenebis(2-oxazoline), 1,4-phenylenebis(2-oxazoline), and 2-isopropenyloxazoline copolymer.

[0197] Specific 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] A specific example of the phenol-based crosslinking agent is a compound represented by the following general formula (10). [ka] (In the formula, Q is a single bond or a q 1 R is a 4-valent hydrocarbon group. 16 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. 1 is an integer between 1 and 5.)

[0199] Q is a single bond or a carbon number of 1 to 20 1 It is a q-valent hydrocarbon group. 1 is an integer of 1 to 5, and more preferably 2 or 3. Specific 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, and eicosane. 16 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, an octyl group, an ethylhexyl group, a decyl group, and an eicosanyl group, and a hydrogen atom or a methyl group is preferable.

[0200] Specific examples of the compound represented by the above general formula (10) include the following compounds. Among these, from the viewpoint of improving the curability and thickness uniformity of the adhesive film, hexamethoxymethylated products of triphenolmethane, triphenolethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene are preferred.

[0201] [ka]

[0202] [ka]

[0203] The above (F) crosslinking agent can be used alone or in combination of two or more. The amount of the (F) crosslinking agent added is preferably 10% by mass to 50% by mass, more preferably 15% by mass to 30% by mass, based on 100 parts of the above (B) surface modifier. If the amount added is 10% by mass or more, sufficient curability is obtained, 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 in adhesion due to a decrease in the ratio of the (B) surface modifier in the metal-containing film-forming composition, and of deterioration in dry etching resistance due to a decrease in the ratio of the (A) metal compound.

[0204] [(G) Surfactant] To the metal-containing film-forming composition of the present invention, a surfactant (G) can be added to improve the coating property in spin coating. The surfactant can be used alone or in combination of two or more. For example, the surfactants described in paragraphs

[0142] to

[0147] of JP-A-2009-269953 can be used. When a surfactant is added, the amount of the surfactant is preferably 0.001 to 20 parts, more preferably 0.01 to 10 parts, based on 100 parts of the metal compound (A). Within such a range, the coating property is reliably improved, and a thin and uniform adhesive film can be formed.

[0205] [Plasticizer] A plasticizer can be added to the metal-containing film-forming composition of the present invention. The plasticizer is not particularly limited, and various known plasticizers can be widely used. Examples include low molecular weight compounds such as phthalates, adipic esters, phosphates, trimellitates, and citrates, and polymers such as polyethers, polyesters, and polyacetal polymers described in JP-A-2013-253227. The amount of the plasticizer to be added is preferably 1% by mass to 500% by mass with respect to 100 parts of the (A) metal compound. When the amount is within such a range, the pattern filling and averaging are excellent.

[0206] <Metal-containing film formation method> In the present invention, the above-mentioned composition for forming a metal-containing film can be used to form a metal-containing film as a resist underlayer film of a multi-layer resist film used in lithography, for example.

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

[0208] In addition, in a method for forming a resist underlayer film using the composition for forming a metal-containing film of the present invention, the composition for forming a metal-containing film of the present invention can be coated on a substrate to be processed by a spin coating method or the like as described above, and the composition for forming a metal-containing film can be baked and cured in an atmosphere having an oxygen concentration of 0.1 vol.% or more and 21 vol.% or less to form a metal-containing film.

[0209] By baking the metal-containing film-forming composition of the present invention in such an oxygen atmosphere, a sufficiently hardened film can be obtained. The atmosphere during baking may be air, but N 2 It is preferable to seal an inert gas such as Ar or He in order to prevent oxidation of the metal-containing film. In order to prevent oxidation, it is necessary to control the oxygen concentration, which is preferably 1000 ppm or less, and more preferably 100 ppm or less (volume basis). Preventing oxidation of the metal-containing film during baking is preferable because it prevents the absorption from increasing and the etching resistance from decreasing.

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

[0211] <Pattern Forming Method Using Composition for Forming Resist Underlayer Film> In addition, the present invention provides a method for forming a pattern by a two-layer resist process using the metal-containing film-forming composition of the present invention, which is a method for forming a pattern on a substrate to be processed, comprising the steps of: (I-1) a step of applying the composition for forming a metal-containing film of the present invention onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (I-2) forming a resist top 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-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (I-4) a step of transferring the pattern to the metal-containing film by dry etching using the resist top layer film on which the pattern is formed as a mask; and (I-5) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. The present invention provides a pattern forming method comprising the steps of:

[0212] The resist top layer film of the two-layer resist process exhibits etching resistance by chlorine-based gas, so in the two-layer resist process, the dry etching of the metal-containing film is preferably performed by using the resist top layer film as a mask with an etching gas mainly made of chlorine-based gas.The metal-containing film exhibits etching resistance by fluorine-based gas, so the dry etching of the substrate to be processed is preferably performed by using the metal-containing film as a mask with an etching gas mainly made of fluorine-based gas.

[0213] In addition, the present invention provides a method for forming a pattern by a three-layer resist process using the metal-containing film-forming composition of the present invention, which is a method for forming a pattern on a substrate to be processed, comprising the steps of: (II-1) forming a resist underlayer film on a substrate to be processed; (II-2) a step of applying a composition for forming a metal-containing film of the present invention onto the resist underlayer film, followed by heat treatment to form a metal-containing film; (II-3) forming a resist top layer film on the metal-containing film using a photoresist material; (II-4) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (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 a pattern to the resist underlayer film by dry etching using the metal-containing film to which the pattern has been transferred as a mask; (II-7) a step of processing the substrate using the resist underlayer film on which the pattern is formed as a mask to form a pattern on the substrate; The present invention provides a pattern forming method comprising the steps of:

[0214] The metal-containing film formed by the metal-containing film-forming composition of the present invention and used as the intermediate film in the above three-layer resist process exhibits etching resistance by oxygen-based gas, so in the above three-layer resist process, the dry etching of the organic resist underlayer film using the metal-containing film as a mask is preferably performed using an etching gas mainly composed of oxygen-based gas.The organic underlayer film exhibits etching resistance by fluorine-based gas, so the dry etching of the substrate to be processed using the organic underlayer film as a mask is preferably performed using an etching gas mainly composed of fluorine.

[0215] In the above pattern forming method, the resist upper layer film may be either positive or negative, and the same photoresist composition as that usually used can be used. When the resist upper layer film is formed from 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 to 180° C. for 10 to 300 seconds. Thereafter, exposure is performed according to a conventional method, post-exposure baking (PEB) and development are performed to obtain a resist pattern. The thickness of the resist upper layer film is not particularly limited, but is preferably 10 to 500 nm, particularly preferably 20 to 400 nm.

[0217] The exposure light is a high-energy ray with a wavelength of 300 nm or less, specifically, far ultraviolet light, KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F 2 Laser light (157 nm), Kr 2 Laser light (146 nm), Ar 2 Examples of the light include laser light (126 nm), soft X-rays (EUV) of 3 to 20 nm, electron beams (EB), ion beams, and X-rays.

[0218] The method for forming the pattern on the resist upper layer film is preferably photolithography with a wavelength of 5 nm or more and 300 nm or less, direct drawing with an electron beam, nanoimprinting, or a combination of these.

[0219] In the pattern forming method, the development method is preferably alkaline development or development using an organic solvent.

[0220] Next, etching is performed using the obtained resist pattern as a mask. For example, etching of a metal-containing film in a two-layer resist process is performed using a chlorine-based gas and the upper layer resist pattern as a mask. This forms a metal-containing film pattern. Next, etching of a substrate to be processed is performed using the obtained metal-containing film pattern as a mask. Etching of the workpiece can be performed by a conventional method, for example, when the workpiece is made of SiO 2 For SiN or silica-based low dielectric constant insulating films, etching is performed mainly with fluorocarbon gases.

[0221] The metal-containing film obtained by using the metal-containing film-forming composition of the present invention is characterized by excellent etching resistance when etching the workpiece.

[0222] Examples of organic resist underlayer film materials that can be used for the resist underlayer film include those already known as underlayer films for a three-layer resist method or a two-layer resist method using a silicon resist composition. For example, JP-A-2012-1687, JP-A-2012-77295, JP-A-2004-264710, JP-A-2005-043471, JP-A-2005-250434, JP-A-2007-293294, JP-A-2008-65303, JP-A-2004-205 685, JP 2007-171895 A, JP 2009-14816 A, JP 2007-199653 A, JP 2008-274250 A, JP 2010-122656 A, JP 2012-214720 A, JP 2014-29435 A, International Publication WO Examples of resins and compositions disclosed in JP-A-2012 / 077640, WO2010 / 147155, WO2012 / 077640, WO2010 / 147155, WO2012 / 176767, JP-A-2005-128509, JP-A-2006-259249, JP-A-2006-259482, JP-A-2006-293298, JP-A-2007-316282, JP-A-2012-145897, JP-A-2017-119671, JP-A-2019-44022, and the like can be mentioned.

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

[0224] Instead of the organic resist underlayer film material, an organic hard mask formed by a CVD method or an ALD method can also be used.

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

[0226] The metal-containing film obtained by using the metal-containing film-forming composition of the present invention is characterized by excellent etching resistance during etching of these resist underlayer films.

[0227] The workpiece (substrate) is not particularly limited, and may be Si, α-Si, p-Si, SiO 2 The substrate may be made of a material such as SiN, SiON, W, TiN, or Al, or a substrate having a layer to be processed formed thereon. 2 Various low-k films and their stopper films such as SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, and Al-Si are used, and can be formed to a thickness of usually 50 to 10,000 nm, particularly 100 to 5,000 nm. When forming a processed layer, the substrate and the processed layer are made of different materials.

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

[0229] In addition, an example of a pattern forming method by the two-layer resist process will be described with reference to FIG. 2. In this example, first, as shown in FIG. 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. Then, as shown in FIG. 2(H), the exposed portion 6 of the resist upper layer film is exposed to light in a pattern. Next, as shown in FIG. 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 FIG. 2(J), the resist upper layer film on which the 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 FIG. 2(K), the workpiece layer 2 on the substrate 1 is processed using the metal-containing film on which the 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 to these.

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

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

[0233] [ka]

[0234] [ka]

[0235] As the metal source M, the following metal compounds were used. (M1): Diisopropoxybis(2,4-pentanedionato)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 solution in 1-butanol) (Tokyo Chemical Industry Co., Ltd., Z0016) (M4):Hf(OBu) 4 : Hafnium(IV) n-butoxide (Sigma-Aldrich Corp, 667943) (M5): Ti(OBu) 4 : Tetrabutyl orthotitanate (Tokyo Chemical Industry Co., Ltd., B0742) (M6): Titanium butoxide tetramer (FUJIFILM Wako Pure Chemical Industries, Ltd.)

[0236] [Synthesis Example A1] Synthesis of metal compound (A-1) Under a nitrogen atmosphere, 50.9 g of diisopropoxybis(2,4-pentanedionato)titanium(IV) (M1) (mass of metal compound: 38.2 g) was dissolved in 180.0 g of propylene glycol monoethyl ether (PGEE), and 20.2 g of deionized water was added dropwise at room temperature over 10 minutes while stirring. Then, the mixture was reacted at 60°C for 2 hours, cooled at room temperature, and 250 g of propylene glycol monoethyl ether was added. 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 a solution of 50.0 g of IPA in 2.7 g of deionized water was added dropwise at room temperature over 2 hours while stirring. 12.4 g of organic group raw material group (G1) was added to the obtained solution and stirred at room temperature for 30 minutes. After concentrating this solution at 30°C under reduced pressure, it was further heated to 60°C and continued to be heated under reduced pressure until no distillate was produced. When no distillate was observed, 120.0 g of PGMEA / PGME (weight ratio 70 / 30) solution was added and heated at 40°C under reduced pressure until no IPA was produced, to obtain a PGMEA / PGME solution of metal compound (A-2).

[0238] [Synthesis Examples A3 to A8] Synthesis of Metal Compounds (A-3) to (A-8) Metal compounds (A-3) to (A-8) shown in Table 1 were obtained under the same reaction conditions as in Synthesis Example A1, except that the metal source M and compound group G were used in the amounts shown in Table 1. [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, the reaction temperature was increased to 50°C while stirring, and 6.5 g of compound H1 was dropped into the solution. After the dropwise addition, the reaction temperature was set to 60°C and stirring was continued for 2 hours. Next, a mixture obtained by suspending 6.4 g of compound G3 in 8.6 g of PGMEA / PGME (weight ratio 70 / 30) solution was added to the reaction system, and stirring was continued for 1 hour while keeping the reaction temperature at 60°C. 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 to A16] Synthesis of Metal Compounds (A-10) to (A-16)] Metal compounds (A-10) to (A-16) shown in Table 2 were obtained under the same reaction conditions as in Synthesis Example A9, except that the metal source M, compound group G, and compound group H were used in the amounts shown in Table 2.

[0241] [Table 2]

[0242] [(B) Synthesis of surface modifier] (B) Polymer compounds (B-1) to (B-14) of surface modifiers and comparative polymer compounds (B-15) to (B-16) were synthesized. The following monomers (J1) to (J13) were used to prepare these polymer compounds.

[0243] [ka]

[0244] [Synthesis Example B1] Synthesis of polymer compound (B-1) In a 500 ml flask, 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, 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 as a polymerization initiator, and the mixture was degassed while stirring to prepare a polymerization initiator solution. In addition, 60 g of PGMEA was weighed in a 1 L flask with a nitrogen atmosphere, and the mixture was degassed while stirring, and then 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 the addition, the mixture was heated and stirred for 16 hours, and then cooled to room temperature. The obtained polymerization liquid was dropped into 1,500 g of stirred hexane, and the precipitated polymer was filtered off. The resulting polymer was washed twice with 600 g of hexane and then vacuum dried at 50° C. for 20 hours to obtain a polymer compound (B-1) in the form of a white powder. As a result of GPC analysis, the weight average molecular weight (Mw) of the polymer compound (B-1) was 10,000 and the dispersity (Mw / Mn) was 2.0.

[0245] [Synthesis Examples B2 to B14 and Comparative Synthesis Examples B15 to B16] Synthesis of polymer compounds (B-2) to (B-16) 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 in the amounts shown in Table 3. Table 3 below also shows the weight average molecular weight (Mw) and dispersity (Mw / Mn) of each polymer compound.

[0246] [Table 3]

[0247] Preparation of metal-containing film-forming compositions (MUL1-16, comparative MUL1-5) The metal-containing film-forming compositions were prepared using any of the above metal compounds (A-1) to (A-16), any of the polymer compounds (B-1) to (B-16) as surface modifiers, the following compounds (AG1) to (AG3) as thermal acid generators, the following compounds (AG4) or (AG5) as photoacid generators, the following compounds (XL1) or (XL2) as crosslinkers, and a solvent (C1: ethylene glycol dibenzyl ether: boiling point 364°C) as a high boiling point solvent. These were dissolved in an organic solvent containing 0.001 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 compositions for forming metal-containing films (MUL-1 to 16, Comparative Examples MUL-1 to 4) prepared above was applied onto a silicon substrate, and the coating film was baked at 250°C for 60 seconds, after which the thickness of the coating film from the center to the outer periphery of the substrate was measured to calculate the average thickness (a [nm]). Next, PGMEA solvent was dispensed onto the coating film, left for 30 seconds, then spin-dried, and then baked at 100°C for 60 seconds to evaporate PGMEA, and the thickness (b [nm]) of the coating film was measured. The difference in thickness (residual film ratio: (b / a) x 100) before and after PGMEA treatment was determined. The results are shown in Table 5 below.

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

[0252] In Comparative Example 1-5, in which the metal-containing film-forming composition (Comparative Example MUL-5) was used, a precipitate was generated after the above sample preparation, and the evaluation was discontinued. In the metal-containing film-forming composition (Comparative Example MUL-5), the polymer compound (B-16) used in the (B) surface modifier contains a structural unit containing a hydroxyl group, and it is presumed that the polymer compound reacted with the metal compound to generate a precipitate.

[0253] [Table 5]

[0254] As shown in Table 5, the metal-containing film materials (MUL-1 to 16) of the present invention all have good film-forming properties, and almost no film loss due to solvent treatment, and it can be seen that a film with good solvent resistance is obtained. In addition, by using a surface modifier, a film with a contact angle to pure water of more than 60° is obtained, and it can be seen that good adhesion to the resist pattern can be expected. In particular, the contact angles of Examples 1-5 to 1-16 using a metal compound containing a crosslinking group represented by any of the general formulas (a-1) to (a-4), (b-1) to (b-4), and (c-1) to (c-3) above are high, and among them, the contact angles of Examples 1-5 to 1-8 using hydrolysis condensates of metal compounds (metal compounds A-5 to A-8), Examples 1-10 to 1-14 using a polymer compound containing a structural unit containing an F atom as a surface modifier, and Example 1-16 using a high boiling point solvent as an additive were found to be high.

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

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

[0257] Silicon-containing resist intermediate film material (SOG-1) The ArF silicon-containing intermediate film polymer (SiP1) and the thermal crosslinking catalyst (CAT1) were dissolved in a solvent (a mixed solvent of solvent 1 and solvent 2 below) containing 0.1 mass % of FC-4430 (manufactured by Sumitomo 3M Limited) in the ratios shown in Table 6, and the solution was filtered through a fluorine resin filter with a pore size of 0.1 μm to prepare a silicon-containing resist intermediate film material (SOG-1).

[0258] [Table 6]

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

[0260] [ka]

[0261] Next, CF was performed under the following conditions using the ULVAC etching equipment CE-300I. 4 Gas and O 2 Each etching was performed using the gas, and the film thickness b was measured. The film thickness etched in one minute using each gas was calculated as the etching rate (nm / min) from the film thickness (film thickness b - film thickness a) etched during the specified time. The results are shown in Table 7.

[0262] CF 4 Gas dry etching conditions Pressure: 1Pa Antenna RF power: 100W Bias RF power: 15W CF 4 Gas flow rate: 15sccm Time: 30sec

[0263] O 2 Gas dry etching conditions Pressure: 1Pa Antenna RF power: 300W Bias RF power: 10W O 2 Gas flow rate: 25sccm Time: 30sec

[0264] [Table 7]

[0265] As shown in Table 7, the compositions for forming metal-containing films (MUL-1 to 16) of the present invention all contained CF 4 Gas and O 2 It was found that the film exhibited excellent etching resistance against gases. CF 4 Because of its excellent etching resistance to gases, it is suitable for use in a two-layer resist process in which a resist pattern is transferred to a substrate to be processed in combination with a photoresist top layer.

[0266] In addition, the metal-containing film compositions of the present invention (MUL-1 to 16) had a lower oxidation resistance than the SOG-1 used in Comparative Example 2-5. 2 Because it has excellent resistance to etching using gas, it is suitable for a three-layer resist process in which a resist pattern is transferred to a substrate to be processed 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 the film was applied by spin coating on a Si wafer, and the coating film was baked at 350°C for 60 seconds to prepare a carbon film with a thickness of 45 nm. The carbon ratio of the carbon film was 88%. A composition obtained 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) was applied thereon, and heated at 250°C for 60 seconds using a hot plate to form a resist intermediate film with a thickness of 10 nm. A single layer resist for ArF, which is a resist upper layer film material, was applied thereon, and the coating film was baked at 105°C for 60 seconds to form a photoresist film with a thickness of 100 nm. An immersion protective film material (TC-1) was applied onto the photoresist film, and the coating was baked at 90° C. for 60 seconds to form a protective film with a thickness of 50 nm.

[0268] In Comparative Example 3-4, a composition prepared by diluting the silicon-containing resist intermediate film 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 intermediate film with a thickness of 10 nm.

[0269] The resist top layer film material (ArF single layer resist) was prepared by dissolving the polymer (RP1), acid generator (PAG1), and basic compound (Amine1) in a solvent containing 0.1 mass % of surfactant FC-4430 (Sumitomo 3M Limited) in the ratios shown in Table 8, and filtering the solution 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 top layer material (ArF single layer resist) 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 ratio shown in Table 9, and filtering 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 film was exposed using an ArF immersion exposure apparatus (Nikon Corporation; NSR-S610C, NA 1.30, σ 0.98 / 0.78, 35 degree dipole s-polarized illumination, 6% halftone phase shift mask), baked at 100°C for 60 seconds (PEB), and developed in a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds to obtain a 50 nm 1:1 positive line and space pattern (resist upper layer film pattern).

[0277] The reflectance was calculated using PROLITH 2020a (LithoTech Japan Co., Ltd.). The film thickness of the metal-containing film was fixed at 10 nm, and the reflectance was calculated when the refractive index n of the metal-containing film at a wavelength of 193 nm was 1.80 to 2.30 and the extinction coefficient k was 0.19 to 0.50. The optical constant (n / k) that can reduce the reflectance from the underlying substrate during pattern exposure is preferable.

[0278] The optical constants of the metal-containing film-forming composition were determined by applying 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 of incidence spectroscopic ellipsometer (VASE) manufactured by JA Woollam.

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

[0280] The results are shown in Table 10.

[0281] Next, the resist intermediate film is etched by dry etching using the resist upper layer film pattern as a mask to form a hard mask pattern, the organic lower layer film is etched using the obtained hard mask pattern as a mask to form a pattern, and the SiO 2 The film was etched under the following etching conditions.

[0282] (Examples 3-1 to 3-3 and Comparative Examples 3-1 to 3-3) Conditions for transferring the hard mask pattern to the metal-containing film (resist intermediate film). Cl 2 Gas dry etching conditions Pressure: 1Pa Antenna RF power: 320W Bias RF power: 30W Cl 2 Gas flow rate: 25sccm Time: 10sec

[0283] (Comparative Example 3-4) Conditions for transferring the hard mask pattern onto the SOG-1 film (resist intermediate film). CF 4 Gas dry etching conditions Pressure: 1Pa Antenna RF power: 100W Bias RF power: 15W CF 4 Gas flow rate: 15sccm Time: 15sec

[0284] Transfer conditions of the resist intermediate film pattern to the organic underlayer film. O 2Gas dry etching conditions Pressure: 1Pa Antenna RF power: 300W Bias RF power: 10W O 2 Gas flow rate: 25sccm Time: 20sec

[0285] SiO of resist underlayer film pattern 2 Membrane transfer conditions. CF 4 Gas dry etching conditions Pressure: 1Pa Antenna RF power: 100W Bias RF power: 15W CF 4 Gas flow rate: 15sccm Time: 60sec

[0286] [Table 10]

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

[0288] Furthermore, after the etching following substrate transfer, the resist upper layer film pattern was successfully transferred to the substrate, confirming that the multilayer resist method is suitable for use in microfabrication.

[0289] In Comparative Examples 3-1 and 3-2 in which no surface modifier was used, and Comparative Example 3-3 in which a polymer compound different from the present invention was used as a surface modifier, collapse of the resist upper layer film pattern was observed after development.

[0290] In Comparative Example 3-4, in which SOG-1 was used as the resist intermediate film material, the LWR after development was confirmed to be inferior to that of Examples 3-1 to 3-3 in which the metal-containing film-forming composition of the present invention (MUL-3, 8, 12) was used, possibly due to the high reflectance at the time of pattern exposure of 4.4%. In addition, in Comparative Example 3-4, it was confirmed that the pattern shape after substrate transfer etching was an undercut shape. This is presumably 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 formation method of the present invention have high adhesion to the resist overlayer film pattern, have the effect of preventing the collapse of the fine pattern, and give a resist overlayer film pattern shape with high rectangularity, and are therefore particularly suitable for use in multilayer resist processes and are extremely useful in fine patterning for manufacturing semiconductor devices.

[0292] The present specification includes the following aspects. [1] (A) a metal compound, (B) a surface modifier; and (C) Solvent and Contains the metal compound contains at least one metal atom selected from the group consisting of Ti, Zr, and Hf, The metal-containing film-forming composition, characterized in that the (B) surface modifier is a polymeric compound containing one or both of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), and the polymeric compound does not contain a repeating unit containing a hydroxyl group. [ka] (In the formula, R 1is a hydrogen atom or a methyl group, and R 2 is a monovalent organic group having 2 to 20 carbon atoms and containing a heterocyclic structure, R 3 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], wherein the heterocyclic structure is a heterocyclic structure containing an oxygen atom. [3] R in the above general formulas (1) and (2) 2 is expressed by the following formula (R 2 -1)~(R 2 The metal-containing film-forming composition according to [1] or [2], wherein the monovalent organic group includes a group selected from the group consisting of -3). [ka] (In the formula, R 4 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the dashed line represents a bond. [4] The metal-containing film-forming composition according to any one of [1] to [3], wherein the (B) surface modifier is a polymeric compound further comprising any one of repeating units 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 is an F atom or a monovalent organic group having 1 to 10 carbon atoms containing one or more F atoms, and R 1 is a hydrogen atom or a methyl group, and n is 1 to 5. [5] The composition for forming a metal-containing film according to any one of [1] to [4], wherein the polymer compound used in the (B) surface modifier has a weight average molecular weight of 6,000 to 50,000. [6] The composition for forming a metal-containing film according to any one of [1] to [5], characterized in that the dispersity, expressed as weight average molecular weight / number average molecular weight, of the polymer compound used in the (B) surface modifier is 3.0 or less. [7] A 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 a metal compound. [8] Furthermore, (D) a thermal acid generator, (E) a photoacid generator, (F) a crosslinker, and (G) Surfactants The composition for forming a metal-containing film according to any one of [1] to [7], which contains at least one of the following: [9] The (C) solvent contains a (C-1) high-boiling point solvent, The metal-containing film-forming composition according to any one of [1] to [8], wherein the (C-1) high boiling point solvent is one or more organic solvents having a boiling point of 180° C. or higher.

[10] The composition for forming a metal-containing film according to any one of [1] to [9], wherein the (A) metal compound is derived from a metal compound represented by the following general formula (4): [ka] (In the formula, M is any one of Ti, Zr, and Hf. L is a monodentate or polydentate ligand having 1 to 30 carbon atoms. X is a halogen atom, an alkoxy group, a carboxylate group, an acyloxy group, -NR a R b R is a hydrolyzable group selected from the group consisting of 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 of 0 to 4.

[11] The metal-containing film-forming composition according to

[10] , wherein 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 and containing at least one crosslinking group represented by any one of the following general formulas (a-1) to (a-4), (b-1) to (b-4), and (c-1) to (c-3): [ka] (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 is 0 or 1, and * is a bond. [ka] (In the above general formula, R b is a hydrogen atom or a methyl group, which may be the same or different in the same formula; 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. [ka] (In the above general formulas (c-1) to (c-3), Y 1 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 that generates one or more hydroxyl groups or carboxyl groups by the action of either or both of an acid and heat represented by the following general formula (c-4), and * represents a bond. [ka] (In the above general formula (c-4), R e is an organic group whose protecting group is removed by the action of either acid or heat, or both, and * is Y 1 )

[12] A method for forming a pattern on a workpiece substrate, comprising the steps of: (I-1) A step of applying a composition for forming a metal-containing film according to any one of [1] to

[11] onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (I-2) forming a resist top 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-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (I-4) a step of transferring the pattern to the metal-containing film by dry etching using the resist top layer film on which the pattern is formed as a mask; and (I-5) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. A pattern forming method comprising the steps of:

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

[11] onto the resist underlayer film, followed by heat treatment to form a metal-containing film; (II-3) forming a resist top layer film on the metal-containing film using a photoresist material; (II-4) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (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 a pattern to the resist underlayer film by dry etching using the metal-containing film to which the pattern has been transferred as a mask; (II-7) a step of processing the substrate using the resist underlayer film on which the pattern is formed as a mask to form a pattern on the substrate; A pattern forming method comprising the steps of:

[0293] The present invention is not limited to the above-described embodiment. The above-described embodiment is merely an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included in the technical scope of the present invention. [Explanation of symbols]

[0294] 1...substrate, 2...processed layer, 2a...pattern (pattern formed on processed layer), 3...resist underlayer film, 3a...resist underlayer film pattern, 4...metal-containing film, 4a...metal-containing film pattern, 5...resist upper layer film, 5a...resist upper layer film pattern, 6...exposed portion, 10...processed substrate.

Claims

1. (A) a metal compound; (B) a surface modifier; and (C) a solvent; Contains the metal compound contains at least one metal atom selected from the group consisting of Ti, Zr, and Hf, The metal-containing film-forming composition, characterized in that the (B) surface modifier is a polymeric compound containing one or both of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), and the polymeric compound does not contain a repeating unit containing a hydroxyl group. 【Chemistry 1】 (In the formula, R １ is a hydrogen atom or a methyl group, R ２ is a monovalent organic group having 2 to 20 carbon atoms and containing a heterocyclic structure, R ３ is a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms.

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

3. R in the general formulas (1) and (2) ２ is expressed by the following formula (R ２ -1) to (R ２ 2. The metal-containing film-forming composition according to claim 1, wherein the monovalent organic group includes a group selected from the group consisting of aryl, aryl- ... 【Chemistry 2】 (In the formula, R ４ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the dashed line represents a bond.)

4. 2. The metal-containing film-forming composition according to claim 1, wherein the surface modifier (B) is a polymer compound further comprising a repeating unit represented by the following formula (3a) or formula (3b): 【Chemistry 3】 (In the above formula, R Ｆ１ is a monovalent organic group having 1 to 20 carbon atoms and containing at least one F atom, R Ｆ２ is an F atom or a monovalent organic group having 1 to 10 carbon atoms and containing one or more F atoms, R １ is a hydrogen atom or a methyl group, and n is 1 to 5.

5. 2. The metal-containing film-forming composition according to claim 1, wherein the polymer compound used in the surface modifier (B) has a weight average molecular weight of 6,000 to 50,000.

6. 2. The metal-containing film-forming composition according to claim 1, wherein the polymer compound used in the surface modifier (B) has a dispersity expressed by weight average molecular weight / number average molecular weight of 3.0 or less.

7. The metal-containing film-forming composition according to claim 1, characterized in that the content of the surface modifier (B) 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. moreover, (D) a thermal acid generator, (E) a photoacid generator, (F) a crosslinker, and (G) Surfactant The metal-containing film-forming composition according to claim 1, which contains at least one of the following:

9. The (C) solvent contains (C-1) a high boiling point solvent, 2. The metal-containing film-forming composition according to claim 1, wherein the high boiling point solvent (C-1) is one or more organic solvents having a boiling point of 180 degrees or higher.

10. 2. The metal-containing film-forming composition according to claim 1, wherein 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, and Hf. L is a monodentate or polydentate ligand having 1 to 30 carbon atoms. X is a halogen atom, an alkoxy group, a carboxylate group, an acyloxy group, -NR ａ R ｂ R is a hydrolyzable group selected from 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-containing film-forming composition according to claim 10, characterized in 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 and 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): 【Chemistry 5】 (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 is 0 or 1, and * is a bond. 【Chemistry 6】 (In the above general formula, R ｂ is a hydrogen atom or a methyl group, which may be the same or different in the same formula; 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 bond. 【Chemistry 7】 (In the above general formulas (c-1) to (c-3), Y １ 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 represented by the following general formula (c-4) which generates one or more hydroxyl groups or carboxyl groups by elimination of a protecting group by the action of either or both of an acid and heat, and * represents a bond. 【Chemistry 8】 (In the above general formula (c-4), R ｅ represents an organic group whose protecting group is removed by the action of either acid or heat, or both, and * represents Y １ It represents the bond with

12. A method for forming a pattern on a workpiece substrate, comprising the steps of: (I-1) A step of forming a metal-containing film by applying the composition for forming a metal-containing film according to any one of claims 1 to 11 onto a substrate to be processed and then subjecting the substrate to a heat treatment; (I-2) forming a resist top layer film on the metal-containing film using a photoresist material; (I-3) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a pattern on the resist upper layer film; (I-4) a step of transferring a pattern to the metal-containing film by dry etching using the resist top layer film on which the pattern is formed as a mask; and (I-5) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. A pattern forming method comprising the steps of:

13. A method for forming a pattern on a workpiece substrate, comprising the steps of: (II-1) forming a resist underlayer film on a substrate to be processed; (II-2) A step of forming a metal-containing film by applying the composition for forming a metal-containing film according to any one of claims 1 to 11 onto the resist underlayer film and then performing a heat treatment; (II-3) forming a resist top layer film on the metal-containing film using a photoresist material; (II-4) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (II-5) a step of transferring a pattern to the metal-containing film by dry etching using the resist top layer film on which the pattern has been formed as a mask; (II-6) a step of transferring a pattern to the resist underlayer film by dry etching using the metal-containing film to 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 has been formed as a mask to form a pattern on the substrate to be processed; A pattern forming method comprising the steps of:

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