Compound for forming metal-containing film, composition for forming metal-containing film, and pattern forming method

Abstract

To provide a metal compound having excellent dry etching resistance to a conventional resist underlayer film material and high filling / planarizing properties, a composition for forming a metal-containing film using the compound, and a pattern forming method using the composition.SOLUTION: A metal-containing film-forming compound for use in a composition for forming a metal-containing film, wherein the metal-containing film-forming compound contains at least one metal atom selected from the group consisting of Ti, Zr, and Hf, and one or more ligands derived from compounds represented by the following general formulae (1-B) to (1-D): SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a compound for forming a metal-containing film, a composition for forming a metal-containing film, and a pattern formation method using the composition. [Background technology]

[0002] As LSIs become more highly integrated and faster, pattern dimensions are becoming increasingly fine. Lithography technology has achieved this by shortening the wavelength of light sources and selecting appropriate resist compositions to match. Single-layer positive photoresist compositions have become the key to this. These single-layer positive photoresist compositions incorporate a backbone that provides etching resistance to dry etching with chlorine- or fluorine-based gas plasma, and a switching mechanism that dissolves exposed areas. This allows the exposed areas to be dissolved to form a pattern, and the remaining resist pattern is then used as an etching mask to dry etch the substrate.

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

[0004] On the other hand, substrate processing typically involves dry etching using a patterned photoresist film as an etching mask. However, in reality, no dry etching method can achieve perfect etching selectivity between the photoresist film and the substrate. As a result, the photoresist film can be damaged and disintegrated during substrate processing, preventing accurate transfer of the resist pattern to the substrate. Therefore, as patterns become finer, resist compositions are required to have higher dry etching resistance. However, to improve resolution, resins used in photoresist compositions must have low light absorption at the exposure wavelength. As a result, as exposure light wavelengths have become shorter (i-line, KrF, and ArF), resins have evolved, such as novolac resins, polyhydroxystyrenes, and resins with aliphatic polycyclic skeletons. However, in reality, the etching rates under dry etching conditions during substrate processing have become faster, and recent photoresist compositions with high resolution tend to have weaker etching resistance.

[0005] This means that substrates to be processed must be dry etched using thinner photoresist films with weaker etching resistance, and there is an urgent need to secure the materials and processes required for this processing step.

[0006] One method for solving these problems is the multilayer resist method, in which a resist underlayer 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 formed on the resist upper layer film, and then the pattern is transferred to the resist underlayer 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 underlayer film as a dry etching mask.

[0007] One type of multilayer resist method is the three-layer resist method, which can be performed using a typical resist composition used in single-layer resist methods. In this three-layer resist method, for example, an organic film made of a novolac resin or the like is deposited on a substrate to be processed as a resist underlayer, a silicon-containing resist intermediate film is deposited on top of that as a resist intermediate film, and a conventional organic photoresist film is deposited on top of that as a resist upper layer. When dry etching is performed using a fluorine-based gas plasma, the organic resist upper layer exhibits a favorable etching selectivity relative to the silicon-containing resist intermediate film, allowing the resist upper layer pattern to be transferred to the silicon-containing resist intermediate film by dry etching with a fluorine-based gas plasma. This method allows for pattern transfer to the silicon-containing resist intermediate film (resist intermediate film) even when using a resist composition that is difficult to directly form a pattern with a sufficient thickness for processing the substrate or that does not have sufficient dry etching resistance for substrate processing. Subsequent pattern transfer by dry etching with an oxygen- or hydrogen-based gas plasma allows for the formation of a pattern in an organic film (resist underlayer) made of a novolac resin or the like that has sufficient dry etching resistance for substrate processing. Many resist underlayer films such as those described above are already known, for example, those described in Patent Document 1.

[0008] On the other hand, in recent years, the miniaturization of DRAM memories has accelerated, and there is an increasing need for resist underlayer films that have further improved dry etching resistance and excellent filling and planarization properties. As a coat-type resist underlayer film material that has excellent filling and planarization properties, for example, the one described in Patent Document 2 has been reported, but in terms of application to the latest generation, there are concerns about dry etching resistance, and the application limit of conventional coat-type resist underlayer film materials is approaching.

[0009] To address the above issues, development of resist underlayer films using materials containing metal elements is being considered. Patent Document 3 reports that materials using Ti compounds exhibit excellent dry etching resistance to CHF3 / CF4-based gases and CO2 / N2-based gases.

[0010] On the other hand, one issue when using metal compounds in resist underlayer films is their embeddability. Patent Document 3 makes no mention of embeddability, but metal oxide compounds generally exhibit significant thermal shrinkage during baking, leading to a significant deterioration in their embedding ability after high-temperature baking. This raises concerns that they may be insufficient as resist underlayer film materials, which require advanced planarization, embedding, and heat resistance. Patent Documents 4 and 5 report that metal compounds modified with specific ligands have excellent embeddability, but the bake temperature used to evaluate embeddability was as low as 150°C, raising concerns that they may be insufficient as resist underlayer films that require heat resistance (e.g., resistance to heat treatments that may be performed after formation of the resist underlayer film). [Prior art documents] [Patent documents]

[0011] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-205685 [Patent Document 2] Patent No. 6714493 [Patent Document 3] Patent No. 6189758 [Patent Document 4] Patent No. 6786391 [Patent Document 5] Patent No. 7050137 Summary of the Invention [Problem to be solved by the invention]

[0012] The present invention has been made in view of the above circumstances, and aims to provide a metal compound that has superior dry etching resistance compared to conventional resist underlayer film materials and also has high-level filling / planarization properties, a metal-containing film-forming composition using the compound, and a pattern formation method using the composition. [Means for solving the problem]

[0013] In order to solve the above problems, the present invention provides a metal-containing film-forming compound used in a metal-containing film-forming composition, comprising: The compound for forming a metal-containing film contains at least one metal atom selected from the group consisting of Ti, Zr, and Hf, and one or more ligands derived from compounds represented by the following general formulas (1-A) to (1-D): [ka] (In the general formulas (1-A) to (1-D), R1 to R3 are hydrogen atoms or monovalent organic groups having 1 to 20 carbon atoms which may contain a crosslinking group represented by the following general formulas (a-1) to (a-4) and (b-1) to (b-4); R4 to R5 are hydrogen atoms or monovalent organic groups having 1 to 20 carbon atoms which may contain a crosslinking group represented by the following general formulas (a-1) to (a-4); R6 to R9 are hydrogen atoms or monovalent organic groups having 1 to 20 carbon atoms which may contain a crosslinking group represented by the following general formulas (a-1) to (a-4) and (b-1) to (b-4); R 10 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and Y is a divalent organic group having 1 to 10 carbon atoms. The compounds of general formulas (1-A) to (1-D) contain one or more bridging groups represented by general formulas (a-1) to (a-4) and (b-1) to (b-4). In general formula (1-B), R4 and R5 may be bonded to each other to form an unsaturated or saturated ring structure. [ka] (In general formulas (a-1) to (a-4), Ra represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.) [ka] (In general formulas (b-1) to (b-4), R' b is a hydrogen atom or a methyl group, and in the same formula, they may be the same or different from each other; R' c represents a hydrogen atom, 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.

[0014] Such a compound for forming a metal-containing film has a multidentate ligand containing one or more of the crosslinking groups represented by (a-1) to (a-4) and (b-1) to (b-4). When used in a composition for forming a metal-containing film, this compound exhibits small volume shrinkage during baking and can provide a material for forming a metal-containing film that has excellent planarization and filling properties even after high-temperature baking.

[0015] In addition, in the present invention, it is preferable that the ligand derived from the compound represented by the general formulas (1-A) to (1-D) contains one or more structures selected from an aromatic ring, a heteroaromatic ring, and an alicyclic structure.

[0016] Such a metal compound can improve the heat resistance of the metal-containing film-forming compound, and when used in a metal-containing film-forming composition, a metal-containing film-forming material exhibiting better planarization properties / filling properties can be provided.

[0017] In the present invention, the metal-containing film-forming compound preferably further contains a ligand derived from a silicon compound represented by the following general formula (2). [ka] (In general formula (2), R 3A , R 3B and R 3Cis any organic group selected from an organic group having 1 to 30 carbon atoms and a crosslinking group having any of the structures represented by the following general formulas (c-1) to (c-3), a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. [ka] (In general formulas (c-1) to (c-3), R'3 represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.)

[0018] The compound further contains a ligand derived from the silicon compound represented by the general formula (2), thereby improving the stability of the metal compound in solution. Furthermore, when the silicon compound contains an organic group having 1 to 30 carbon atoms and a crosslinking group having any of the structures represented by the general formulas (c-1) to (c-3), the metal-containing film-forming compound can achieve high levels of both thermal fluidity and thermosetting properties. When this compound is used in a metal-containing film-forming composition, a metal-containing film-forming material exhibiting superior planarization and filling properties can be provided.

[0019] The present invention also provides a metal-containing film-forming composition used in semiconductor manufacturing, which contains the above-described (A) metal-containing film-forming compound and (B) organic solvent.

[0020] Such a composition for forming a metal-containing film contains a metal-containing compound that has excellent heat resistance and thermal fluidity, and therefore can provide a material for forming a metal-containing film that has excellent dry etching resistance compared to conventional resist underlayer film materials and also has advanced filling / planarization properties compared to conventional resist underlayer film materials.

[0021] In this case, it is preferable that the metal-containing film-forming composition further contains one or more of (C) a crosslinking agent, (E) a surfactant, and (F) an acid generator.

[0022] A metal-containing film-forming composition containing the above additives will have better coatability, dry etching resistance, and filling / planarization properties.

[0023] In the present invention, the (B) organic solvent preferably contains one or more organic solvents having a boiling point of 180° C. or higher as the (B1) high-boiling-point solvent.

[0024] By adding a high boiling point solvent to the compound for forming a metal-containing film, thermal fluidity is imparted to the compound for forming a metal-containing film, and the composition for forming a metal-containing film also has higher filling / planarizing properties.

[0025] In the present invention, it is preferable that the metal-containing film-forming composition further contains (G) metal oxide nanoparticles having an average primary particle size of 100 nm or less.

[0026] In this case, the (G) metal oxide nanoparticles are preferably selected from the group consisting of zirconium oxide nanoparticles, hafnium oxide nanoparticles, titanium oxide nanoparticles, tin oxide nanoparticles, and tungsten oxide nanoparticles.

[0027] By using such metal oxide nanoparticles, it is possible to easily increase the metal content in the composition, and further improve the dry etching resistance of the metal-containing film-forming composition.

[0028] In the present invention, it is preferable that the metal-containing film-forming composition further contains a flowability promoter (BP) having an organic group and an aromatic ring, which is represented by the following general formula (3). [ka] (In the general formula (3), * represents a bonding site to an oxygen atom, and R B is a divalent organic group having 1 to 10 carbon atoms, R A is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.

[0029] By adding a flow promoter (BP) to the above-mentioned metal-containing film-forming compound to impart heat resistance and thermal flowability, the metal-containing film-forming composition also has even more advanced filling / planarizing properties.

[0030] In this case, it is preferable that the flow promoter (BP) has at least one structural unit represented by the following general formulas (BP-1), (BP-2), (BP-3), (BP-4) and (BP-5). [ka] In general formulas (BP-1) and (BP-2), W1 and W2 each independently represent a benzene ring or a naphthalene ring, and the hydrogen atoms in the benzene ring and the naphthalene ring may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. R a is a group represented by the following formula (4). Y' is a group represented by the following formula (5). n1 is 0 or 1, n2 is 1 or 2, and each V independently represents a hydrogen atom or a linking moiety. [ka] (In general formula (BP-3), Z1 is a group represented by the following general formula (6), and R a is a group represented by the following formula (4), where n4 is 0 or 1, n5 is 1 or 2, and each V independently represents a hydrogen atom or a linking moiety. [ka] (In formula (4), * represents a bond to an oxygen atom.) [ka] (In formula (5), * represents a bond.) [ka] (In the general formula (6), W1, W2, Y', and n1 are the same as above.) [ka] In general formula (BP-4), m3 and m4 represent 1 or 2, and Z represents a single bond or a structure represented by the following general formula (7). R x is any of the structures represented by the following general formula (8). [ka] (In the general formula (7), * represents a bond, 1 represents an integer of 0 to 3, and R a ~R f each independently represents a hydrogen atom, an optionally fluorine-substituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or a phenylethyl group; R a and R b may be bonded to form a cyclic compound.) [ka] (In general formula (8), * represents a bonding site to the aromatic ring, and Q1 is a linear saturated hydrocarbon group having 1 to 30 carbon atoms, or a structure represented by the following general formula (9).) [ka] (In the general formula (9), * represents a bonding site to a carbonyl group, and R i is a group represented by the formula (4). j represents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. n3 and n4 represent the number of substituents on the aromatic ring, and each represents an integer of 0 to 7, provided that n3 + n4 is 0 or more and 7 or less. n5 represents 0 to 2. [ka] (In general formula (BP-5), R 1 is a saturated monovalent organic group having 1 to 30 carbon atoms or an unsaturated monovalent organic group having 2 to 30 carbon atoms, X is a divalent organic group having 1 to 30 carbon atoms, and R ais a group represented by the formula (4), where p is an integer of 0 to 5, q1 is an integer of 1 to 6, p+q1 is an integer of 1 or more and 6 or less, and q2 is 0 or 1.

[0031] A metal-containing film-forming composition to which a flowability promoter (BP) having at least one of the structural units (BP-1) to (BP-5) above has been added will have better filling / planarizing properties.

[0032] The present invention also provides a method for forming a pattern on a substrate to be processed, comprising the steps of: (I-1) a step of applying the above-described composition for forming a metal-containing film 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 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 the pattern to the metal-containing film by dry etching using the resist upper layer film on which the pattern has been 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:

[0033] By using the pattern forming method using the two-layer resist process, a fine pattern can be formed on a workpiece (substrate).

[0034] The present invention also provides a method for forming a pattern on a substrate to be processed, comprising the steps of: (II-1) A step of applying the above-described composition for forming a metal-containing film onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (II-2) forming a silicon-containing resist intermediate film on the metal-containing film; (II-3) forming a resist upper layer film on the silicon-containing resist intermediate film using a photoresist material; (II-4) 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; (II-5) a step of transferring the pattern to the silicon-containing resist intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (II-6) a step of transferring a pattern to the metal-containing film by dry etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; and (II-7) 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:

[0035] The pattern formation method using the three-layer resist process described above makes it possible to form a fine pattern on a workpiece with high precision.

[0036] The present invention also provides a method for forming a pattern on a substrate to be processed, comprising the steps of: (III-1) A step of applying the above-described composition for forming a metal-containing film onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (III-2) forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the metal-containing film; (III-3) forming an organic thin film on the inorganic hard mask intermediate film; (III-4) forming a resist top layer film on the organic thin film using a photoresist material; (III-5) 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; (III-6) a step of transferring the pattern to the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (III-7) transferring a pattern to the metal-containing film by dry etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; and (III-8) 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:

[0037] The pattern formation method using the four-layer resist process described above makes it possible to form a fine pattern on a workpiece with high precision.

[0038] In this case, the inorganic hard mask intermediate film is preferably formed by a CVD method or an ALD method.

[0039] When the inorganic hard mask intermediate film is formed by the CVD method or the ALD method, a fine pattern can be formed on the workpiece with higher precision.

[0040] The present invention also provides a method for forming a pattern on a substrate to be processed, comprising the steps of: (IV-1) A step of applying the above-described composition for forming a metal-containing film onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (IV-2) forming a resist underlayer film on the metal-containing film; (IV-3) forming a silicon-containing resist intermediate film or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film on the resist underlayer film; (IV-4) forming a resist upper layer film on the silicon-containing resist intermediate film or the organic thin film using a photoresist material; (IV-5) 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; (IV-6) a step of transferring a pattern to the silicon-containing resist intermediate film or the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (IV-7) a step of transferring a pattern to the resist underlayer film by dry etching using the silicon-containing resist interlayer film or inorganic hard mask interlayer film to which the pattern has been transferred as a mask; (IV-8) a step of transferring a pattern to the metal-containing film by dry etching using the resist underlayer film to which the pattern has been transferred as a mask; and (IV-9) 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:

[0041] By using the pattern forming method using the multilayer resist process, a fine pattern can be formed on a workpiece with high precision.

[0042] The present invention also provides a method for forming a pattern on a substrate to be processed, comprising the steps of: (V-1) forming a resist underlayer film on a substrate to be processed; (V-2) forming a resist intermediate film or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film on the resist underlayer film; (V-3) forming a resist upper layer film using a photoresist material on the resist intermediate film or the combination of the inorganic hard mask intermediate film and the organic thin film; (V-4) 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; (V-5) a step of transferring a pattern to the resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film, by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (V-6) a step of transferring a pattern to the resist underlayer film by dry etching using the resist interlayer film or inorganic hard mask interlayer film to which the pattern has been transferred as a mask; (V-7) a step of applying the above-described composition for forming a metal-containing film onto the resist underlayer film on which the pattern has been formed, followed by heat treatment to cover the resist underlayer film with a metal-containing film and filling spaces between the resist underlayer film patterns with the metal-containing film; (V-8) a step of etching back the metal-containing film covering the resist underlayer film on which the pattern has been formed by a chemical stripper or dry etching to expose the upper surface of the resist underlayer film on which the pattern has been formed; (V-9) a step of removing the resist intermediate film or the inorganic hard mask intermediate film remaining on the upper surface of the resist underlayer film by dry etching; (V-10) a step of removing the resist underlayer film on which the pattern is formed and the surface is exposed by dry etching, thereby forming a reverse pattern of the original pattern on the metal-containing film; (V-11) A step of processing the substrate to be processed using the metal-containing film on which the reverse pattern has been formed as a mask to form a reverse pattern on the substrate to be processed. The present invention provides a tone-reversal pattern formation method having the steps of:

[0043] The pattern forming method using the above-described reversal process makes it possible to form a fine pattern on a workpiece with even higher precision. [Effects of the Invention]

[0044] As explained above, the compound for forming a metal-containing film of the present invention has a multidentate ligand containing one or more of the crosslinking groups represented by general formulas (a-1) to (a-4) and (b-1) to (b-4). Therefore, when this compound is used in a composition for forming a metal-containing film, it is possible to provide a material for forming a metal-containing film that exhibits small volume shrinkage during baking and has excellent planarization and filling properties even after high-temperature baking.

[0045] In particular, in fine patterning processes using multilayer resist methods in semiconductor device manufacturing processes, this material can be filled without causing defects such as voids or peeling, even on substrates that have areas that are difficult to fill / planarize, such as dense areas of high-aspect ratio fine pattern structures such as those in DRAM memories, which are becoming increasingly miniaturized.In addition, it has superior dry etching resistance compared to conventional coating-type resist underlayer film materials, making it possible to form fine patterns on the workpiece with even greater precision than with resist underlayer films. [Brief explanation of the drawings]

[0046] [Figure 1] FIG. 1 is an explanatory diagram of an example of the pattern forming method of the present invention (three-layer resist process). [Figure 2] FIG. 2 is an explanatory diagram of an example of the tone reversal pattern forming method of the present invention (reversal of the SOC pattern in a three-layer resist process). [Figure 3] FIG. 3 is an explanatory diagram of the embedding characteristic evaluation method. [Figure 4] FIG. 4 is an explanatory diagram of a method for evaluating flattening characteristics. DETAILED DESCRIPTION OF THE INVENTION

[0047] As described above, there has been a need for the development of a metal-containing film-forming composition that has excellent embedding ability and flatness and is used to form a resist underlayer film that can transfer a resist pattern to a substrate to be processed with higher precision in a fine patterning process using a multilayer resist method, a metal-containing film-forming compound useful for the composition, and a pattern formation method using the composition.

[0048] The present inventors have focused on metal materials that exhibit superior etching resistance compared to conventional resist underlayer film materials and conducted extensive research. However, conventional metal compounds for forming resist underlayer films have poor heat resistance and undergo rapid volumetric shrinkage during baking, making it difficult to fill in and flatten uneven surfaces on a substrate to be processed after high-temperature baking. The present inventors believed that compounds containing organic groups with excellent heat resistance would be able to reduce rapid volumetric shrinkage during baking and improve thermal fluidity, thereby enabling the filling of uneven surfaces on a substrate to be processed without generating voids even after high-temperature baking. Furthermore, they hypothesized that a structure containing a crosslinking group at the terminal would provide excellent thermosetting properties during baking, resulting in a compound for forming a metal-containing film with even better heat resistance.

[0049] The inventors further conducted extensive research and discovered that a compound for forming a metal-containing film containing a multidentate ligand containing one or more of the crosslinking groups represented by general formulas (a-1) to (a-4) and (b-1) to (b-4) has excellent thermosetting properties, thereby reducing rapid volume shrinkage during baking, and also has good thermal fluidity, thereby achieving advanced filling / planarization properties, and thus completed the present invention.

[0050] That is, the present invention provides a metal-containing film-forming compound used in a metal-containing film-forming composition, comprising: The compound for forming a metal-containing film contains at least one metal atom selected from the group consisting of Ti, Zr, and Hf and one or more ligands derived from compounds represented by the following general formulas (1-A) to (1-D): [ka] (In the general formulas (1-A) to (1-D), R1 to R3 are hydrogen atoms or monovalent organic groups having 1 to 20 carbon atoms which may contain a crosslinking group represented by the following general formulas (a-1) to (a-4) and (b-1) to (b-4); R4 to R5 are hydrogen atoms or monovalent organic groups having 1 to 20 carbon atoms which may contain a crosslinking group represented by the following general formulas (a-1) to (a-4); R6 to R9 are hydrogen atoms or monovalent organic groups having 1 to 20 carbon atoms which may contain a crosslinking group represented by the following general formulas (a-1) to (a-4) and (b-1) to (b-4); R 10 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and Y is a divalent organic group having 1 to 10 carbon atoms. The compounds of general formulas (1-A) to (1-D) contain one or more bridging groups represented by general formulas (a-1) to (a-4) and (b-1) to (b-4). In general formula (1-B), R4 and R5 may be bonded to each other to form an unsaturated or saturated ring structure. [ka] (In general formulas (a-1) to (a-4), Ra represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.) [ka] (In general formulas (b-1) to (b-4), R' b is a hydrogen atom or a methyl group, and in the same formula, they may be the same or different from each other; R' c represents a hydrogen atom, 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.

[0051] The present invention will be described in detail below, but the present invention is not limited thereto.

[0052] <Compounds for forming metal-containing films> The compound for forming a metal-containing film of the present invention is a compound for forming a metal-containing film that contains at least one metal atom selected from the group consisting of Ti, Zr, and Hf and one or more ligands derived from compounds represented by the following general formulas (1-A) to (1-D): [ka] (In the general formulas (1-A) to (1-D), R1 to R3 are hydrogen atoms or monovalent organic groups having 1 to 20 carbon atoms which may contain a crosslinking group represented by the following general formulas (a-1) to (a-4) and (b-1) to (b-4); R4 to R5 are hydrogen atoms or monovalent organic groups having 1 to 20 carbon atoms which may contain a crosslinking group represented by the following general formulas (a-1) to (a-4); R6 to R9 are hydrogen atoms or monovalent organic groups having 1 to 20 carbon atoms which may contain a crosslinking group represented by the following general formulas (a-1) to (a-4) and (b-1) to (b-4); R 10 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and Y is a divalent organic group having 1 to 10 carbon atoms. The compounds of general formulas (1-A) to (1-D) contain one or more bridging groups represented by general formulas (a-1) to (a-4) and (b-1) to (b-4). In general formula (1-B), R4 and R5 may be bonded to each other to form an unsaturated or saturated ring structure. [ka] (In general formulas (a-1) to (a-4), Ra represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.) [ka] (In general formulas (b-1) to (b-4), R' b is a hydrogen atom or a methyl group, and in the same formula, they may be the same or different from each other; R' c represents a hydrogen atom, 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.

[0053] In the above general formula (1-A), R1 to R3 are each a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a bridging group represented by the above general formulae (a-1) to (a-4) and (b-1) to (b-4); R1 and R3 are preferably an alkyl group having 1 to 10 carbon atoms or a monovalent organic group having 1 to 20 carbon atoms which contains a bridging group represented by the above general formulae (a-1) to (a-4) and (b-1) to (b-4); and R2 is preferably a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which contains a bridging group represented by the above general formulae (a-1) to (a-4) and (b-1) to (b-4).

[0054] In the above general formula (1-B), R4 and R5 are each a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms which may contain a bridging group represented by the above general formulas (a-1) to (a-4), and it is preferable that R4 is a hydrogen atom and R5 is a monovalent organic group having 1 to 20 carbon atoms which contains a bridging group represented by the above general formulas (a-1) to (a-4), or a structure represented by the following formula: [ka] (In the formula, R5' is a monovalent organic group having 1 to 20 carbon atoms and containing a crosslinking group represented by the above general formulae (a-1) to (a-4).)

[0055] In the above general formulas (1-C) to (1-D), R6 to R9 are each a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms and optionally containing a bridging group represented by the above general formulas (a-1) to (a-4) and (b-1) to (b-4), and R6 and R8 are preferably a hydrogen atom, and R7 and R9 are preferably a monovalent organic group having 1 to 20 carbon atoms and containing a bridging group represented by the above general formulas (a-1) to (a-4) and (b-1) to (b-4).

[0056] In the above general formula (1-C), R 10 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom or a methyl group.

[0057] In the above general formula (1-D), Y is a divalent organic group having 1 to 10 carbon atoms, preferably a divalent hydrocarbon group having 1 to 10 carbon atoms, and from the viewpoint of availability of raw materials, more preferably a hydrocarbon group having 1 to 5 carbon atoms, further preferably a methylene group or an ethylene group, and particularly preferably an ethylene group.

[0058] In the above general formulas (b-1) and (b-3), R' b is a hydrogen atom or a methyl group, and in the same formula, they may be the same or different from each other. In the above general formulas (b-3) and (b-4), R' c is a hydrogen atom, 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 R' is b , R' c Preferably, both are hydrogen atoms.

[0059] Among the structures of the general formulae (b-1) to (b-4), the following structures are more preferred, but not limited to these: From the viewpoint of thermosetting properties, the structures of the following formulae (Wa) and (Wb) are particularly preferred. [ka]

[0060] The structure of formula (Wa) or (Wb) has more crosslinking groups, and therefore provides a metal-containing film with superior thermosetting properties. When this structure is used in a metal-containing film-forming composition, volume shrinkage during high-temperature baking can be reduced, and a metal-containing film-forming material with excellent filling / planarization properties can be provided.

[0061] Since the compounds represented by the general formulae (1-A) to (1-D) above contain one or more crosslinking groups represented by the general formulae (a-1) to (a-4) and (b-1) to (b-4) above, when a metal-containing film-forming compound containing one or more polydentate ligands derived therefrom is used in a metal-containing film-forming composition, volume shrinkage during high-temperature baking can be reduced, and a metal-containing film-forming material with excellent filling / planarization properties can be provided.

[0062] Examples of the structure of the ligand derived from the compound represented by the above general formula (1-A) include the following compounds, but the present invention is not limited to these. [ka] (In the above formula, X1 and X2 represent a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.)

[0063] [ka] (In the above formula, X1 and X2 represent a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.)

[0064] [ka] (In the above formula, R 2 represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and X1 and X2 represent a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.

[0065] [ka] (In the above formula, R' c represents a hydrogen atom, 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 X1 and X2 represent a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.

[0066] The following compounds can be given as examples of the structure of the ligand derived from the compound represented by the above general formula (1-B), but the present invention is not limited to these. [ka] (In the above formula, R d represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.

[0067] [ka]

[0068] Examples of the structure of the ligand derived from the compound represented by the above general formula (1-C) include the following compounds, but the present invention is not limited to these. [ka] (In the above formula, X1 and X2 represent a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.)

[0069] [ka] (In the above formula, X1 and X2 represent a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.)

[0070] [ka] (In the above formula, R' c represents a hydrogen atom, 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 X1 and X2 represent a hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.

[0071] The following compounds can be given as examples of the structure of the ligand derived from the compound represented by the above general formula (1-D), but the present invention is not limited to these. [ka] (In the above formula, Y is a divalent organic group having 1 to 10 carbon atoms.)

[0072] [ka] (In the above formula, Y is a divalent organic group having 1 to 10 carbon atoms.)

[0073] From the viewpoint of heat resistance, it is preferable that the ligand derived from the compound represented by the above general formulas (1-A) to (1-D) contains one or more structures selected from an aromatic ring, a heteroaromatic ring, and an alicyclic structure.

[0074] When the ligand contains one or more structures selected from an aromatic ring, a heteroaromatic ring, and an alicyclic structure, the heat resistance of the metal-containing film-forming compound is improved, and a metal-containing film with excellent embedding properties can be formed.

[0075] The compound for forming a metal-containing film is preferably a compound for forming a metal-containing film that further contains a ligand derived from a silicon compound represented by the following general formula (2). [ka] (In general formula (2), R 3A , R 3B and R 3C is any organic group selected from an organic group having 1 to 30 carbon atoms and a crosslinking group having any of the structures represented by the following general formulas (c-1) to (c-3), a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. [ka] (In general formulas (c-1) to (c-3), R'3 represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.)

[0076] In the above general formula (2), R 3A , R 3B and R 3C is any one of organic groups selected from an organic group having 1 to 30 carbon atoms and a crosslinking group having any of the structures represented by the above general formulas (c-1) to (c-3), a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, and is more preferably an organic group having 1 to 30 carbon atoms and a crosslinking group having any of the structures represented by the above general formulas (c-1) to (c-3) or an unsubstituted alkyl group having 1 to 10 carbon atoms. Among the unsubstituted alkyl groups having 1 to 10 carbon atoms, a methyl group or an ethyl group is more preferred.

[0077] In the above general formulae (c-1) to (c-3), R'3 each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and q each independently represents 0 or 1.

[0078] When the compound for forming a metal-containing film contains a ligand derived from the silicon compound represented by the general formula (2), the storage stability of the compound for forming a metal-containing film can be improved.

[0079] From the viewpoint of thermosetting properties, it is more preferable that the ligand derived from the silicon compound represented by the above general formula (2) has any of the structures represented by the following general formula (2A). [ka] (In the above general formula (2A), R 3D and R 3E represents an organic group selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms and aryl groups having 6 to 20 carbon atoms, R'3 is the same as above, and s is 1 to 10.

[0080] In the above general formula (2A), R 3D and R 3Eis more preferably a methyl group from the viewpoint of raw material availability.

[0081] In the compound for forming a metal-containing film, when both the ligand derived from the compound represented by any one of the general formulas (1-A) to (1-D) and the ligand derived from the silicon compound contain a crosslinking group, the thermosetting properties of the compound for forming a metal-containing film can be further improved, and when this compound is used in a composition for forming a metal-containing film, it becomes possible to form a metal-containing film with excellent filling / planarization properties.

[0082] The metal-containing film-forming compound may be modified with ligands derived from compounds represented by the general formulas (1-A) to (1-D) having different structures on the metal atom, or with ligands derived from silicon compounds, and can be appropriately adjusted according to the required properties. Furthermore, the compound may have a ligand other than a polydentate ligand or a ligand derived from a silicon compound. For example, it may contain a ligand derived from an alkyl group having 1 to 10 carbon atoms.

[0083] In the metal-containing film-forming compound, the content of the ligands derived from the compounds represented by the general formulas (1-A) to (1-D) is preferably 10 mol % to 90 mol %, more preferably 20 mol % to 80 mol %, of the total amount of ligands coordinated to the metal atom. The content of the ligands derived from silicon compounds is preferably 10 mol % to 90 mol %, more preferably 20 mol % to 80 mol %, of the total amount of ligands coordinated to the metal atom. The content of ligands other than the ligands derived from the compounds represented by the general formulas (1-A) to (1-D) and the ligands derived from silicon compounds, such as ligands derived from alkyl groups having 1 to 10 carbon atoms, is preferably 0 mol % to 50 mol %, more preferably 0 mol % to 20 mol %, of the total amount of ligands coordinated to the metal atom.

[0084] The metal-containing film-forming compound of the present invention may contain a ligand derived from a compound represented by one of the general formulae (1-A) to (1-D) containing a bridging group represented by any of the general formulae (a-1) to (a-4) and (b-1) to (b-4). The synthesis method is not particularly limited. For example, the metal-containing film-forming compound can be produced from a metal alkoxide or acetylacetonate (acac) of the metal by reacting the alkoxide or acac metal with a multidentate ligand. The alkoxide or acac metal may be subjected to a hydrolysis-condensation reaction followed by reaction with a ligand derived from a compound represented by one of the general formulae (1-A) to (1-D). Alternatively, the alkoxide or acac metal may be reacted with a ligand derived from a compound represented by one of the general formulae (1-A) to (1-D) followed by hydrolysis-condensation. If the hydrolysis-condensation reaction is difficult to control, the compound may be reacted with a ligand derived from a compound represented by one of the general formulae (1-A) to (1-D) in a non-aqueous environment. These are preferably adjusted appropriately depending on the properties of the metal-containing film-forming compound and the properties required for the metal-containing film. When a ligand derived from a silicon compound is to be added, it is preferable to react an alkoxide or acac metal with the silicon compound, and then react it with a ligand derived from the compound represented by the above general formulas (1-A) to (1-D). Alternatively, a metal compound containing a ligand derived from the compound represented by the above general formulas (1-A) to (1-D) and a ligand derived from the silicon compound may be hydrolyzed and condensed.

[0085] The optional C1-C10 alkyl groups that can comprise some of the ligands in the metal-containing film-forming compounds can result from the use of residual alkoxides or alkoxide metal precursors, or from the use of C1-C10 alcohols as additional reagents in the preparation of the metal-containing film-forming compounds. The reaction is carried out in a solvent that can dissolve the alkoxide or acac precursor and other reagents. Typical solvents and solvent mixtures contain ester, ether, or alcohol functional groups, such as 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-propyl ether ... Examples include propanol, 4-methyl-2-pentanol, 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.

[0086] <Metal-containing film forming composition> The present invention also provides a metal-containing film-forming composition used in semiconductor manufacturing, the metal-containing film-forming composition containing the above-mentioned (A) metal-containing film-forming compound and (B) organic solvent.

[0087] Such a composition for forming a metal-containing film contains a compound for forming a metal-containing film that has both high thermal fluidity and high thermosetting properties, and therefore can provide a material for forming a metal-containing film that has excellent dry etching resistance compared to conventional resist underlayer film materials and also has high filling / planarization properties.

[0088] Hereinafter, components contained in the metal-containing film-forming composition of the present invention other than the (A) metal-containing film-forming compound will be described.

[0089] <(B) Organic solvent> The (B) organic 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 or disperses the above-mentioned (A) metal-containing film-forming compound, and if contained, the later-described (C) crosslinking agent, (E) surfactant, (F) acid generator, (G) metal oxide nanoparticles having an average primary particle size of 100 nm or less, and other additives.

[0090] Specifically, in Japanese Patent Laid-Open No. 2007-199653

[0091] ~

[0092] The organic solvents described in paragraph 1 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.

[0091] The amount of the organic solvent to be added is preferably in the range of 200 to 10,000 parts by mass, more preferably 250 to 5,000 parts by mass, per 100 parts by mass of the (A) compound for forming a metal-containing film.

[0092] The metal-containing film-forming composition may contain additives such as (C) a crosslinking agent, (E) a surfactant, (F) an acid generator, and (G) metal oxide nanoparticles having an average primary particle size of 100 nm or less, as needed. That is, the metal-containing film-forming composition preferably further contains one or more of (C) a crosslinking agent, (E) a surfactant, and (F) an acid generator, and the metal-containing film-forming composition preferably further contains (G) metal oxide nanoparticles having an average primary particle size of 100 nm or less. Hereinafter, components contained in the composition for forming a metal-containing film of the present invention other than (A) the compound for forming a metal-containing film and (B) the organic solvent will be described.

[0093] <(B1) High-boiling point solvent> In the metal-containing film-forming composition of the present invention, the (B) organic solvent may be used as a mixture of one or more organic solvents having a boiling point of less than 180° C. and one or more organic solvents ((B1) high-boiling-point solvents) having a boiling point of 180° C. or higher. That is, the (B) organic solvent preferably contains one or more organic solvents having a boiling point of 180° C. or higher as the (B1) high-boiling-point solvent.

[0094] The (B1) high-boiling point solvent is not particularly limited as long as it can dissolve or disperse each component of the metal-containing film-forming composition of the present invention, and may be any of hydrocarbons, alcohols, ketones, esters, ethers, chlorinated solvents, etc., but specific examples include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-Hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, n-nonyl acetate, monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol-n-butyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, propylene glycol diacetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,Examples of the diester include 6-hexanediol diacetate, triethylene glycol diacetate, γ-butyrolactone, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, and dibutyl adipate, and these may be used alone or in combination.

[0095] The (B1) high-boiling-point solvent may be appropriately selected from, for example, those listed above, depending on 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, and more preferably 200°C to 300°C. Such a boiling point is unlikely to cause excessively rapid evaporation during baking (heat treatment), thereby ensuring sufficient thermal fluidity during film formation and enabling the formation of a metal-containing film with excellent filling / planarization properties. Furthermore, such a boiling point is unlikely to cause the solvent to remain in the film after baking without volatilizing, thereby eliminating the risk of adversely affecting film properties such as etching resistance.

[0096] When a (B1) 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. This blending amount is preferable because it can impart sufficient thermal fluidity during baking and does not remain in the film, leading to deterioration of film properties such as etching resistance.

[0097] [(C) Crosslinking agent] The metal-containing film-forming composition of the present invention may further contain a (C) crosslinking agent to enhance the curability of the metal-containing film-forming compound and further suppress intermixing with the resist upper layer film. The (C) crosslinking agent is not particularly limited, and a wide variety of known crosslinking agents can be used. Examples include melamine-based crosslinking agents, acrylate-based crosslinking agents, glycoluril-based crosslinking agents, benzoguanamine-based crosslinking agents, urea-based crosslinking agents, β-hydroxyalkylamide-based crosslinking agents, isocyanurate-based crosslinking agents, aziridine-based crosslinking agents, oxazoline-based crosslinking agents, epoxy-based crosslinking agents, and phenol-based crosslinking agents (e.g., methylol or alkoxymethyl-type crosslinking agents of polynuclear phenols). The content of the (C) crosslinking agent is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, per 100 parts by mass of the (A) metal-containing film-forming compound.

[0098] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylated melamine, hexabutoxymethylated melamine, alkoxy- and / or hydroxy-substituted products thereof, and partial self-condensates thereof. A specific example of the acrylate crosslinking agent is dipentaerythritol hexaacrylate. Specific examples of glycoluril crosslinking agents include tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, alkoxy and / or hydroxy substituted products thereof, and partial self-condensates thereof. Specific examples of benzoguanamine-based crosslinking agents include tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, alkoxy- and / or hydroxy-substituted products thereof, and partial self-condensates thereof. Specific examples of urea-based crosslinking agents include dimethoxymethylated dimethoxyethylene urea, its alkoxy and / or hydroxy substituted derivatives, and partial self-condensates thereof. A specific example of the β-hydroxyalkylamide crosslinking agent is N,N,N',N'-tetra(2-hydroxyethyl)adipamide. Specific examples of the isocyanurate crosslinking agent include triglycidyl isocyanurate and triallyl isocyanurate. Specific examples of the aziridine crosslinking agent include 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate]. Specific examples of the oxazoline-based crosslinking agent include 2,2'-isopropylidenebis(4-benzyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), 2,2'-methylenebis-4,5-diphenyl-2-oxazoline, 2,2'-methylenebis-4-phenyl-2-oxazoline, 2,2'-methylenebis-4-tertbutyl-2-oxazoline, 2,2'-bis(2-oxazoline), 1,3-phenylenebis(2-oxazoline), 1,4-phenylenebis(2-oxazoline), and 2-isopropenyloxazoline copolymer. Specific examples of epoxy-based 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.

[0099] Specific examples of polynuclear phenol-based crosslinking agents include compounds represented by the following general formula (XL-1). [ka] (In general formula (XL-1), Q is a single bond or a q'-valent hydrocarbon group having 1 to 20 carbon atoms. R"3 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. q' is an integer of 1 to 5.)

[0100] Q is a single bond or a q'-valent hydrocarbon group having 1 to 20 carbon atoms. q' is an integer of 1 to 5, and more preferably 2 or 3. Specific examples of Q include groups in which q' hydrogen atoms have been removed from methane, ethane, propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, methylpentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylisopropylbenzene, diisopropylbenzene, methylnaphthalene, ethylnaphthalene, and eicosane. R"3 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, an octyl group, an ethylhexyl group, a decyl group, and an eicosanyl group, with a hydrogen atom or a methyl group being preferred.

[0101] Specific examples of the compound represented by the general formula (XL-1) include the following compounds. Among these, hexamethoxymethylated triphenolmethane, triphenolethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene are preferred from the viewpoint of improving the curability and film thickness uniformity of the metal-containing film. R"3 is the same as above. [ka]

[0102] [ka]

[0103] <(E) Surfactant> A surfactant (E) can be added to the metal-containing film-forming composition of the present invention to improve the coating properties during spin coating. Examples of surfactants that can be used include those described in paragraphs

[0142] to

[0147] of JP-A No. 2009-269953. When surfactant (E) is added, the amount of surfactant added is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the compound (A) for forming a metal-containing film.

[0104] <(F) Acid Generator> In the metal-containing film-forming composition of the present invention, an acid generator (F) can be added to further accelerate the curing reaction of the metal-containing film-forming compound (A). The acid generator (F) can be one that generates an acid upon thermal decomposition or one that generates an acid upon light irradiation, and either can be added. Specifically, the materials described in paragraphs

[0061] to

[0085] of JP-A-2007-199653 can be added, but are not limited to these.

[0105] The acid generator (F) can be used alone or in combination of two or more. When the acid generator (F) is added, the amount added is preferably 0.05 to 50 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the compound (A) for forming a metal-containing film.

[0106] <(G) Metal oxide nanoparticles> Furthermore, in order to further improve dry etching resistance, (G) metal oxide nanoparticles can be added to the metal-containing film-forming composition of the present invention. Specifically, metal oxide nanoparticles selected from the group consisting of zirconium oxide nanoparticles, hafnium oxide nanoparticles, titanium oxide nanoparticles, tin oxide nanoparticles, and tungsten oxide nanoparticles are preferred.

[0107] By selecting the above metal oxide nanoparticles, it is possible to form a metal-containing film with better dry etching resistance.

[0108] The (G) metal oxide nanoparticles preferably have an average primary particle size of 100 nm or less, more preferably 50 nm or less, even more preferably 30 nm or less, and particularly preferably 15 nm or less. The average primary particle size of the (G) metal oxide nanoparticles before dispersion in an organic solvent can be determined by directly measuring the size of the primary particles from an electron microscope photograph. Specifically, the minor axis diameter and major axis diameter of each primary particle are measured, and the average is taken as the particle size of that particle. Next, the volume (mass) of each of 100 or more particles is calculated by approximating it to a rectangular parallelepiped of the calculated particle size, and the volume-average particle size is calculated and used as the average particle size. Note that the same results can be obtained using any of a transmission electron microscope (TEM), a scanning electron microscope (SEM), and a scanning transmission electron microscope (STEM).

[0109] Within this particle size range, the metal-containing particles can exhibit good dispersibility in the metal-containing film-forming composition, and can improve the dry etching resistance of the metal-containing film without deteriorating the filling / planarization properties of dense portions of a fine pattern structure.

[0110] When (G) metal oxide nanoparticles are added, the amount added is preferably 5 to 50 parts by mass, more preferably 5 to 30 parts by mass, per 100 parts by mass of (A) the compound for forming a metal-containing film.

[0111] <Other additives> Furthermore, in the metal-containing film-forming composition of the present invention, additives for imparting filling / planarization properties are preferably used, such as liquid additives having a polyethylene glycol or polypropylene glycol structure, or thermally decomposable polymers having a weight loss rate of 40% by mass or more between 30° C. and 250° C. and a weight-average molecular weight of 300 to 200,000. These thermally decomposable polymers preferably contain repeating units having an acetal structure represented by the following general formulas (DP1) and (DP1a):

[0112] [ka] (In general formula (DP1), R'6 is a hydrogen atom or an optionally substituted saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms. Y" is a saturated or unsaturated divalent organic group having 2 to 30 carbon atoms.)

[0113] [ka] (In general formula (DP1a), R 6a is an alkyl group having 1 to 4 carbon atoms. a is a saturated or unsaturated divalent hydrocarbon group having 4 to 10 carbon atoms, which may have an ether bond; and n represents the average number of repeating units and is 3 to 500.

[0114] <Flow promoter (BP)> Furthermore, a flowability promoter (BP) can be added to the metal-containing film-forming composition of the present invention as an additive for imparting filling / planarization properties. The flowability promoter (BP) preferably has an organic group represented by the following general formula (3) and an aromatic ring. That is, the metal-containing film-forming composition preferably further contains a flowability promoter (BP) having an organic group represented by the following general formula (3) and an aromatic ring. [ka] (In the general formula (3), * represents a bonding site to an oxygen atom, and R B is a divalent organic group having 1 to 10 carbon atoms, R A is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.

[0115] The flowability promoter (BP) having the organic group of general formula (3) can impart thermal flowability and thermosetting properties to the metal-containing film-forming compound, and the flowability promoter (BP) having an aromatic ring can mitigate the deterioration of the dry etching resistance of the metal-containing film-forming compound.

[0116] The flow promoter (BP) preferably has at least one structural unit represented by the following general formulas (BP-1), (BP-2), (BP-3), (BP-4) and (BP-5). (Constituent units: BP-1, BP-2 and BP-3) [ka] In general formulas (BP-1) and (BP-2), W1 and W2 each independently represent a benzene ring or a naphthalene ring, and the hydrogen atoms in the benzene ring and the naphthalene ring may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. R a is a group represented by the following formula (4). Y' is a group represented by the following formula (5). n1 is 0 or 1, n2 is 1 or 2, and each V independently represents a hydrogen atom or a linking moiety. [ka] (In general formula (BP-3), Z1 is a group represented by the following general formula (6), and R a is a group represented by the following formula (4), where n4 is 0 or 1, n5 is 1 or 2, and each V independently represents a hydrogen atom or a linking moiety. [ka] (In formula (4), * represents a bond to an oxygen atom.) [ka] (In formula (5), * represents a bond.) [ka] (In the general formula (6), W1, W2, Y', and n1 are the same as above.)

[0117] Resins containing structural units represented by the general formulas (BP-1), (BP-2), and (BP-3) have excellent heat resistance because they incorporate high-carbon-density fused carbon rings containing cardo structures. Because of these characteristics, metal-containing films capable of filling uneven substrates without generating voids can be formed even after high-temperature baking. Furthermore, because they also have excellent dry etching resistance, adding them to the metal-containing film-forming composition of the present invention can impart heat resistance and thermal fluidity without significantly deteriorating the excellent dry etching resistance inherent in the metal-containing film-forming composition.

[0118] The resin having the structural units represented by the above general formulae (BP-1), (BP-2), and (BP-3) can be a compound represented by the following general formulae (bp-1), (bp-2), and / or (bp-3). [ka] (In general formulas (bp-1) and (bp-2), W1, W2, R a , Y', n1, and n2 are the same as above.)

[0119] In the above general formulae (bp-1) and (bp-2), W1, W2, R a , Y', n1, and n2 are as explained above in relation to general formulae (BP-1) and (BP-2).

[0120] [ka] (In general formula (bp-3), Z1, R a , n4, and n5 are the same as above.)

[0121] In the above general formula (bp-3), Z1 and R a , n4, and n5 are as explained above in relation to general formula (BP-3).

[0122] Specific examples of resins having structural units represented by the above general formulae (bp-1), (bp-2) and / or (bp-3) include, but are not limited to, the following compounds. [ka] (In the formula, R a is the same as above.)

[0123] The resins (bp-1), (bp-2) and (bp-3) preferably have a ratio Mw / Mn (i.e., dispersity) of the weight average molecular weight Mw to the number average molecular weight Mn in terms of polystyrene, as determined by gel permeation chromatography, within the range of 1.00≦Mw / Mn≦1.25, and more preferably 1.00≦Mw / Mn≦1.10.

[0124] A compound having a dispersity within such a range can provide a metal-containing film-forming composition with better thermal fluidity, and when blended into a material, can provide a metal-containing film-forming composition with better embedding / planarization properties.

[0125] The resin having the structural units represented by the above general formulae (BP-1), (BP-2), and (BP-3) can be a polymer having repeating units represented by the following general formulae (bp-4), (bp-5), and / or (bp-6). [ka] (In general formulas (bp-4) and (bp-5), W1, W2, R a Y', n1, and n2 are the same as above, and L is a divalent organic group having 1 to 40 carbon atoms.

[0126] In the above general formulae (bp-4) and (bp-5), W1, W2, R a , Y', n1, and n2 are as explained above in relation to general formulae (BP-1) and (BP-2).

[0127] [ka] (In general formula (bp-6), Z1, R a n4 and n5 are the same as above, and L is a divalent organic group having 1 to 40 carbon atoms.

[0128] In the above general formula (bp-6), Z1 and R a , n4, and n5 are as explained above in relation to general formula (BP-3).

[0129] These polymers are obtained using the compounds represented by the general formulas (bp-1), (bp-2), and (bp-3), and because they use the compounds, they have excellent dry etching resistance and heat resistance. In addition, because they are polymers having repeating units rather than monomers, they have low outgassing components, and because they are polymers with molecular weight distribution, crystallinity is alleviated, and improved film formability can be expected.

[0130] L, which is a linking group constituting the repeating units of the above general formulae (bp-4), (bp-5) and (bp-6), is a divalent organic group having 1 to 40 carbon atoms, and specific examples include the following. [ka]

[0131] Furthermore, the linking group L of the polymer is preferably represented by the following general formula (10). [ka] (In general formula (10), R'1 represents a hydrogen atom or an organic group containing an aromatic ring having 6 to 20 carbon atoms, and the dashed line represents a bond.)

[0132] Specific examples of the general formula (10) are as follows, and among the following, a methylene group, that is, R'1 is a hydrogen atom, is preferred in view of the ease of obtaining raw materials. [ka]

[0133] Furthermore, the weight average molecular weight (Mw) of the polymer having repeating structural units represented by the above general formulae (bp-4), (bp-5) and (bp-6) in terms of polystyrene, as determined by gel permeation chromatography, is preferably 1,000 to 12,000, and more preferably 2,000 to 10,000.

[0134] Within this molecular weight range, the solubility in organic solvents can be ensured, the formation of sublimed products during baking can be suppressed, and the thermal fluidity of the metal-containing film-forming composition can be improved, thereby providing a metal-containing film-forming composition with superior embedding and planarization properties when blended into a material.

[0135] (Composition unit: BP-4) [ka] In general formula (BP-4), m3 and m4 represent 1 or 2, and Z represents a single bond or a structure represented by the following general formula (7). R x is any of the structures represented by the following general formula (8). [ka] (In the general formula (7), * represents a bond, 1 represents an integer of 0 to 3, and R a ~R f each independently represents a hydrogen atom, an optionally fluorine-substituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or a phenylethyl group; R a and R b may be bonded to form a cyclic compound.) [ka] (In general formula (8), * represents a bonding site to the aromatic ring, and Q1 is a linear saturated hydrocarbon group having 1 to 30 carbon atoms, or a structure represented by the following general formula (9).) [ka] (In the general formula (9), * represents a bonding site to a carbonyl group, and R i is a group represented by the formula (4). j represents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. n3 and n4 represent the number of substituents on the aromatic ring, and each represents an integer of 0 to 7, provided that n3 + n4 is 0 or more and 7 or less. n5 represents 0 to 2.

[0136] In the general formula (BP-4), m3 and m4 represent 1 or 2, and Z is either a single bond or a structure represented by the general formula (7). x is any of the structures represented by the above general formula (8).

[0137] From the viewpoint of dry etching resistance and heat resistance, in the above general formula (BP-4), Z is preferably either a single bond or a structure represented by the following general formula (4A). [ka] (In general formula (4A), * represents a bond, and l is the same as in general formula (7) above.)

[0138] In the general formula (8), * represents a bonding site to the aromatic ring, and Q1 is a linear saturated hydrocarbon group having 1 to 30 carbon atoms, or a structure represented by the general formula (9). When Q1 represents a linear hydrocarbon group having 1 to 30 carbon atoms, a methylene group constituting Q1 may be substituted with an oxygen atom or a carbonyl group. From the viewpoints of dry etching resistance and heat resistance, Q1 is preferably a structure represented by the general formula (9).

[0139] In the above general formula (9), * represents the bonding site to the carbonyl group, and R i is a group represented by the formula (4). jrepresents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. n3 and n4 represent the number of substituents on the aromatic ring, and each represents an integer of 0 to 7, provided that n3 + n4 is 0 or more and 7 or less. n5 represents 0 to 2.

[0140] Compounds containing the structural unit represented by the general formula (BP-4) have a structure in which aromatic rings are linked by a single bond or general formula (7), and therefore have a high carbon density. Therefore, metal-containing film-forming compositions containing these compounds have excellent heat resistance. Furthermore, as shown in the general formula (7), the linking group Z can be appropriately selected from various linking groups to suit the desired performance. In particular, by introducing the structure represented by the general formula (4A) as Z, heat resistance / etching resistance can be imparted without impairing film-forming properties. Furthermore, the highly flexible terminal portion R x Since the terminal portion R x contains a terminal group Q1 that imparts thermal fluidity, and as the terminal group Q1, a flexible hydrocarbon structure that contributes to improving thermal fluidity and a rigid aromatic ring structure that contributes to etching resistance and heat resistance can be introduced in any ratio according to the required performance. As described above, a metal-containing film-forming composition to which these compounds have been added can achieve both high levels of embedding ability / planarization properties and heat resistance, and can form a thick film according to the required properties.

[0141] (Composition unit: BP-5) [ka] (In general formula (BP-5), R 1 is a saturated monovalent organic group having 1 to 30 carbon atoms or an unsaturated monovalent organic group having 2 to 30 carbon atoms, X is a divalent organic group having 1 to 30 carbon atoms, and R ais a group represented by the formula (4), where p is an integer of 0 to 5, q1 is an integer of 1 to 6, p+q1 is an integer of 1 or more and 6 or less, and q2 is 0 or 1.

[0142] In the general formula (BP-5), examples of the divalent organic group having 1 to 30 carbon atoms represented by X include alkanediyl groups such as methylene, ethanediyl, propanediyl, butanediyl, pentanediyl, hexanediyl, octanediyl, and decanediyl groups; monocyclic cycloalkanediyl groups such as cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, cyclohexanediyl, cycloheptanediyl, cyclooctanediyl, cyclodecanediyl, methylcyclohexanediyl, and ethylcyclohexanediyl groups; bicyclo[2.2.1]heptanediyl, bicyclo[2.2.2]octanediyl, and tricyclo[5.2.1.0]octanediyl groups; 2,6 ]decanediyl group (dicyclopentylene group), tricyclo[3.3.1.1 3,7 ]decanediyl group, tetracyclo[6.2.1.1 3,6 .0 2,7 ] Polycyclic cycloalkanediyl groups such as dodecanediyl group and adamantanediyl group, and arenediyl groups such as phenylene group and naphthylene group.

[0143] Examples of the alkanediyloxy group represented by X include groups formed by combining the above alkanediyl group with an oxygen atom, and examples of the cycloalkanediyloxy group represented by X include groups formed by combining the above cycloalkanediyl group with an oxygen atom.

[0144] Some or all of the hydrogen atoms of the alkanediyl group, cycloalkanediyl group, alkanediyloxy group, cycloalkanediyloxy group, and arenediyl group may be substituted, and examples of the substituent include the above-mentioned R a Examples of the substituent that the organic group represented by the following formula may have include the same groups as those mentioned above.

[0145] Examples of the organic group represented by X include groups represented by the following formulas. [ka] (In the above formula, * represents a bond.)

[0146] From the viewpoint of raw material availability, the organic group represented by X is preferably a methylene group.

[0147] Specific examples of resins having a structural unit represented by the above general formula (BP-5) include the following. [ka] (In the formula, R a is the same as above.)

[0148] [ka] (In the formula, R a is the same as above.)

[0149] Polymers containing structural units represented by the general formula (BP-5) have a structure in which aromatic rings are linked by an organic group X, resulting in high carbon density. Therefore, metal-containing film-forming compositions containing these compounds exhibit high dry etching resistance and excellent heat resistance. Furthermore, because the organic group represented by the formula (4), which contributes to improved thermal fluidity, is directly bonded to the aromatic ring, which is the core structure of the resin, via an oxygen atom, metal-containing film-forming compositions containing these polymers can achieve high levels of both embedding / planarization properties and heat / etching resistance. Furthermore, because the core aromatic ring structure is not too rigid and forms a repeating structure via the organic group X, which is the linking group, metal-containing films can be formed without defects such as cracks.

[0150] In the metal-containing film-forming composition of the present invention, the content of the flow promoter (BP) is preferably 50 mass% or less, more preferably 30 mass% or less, and even more preferably 20 mass% or less, relative to 100 mass parts of the (A) metal-containing film-forming compound.

[0151] The amount of flow promoter (BP) added can be adjusted to any ratio depending on the required properties of the process using the metal-containing film-forming composition of the present invention. If you want to minimize the deterioration of dry etching resistance, you can reduce the ratio of flow promoter (BP). If you want to tolerate some deterioration of dry etching resistance and further improve filling ability / planarization ability, you can increase the ratio of flow promoter (BP).

[0152] <Method for forming resist underlayer film and filling film> The present invention provides a method for forming a filling film that functions as a resist underlayer film of a multilayer resist film used in lithography or a planarizing film for semiconductor manufacturing, using the above-mentioned metal-containing film-forming composition.

[0153] In the method for forming a resist underlayer film using the metal-containing film-forming composition of the present invention, the metal-containing film-forming composition is coated onto a substrate to be processed by spin coating or the like. By using spin coating or the like, excellent embedding properties can be obtained. After spin coating, the solvent is evaporated, and baking (heat treatment) is performed to promote crosslinking reactions and prevent mixing with the resist top layer film or resist intermediate film. Baking is preferably performed at 100°C or higher and 600°C or lower for 10 to 600 seconds, more preferably 200°C or higher and 500°C or lower for 10 to 300 seconds. Considering the effects on device damage and wafer deformation, the upper limit of the heating temperature in lithography wafer processing is preferably 600°C or lower, more preferably 500°C or lower.

[0154] Furthermore, in a method for forming a resist underlayer film using the metal-containing film-forming composition of the present invention, the metal-containing film-forming composition 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 metal-containing film-forming composition can be baked and cured in an atmosphere with an oxygen concentration of 0.1% by volume or more and 21% by volume or less, thereby forming a metal-containing film as a resist underlayer film.

[0155] By baking the metal-containing film-forming composition of the present invention in such an oxygen atmosphere, a sufficiently cured film can be obtained. Although air can be used as the atmosphere during baking, it is preferable to seal in an inert gas such as N2, Ar, or He to reduce the oxygen content and prevent oxidation of the metal-containing film. To prevent oxidation, the oxygen concentration must be controlled, preferably to 1,000 ppm or less, more preferably 100 ppm or less (volume basis). Preventing oxidation of the metal-containing film during baking is preferable because it prevents increased absorption and reduced etching resistance.

[0156] The filling film formation method can be the same as the resist underlayer film formation method described above.

[0157] <Pattern Forming Method Using Metal-Containing Film-Forming Composition> Further, in the present invention, a pattern formation method by a two-layer resist process using the above-mentioned metal-containing film-forming composition is a method for forming a pattern on a substrate to be processed, comprising the steps of: (I-1) a step of applying the above-described composition for forming a metal-containing film 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 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 the pattern to the metal-containing film by dry etching using the resist upper layer film on which the pattern has been 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:

[0158] The resist top layer film in the two-layer resist process exhibits etching resistance to chlorine-based gases, and therefore, in the two-layer resist process, dry etching of the metal-containing film using the resist top layer film as a mask is preferably performed using an etching gas mainly containing a chlorine-based gas.

[0159] Further, in the present invention, a pattern formation method by a three-layer resist process using such a metal-containing film-forming composition is a method for forming a pattern on a substrate to be processed, comprising the steps of: (II-1) A step of applying the above-described composition for forming a metal-containing film onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (II-2) forming a silicon-containing resist intermediate film on the metal-containing film; (II-3) forming a resist upper layer film on the silicon-containing resist intermediate film using a photoresist material; (II-4) 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; (II-5) a step of transferring the pattern to the silicon-containing resist intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (II-6) a step of transferring a pattern to the metal-containing film by dry etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; and (II-7) 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:

[0160] A pattern formation method using a three-layer resist process will be described with reference to Figure 1. In the present invention, the pattern formation method using such a three-layer resist process using a metal-containing film-forming composition involves forming a metal-containing film 3 on a processable layer 2 on a processable substrate 1 using the metal-containing film-forming composition, forming a silicon-containing resist intermediate film 4 on the metal-containing film using a silicon-containing resist intermediate film material, and forming a resist upper layer film 5 on the silicon-containing resist intermediate film using a photoresist material, as shown in Figure 1(A). Next, as shown in FIG. 1(B), the exposed portion 6 of the resist top layer film is pattern-exposed, and then developed with a developer as shown in FIG. 1(C) to form a resist top layer film pattern 5a on the resist top layer film; as shown in FIG. 1(D), using the patterned resist top layer film as a mask, a silicon-containing resist intermediate film pattern 4a is transferred to the silicon-containing resist intermediate film by dry etching; as shown in FIG. 1(E), using the patterned silicon-containing resist intermediate film as a mask, a metal-containing film pattern 3a is transferred to the metal-containing film by dry etching; and as shown in FIG. 1(F), a pattern forming method is provided in which the processable layer on the processable substrate is processed using the patterned metal-containing film as a mask, thereby forming a pattern 2a on the processable substrate 1.

[0161] The silicon-containing resist intermediate film in the three-layer resist process exhibits etching resistance to chlorine-based gases. Therefore, in the three-layer resist process, the dry etching of the metal-containing film using the silicon-containing resist intermediate film as a mask is preferably performed using an etching gas mainly containing a chlorine-based gas.

[0162] Polysiloxane-based interlayers are also preferred as the silicon-containing resist interlayer in the three-layer resist process. By providing the silicon-containing resist interlayer with anti-reflection properties, reflection can be reduced. For 193 nm exposure, in particular, using an organic film containing many aromatic groups and exhibiting high etching selectivity with the substrate results in a high k value and high substrate reflection. However, by providing the silicon-containing resist interlayer with an absorption that results in an appropriate k value, reflection can be reduced, reducing substrate reflection to 0.5% or less. For silicon-containing resist interlayers with anti-reflection properties, anthracene is preferred for 248 nm and 157 nm exposure, while for 193 nm exposure, polysiloxanes with pendant light-absorbing groups containing phenyl groups or silicon-silicon bonds and crosslinked by acid or heat are preferred.

[0163] In addition, in the present invention, a pattern formation method by a four-layer resist process using such a metal-containing film-forming composition is provided, forming a metal-containing film on a substrate to be processed using the composition for forming a metal-containing film; forming a silicon-containing resist intermediate film on the metal-containing film using a silicon-containing resist intermediate film material; forming an organic antireflective coating (BARC) or an adhesion film on the silicon-containing resist intermediate film; forming a resist top layer film on the BARC or the adhesion film using a photoresist material; the resist upper layer film is pattern-exposed and then developed with a developer to form a pattern on the resist upper layer film; Using the resist upper layer film on which the pattern has been formed as a mask, the pattern is transferred to the BARC or the adhesion film and the silicon-containing resist intermediate film by dry etching; using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask, transferring the pattern to the metal-containing film by dry etching; The present invention provides a pattern forming method, which includes a step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask, thereby forming a pattern on the substrate to be processed.

[0164] In addition, an inorganic hard mask intermediate film may be formed instead of the silicon-containing resist intermediate film. In this case, at least forming a metal-containing film on a substrate to be processed using the composition for forming a metal-containing film of the present invention; forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the metal-containing film; forming a resist upper layer film on the inorganic hard mask intermediate film using a photoresist composition, and forming a circuit pattern on the resist upper layer film; transferring the pattern to the inorganic hard mask intermediate film using the resist upper layer film on which the pattern has been formed as a mask; transferring a pattern to the metal-containing film using the patterned inorganic hard mask intermediate film as a mask; Furthermore, by 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 semiconductor device circuit pattern can be formed on the substrate.

[0165] In the present invention, there is provided a method for forming a pattern on a substrate to be processed, comprising the steps of: (III-1) A step of applying the above-described composition for forming a metal-containing film onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (III-2) forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the metal-containing film; (III-3) forming an organic thin film on the inorganic hard mask intermediate film; (III-4) forming a resist top layer film on the organic thin film using a photoresist material; (III-5) 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; (III-6) a step of transferring the pattern to the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (III-7) transferring a pattern to the metal-containing film by dry etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; and (III-8) 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:

[0166] As described above, when forming an inorganic hard mask intermediate film on a metal-containing film, a silicon oxide film, a silicon nitride film, or a silicon oxynitride film (SiON film) can be formed by a CVD method, an ALD method, or the like. For example, methods for forming a silicon nitride film are described in JP 2002-334869 A and WO 2004 / 066377 A. The thickness of the inorganic hard mask intermediate film is preferably 5 to 200 nm, more preferably 10 to 100 nm. Furthermore, a SiON film, which is highly effective as an anti-reflective coating, is most preferably used as the inorganic hard mask intermediate film. Since the substrate temperature during SiON film formation is 300 to 500°C, the metal-containing film must be able to withstand temperatures of 300 to 500°C. The metal-containing film-forming composition used in the present invention has high heat resistance and can withstand high temperatures of 300 to 500°C, making it possible to combine an inorganic hard mask intermediate film formed by a CVD method or an ALD method with a metal-containing film formed by a spin-coating method.

[0167] As described above, a photoresist film can be formed as a resist top layer on the inorganic hard mask intermediate film. Alternatively, an organic antireflective coating (BARC) or adhesion film can be formed on the inorganic hard mask intermediate film by spin coating, and then a photoresist film can be formed on top of that. In particular, when a SiON film is used as the inorganic hard mask intermediate film, the two-layer antireflective coating consisting of the SiON film and the BARC can suppress reflection even in immersion exposure with a high NA exceeding 1.0. Another advantage of forming a BARC is that it reduces the footing of the photoresist pattern directly above the SiON film.

[0168] In the pattern formation method, the resist top layer film may be either positive or negative, and the same photoresist composition as commonly used may be used. The photoresist composition may also contain metal atoms such as Sn, In, Ga, Ge, Al, Ce, La, Cs, Zr, Hf, Ti, Bi, Sb, and Zn. When forming the resist top layer film using the photoresist composition, it may be formed by spin coating or by vapor deposition using CVD or ALD.

[0169] When forming a photoresist upper layer film by spin coating, the resist is prebaked after application, preferably at 60 to 180°C for 10 to 300 seconds. Then, exposure is performed according to a conventional method, followed by post-exposure baking (PEB) and development to obtain a resist pattern. The thickness of the resist upper layer film is not particularly limited, but is preferably 10 to 500 nm, and more preferably 20 to 400 nm.

[0170] When forming a resist top layer film by deposition processing using a CVD method or an ALD method, the photoresist composition is an EUV-sensitive metal oxide-containing film, and the metal is selected from Sn, Zr, Hf, Ti, Bi, Sb, etc., with Sn being preferred due to its excellent EUV sensitivity. The metal oxide-containing film may be a photosensitive organometallic oxide film such as an organotin oxide (e.g., haloalkyltin, alkoxyalkyltin, or amidoalkyltin). Specific examples of suitable precursors include trimethyltin chloride, dimethyltin dichloride, methyltin trichloride, tris(dimethylamino)methyltin(IV), and (dimethylamino)trimethyltin(IV).

[0171] Metal oxide-containing films may be deposited by PECVD or PEALD, for example, using a Lam Vector® tool. In the ALD example, the Sn oxide precursor is separated from the O precursor / plasma. The deposition temperature is preferably in the range of 50°C to 600°C. The deposition pressure is preferably between 100 and 6,000 mTorr. The metal oxide-containing film precursor liquid flow rate (e.g., organotin oxide precursor) may be 0.01 to 10 cm / s, and the gas flow rate (CO2, CO, Ar, N2) may be 100 to 10,000 sccm. The plasma power may be 200 to 1,000 W per 300 mm wafer station using a high frequency plasma (e.g., 13.56 MHz, 27.1 MHz, or higher). The deposition thickness is preferably 100 to 2,000 Å.

[0172] Examples of exposure light include high energy rays with a wavelength of 300 nm or less, specifically excimer lasers with wavelengths of 248 nm, 193 nm, and 157 nm, soft X-rays with wavelengths of 3 to 20 nm, electron beams, and X-rays.

[0173] The method for forming a pattern on the resist upper layer film is preferably photolithography with a wavelength of 5 nm or more and 300 nm or less, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[0174] In the pattern forming method, the development method is preferably alkaline development or development using an organic solvent.

[0175] Next, etching is performed using the obtained resist pattern as a mask. In the three-layer resist process, etching of the silicon-containing resist intermediate film or inorganic hard mask intermediate film is performed using a fluorocarbon-based gas and the resist upper layer film pattern as a mask. This forms a silicon-containing resist intermediate film pattern or an inorganic hard mask intermediate film pattern.

[0176] Next, the metal-containing film is etched using the silicon-containing resist intermediate film pattern or inorganic hard mask intermediate film pattern as a mask, preferably using an etching gas mainly containing a chlorine-based gas.

[0177] The next step, etching of the substrate to be processed, can also be done using standard methods. For example, if the substrate to be processed is made of SiO2, SiN, or a silica-based low-k insulating film, etching is done using mainly fluorocarbon gases. When etching the substrate with fluorocarbon gases, the silicon-containing resist intermediate film pattern in the three-layer resist process is peeled off at the same time as the substrate is processed.

[0178] The metal-containing film obtained using the metal-containing film-forming composition of the present invention is characterized by excellent etching resistance when etching the substrate to be processed.

[0179] The workpiece (substrate) is not particularly limited, and may be a substrate such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, or Al, or a substrate with a workpiece layer formed thereon. The workpiece layer may be a low-k film or a stopper film thereof, such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, or Al-Si, and may be formed to a thickness of typically 50 to 10,000 nm, particularly 100 to 5,000 nm. When forming a workpiece layer, the substrate and workpiece layer are made of different materials.

[0180] The pattern formation method using the metal-containing film-forming composition of the present invention preferably uses a substrate to be processed having structures or steps with a height of 30 nm or more. As described above, the metal-containing film-forming composition of the present invention has excellent filling / planarization properties, so that a flat metal-containing film can be formed even if the substrate to be processed has structures or steps (unevenness) with a height of 30 nm or more. The height of the structures or steps on the substrate to be processed is preferably 30 nm or more, more preferably 50 nm or more, and even more preferably 100 nm or more. In the method for processing a stepped substrate having a pattern with the above height, forming a film using the metal-containing film-forming composition of the present invention and performing filling / planarization makes it possible to uniformize the film thickness of the subsequently formed resist intermediate film and resist top layer film, which is highly preferable, as it makes it easier to ensure a depth of exposure margin (DOF) during photolithography.

[0181] Furthermore, in the present invention, a pattern formation method by a four-layer resist process using such a metal-containing film-forming composition includes: forming a metal-containing film on a substrate to be processed using the composition for forming a metal-containing film; forming an organic underlayer film on the metal-containing film using an organic resist underlayer film material; forming a silicon-containing resist intermediate film on the organic underlayer film using a silicon-containing resist intermediate film material; If necessary, an organic anti-reflective coating (BARC) or an adhesion film is formed on the silicon-containing resist intermediate film; forming a resist upper layer film on the silicon-containing resist intermediate film, the BARC, or the adhesion film using a photoresist material; the resist upper layer film is pattern-exposed and then developed with a developer to form a pattern on the resist upper layer film; Using the resist upper layer film on which the pattern has been formed as a mask, the pattern is transferred to the BARC or the adhesion film and the silicon-containing resist intermediate film by dry etching; using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask, to transfer the pattern to the organic underlayer film by dry etching; transferring a pattern to the metal-containing film using the organic underlayer film as a mask; The present invention provides a pattern forming method, which includes a step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask, thereby forming a pattern on the substrate to be processed.

[0182] Organic resist underlayer film materials that can be used for the organic underlayer film include those already known as underlayer films for three-layer resist methods or two-layer resist methods using silicon resist compositions, such as the 4,4'-(9-fluorenylidene)bisphenol novolac resin (molecular weight 11,000) described in JP 2005-128509 A, as well as many other resins, including novolac resins, that are known as resist underlayer film materials for two-layer and three-layer resist methods. Furthermore, if higher heat resistance than conventional novolacs is desired, a polycyclic skeleton such as 6,6'-(9-fluorenylidene)-di(2-naphthol) novolac resin can be incorporated, and polyimide-based resins can also be selected (for example, JP 2004-153125 A).

[0183] The organic underlayer film can be formed on a substrate to be processed by spin coating or the like using a composition solution, similar to the case of a photoresist composition. After forming the organic 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 80 to 400°C, and the baking time is preferably in the range of 10 to 300 seconds.

[0184] Instead of the organic underlayer film, an organic hard mask formed by the CVD method or the ALD method can also be used.

[0185] The organic intermediate film in the above multilayer resist process exhibits etching resistance to chlorine-based gases. Therefore, in the above multilayer resist process, dry etching of the metal-containing film using the organic intermediate film as a mask is preferably performed using an etching gas mainly containing a chlorine-based gas.

[0186] Further, in the present invention, a pattern formation method by a four-layer resist process using such a metal-containing film-forming composition is a method for forming a pattern on a substrate to be processed, comprising the steps of: (IV-1) A step of applying the above-described composition for forming a metal-containing film onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (IV-2) forming a resist underlayer film on the metal-containing film; (IV-3) forming a silicon-containing resist intermediate film or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film on the resist underlayer film; (IV-4) forming a resist upper layer film on the silicon-containing resist intermediate film or the organic thin film using a photoresist material; (IV-5) 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; (IV-6) a step of transferring a pattern to the silicon-containing resist intermediate film or the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (IV-7) a step of transferring a pattern to the resist underlayer film by dry etching using the silicon-containing resist interlayer film or inorganic hard mask interlayer film to which the pattern has been transferred as a mask; (IV-8) a step of transferring a pattern to the metal-containing film by dry etching using the resist underlayer film to which the pattern has been transferred as a mask; and (IV-9) 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:

[0187] <Method for forming a tone-reversal pattern using a composition for forming a metal-containing film> Further, in the present invention, a tone-reversal pattern forming method using such a metal-containing film-forming composition is a method for forming a pattern on a workpiece substrate, the method comprising: (V-1) forming a resist underlayer film on a substrate to be processed; (V-2) forming a resist intermediate film or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film on the resist underlayer film; (V-3) forming a resist upper layer film using a photoresist material on the resist intermediate film or the combination of the inorganic hard mask intermediate film and the organic thin film; (V-4) 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; (V-5) a step of transferring a pattern to the resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film, by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (V-6) a step of transferring a pattern to the resist underlayer film by dry etching using the resist interlayer film or inorganic hard mask interlayer film to which the pattern has been transferred as a mask; (V-7) a step of applying the above-described composition for forming a metal-containing film onto the resist underlayer film on which the pattern has been formed, followed by heat treatment to cover the resist underlayer film with a metal-containing film and filling spaces between the resist underlayer film patterns with the metal-containing film; (V-8) a step of etching back the metal-containing film covering the resist underlayer film on which the pattern has been formed by a chemical stripper or dry etching to expose the upper surface of the resist underlayer film on which the pattern has been formed; (V-9) a step of removing the resist intermediate film or the inorganic hard mask intermediate film remaining on the upper surface of the resist underlayer film by dry etching; (V-10) a step of removing the resist underlayer film on which the pattern is formed and the surface is exposed by dry etching, thereby forming a reverse pattern of the original pattern on the metal-containing film; (V-11) A step of processing the substrate to be processed using the metal-containing film on which the reverse pattern has been formed as a mask to form a reverse pattern on the substrate to be processed. The present invention provides a tone-reversal pattern formation method having the steps of:

[0188] A tone-reversal pattern formation method using a metal-containing film-forming composition will be described with reference to Figure 2. In the tone-reversal pattern formation method using such a metal-containing film-forming composition, as shown in Figure 2(G), a resist underlayer film 7 is formed on a processable layer 2 on a processable substrate 1, a resist intermediate film 4 or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film is formed on the resist underlayer film 7, and a resist upper layer film 5 is formed on the resist intermediate film 4 or the combination of the inorganic hard mask intermediate film and the organic thin film using a photoresist material.Subsequently, as shown in FIG. 2(H), the exposed portion 6 of the resist upper layer film is pattern-exposed, and then developed with a developer as shown in FIG. 2(I), to form a resist upper layer film pattern 5a on the resist upper layer film. As shown in FIG. 2(J), using the resist upper layer film on which the pattern has been formed as a mask, a resist intermediate film pattern 4a or an inorganic hard mask intermediate film pattern is transferred to the resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film, by dry etching. As shown in FIG. 2(K), using the resist intermediate film or inorganic hard mask intermediate film on which the pattern has been transferred as a mask, a resist underlayer film pattern 7a is transferred to the resist underlayer film by dry etching. As shown in FIG. 2(L), the resist underlayer film on which the pattern has been formed is coated with a metal-containing film 8 using the metal-containing film-forming composition, and a metal-containing film 8 is formed between the resist underlayer film patterns 7a. 2(M), the metal-containing film covering the resist underlayer film on which the pattern is formed is etched back using a chemical stripper or dry etching to form an inverted metal-containing film pattern 8a, exposing the top surface of the resist underlayer film on which the pattern is formed, removing the resist interlayer film or inorganic hard mask interlayer film remaining on the top surface of the resist underlayer film pattern 7a by dry etching as shown in FIG. 2(N), removing the exposed surface of the resist underlayer film on which the pattern is formed by dry etching as shown in FIG. 2(O), forming an inverted pattern of the original pattern in the metal-containing film, and processing the workpiece using the metal-containing film on which the inverted pattern is formed as a mask to form an inverted pattern 2b in the workpiece layer as shown in FIG. 2(P).

[0189] As described above, when forming a resist underlayer film on a substrate to be processed, the resist underlayer film can be formed by a method using a coating-type resist underlayer film material, a CVD method, an ALD method, or the like. Coating-type resist underlayer film materials include those described in JP 2012-001687 A, JP 2012-077295 A, JP 2004-264710 A, JP 2005-043471 A, JP 2005-250434 A, JP 2007-293294 A, JP 2008-065303 A, JP 2004-205685 A, JP 2007-171895 A, JP 2009-014816 A, JP 2007-199653 A, JP 2008-274250 A, JP 2010-122656 A, JP 2012 -214720, JP 2014-029435, WO 2012 / 077640, WO 2010 / 147155, WO 2012 / 176767, JP 2005-128509, JP 2006-259249, JP 2006-259482, JP 2006-293298, JP 2007-316282, JP 2012-145897, JP 2017-119671, JP 2019-044022 and the like.

[0190] In the tone reversal pattern formation method, after the obtained resist underlayer film pattern is coated with a metal-containing film-forming composition, the metal-containing film is preferably removed using a dry etching gas mainly containing a chlorine-based gas to expose the upper surface of the resist underlayer film pattern. Then, the resist intermediate film or inorganic hard mask intermediate film remaining on the resist underlayer film is removed by dry etching with a fluorocarbon-based gas, and the exposed surface of the resist underlayer film pattern is removed by dry etching with an oxygen-based gas to form the metal-containing film pattern.

[0191] In the tone reversal patterning method, the resist underlayer film pattern preferably has structures or steps with a height of 30 nm or more. As described above, the metal-containing film-forming composition of the present invention has excellent filling / planarization properties, making it possible to form a flat metal-containing film even if the film to be processed has structures or steps (unevenness) with a height of 30 nm or more. The height of the structures or steps in the resist underlayer film pattern is preferably 30 nm or more, more preferably 50 nm or more, and even more preferably 100 nm or more. In a method for reversing a resist underlayer film pattern having a pattern with the above height, forming a film using the metal-containing film-forming composition of the present invention and performing filling / planarization enables high-precision pattern reversal / transfer, which is highly preferred. Compared to resist underlayer films made using conventional coating-type resist underlayer film materials, the metal-containing film-forming composition has superior dry etching resistance using fluorocarbon-based gases. Therefore, by reversing the resist underlayer film pattern with the metal-containing film-forming composition, a desired resist pattern can be formed on the film to be processed with high precision. [Example]

[0192] The present invention will be explained in more detail below by showing synthesis examples, comparative synthesis examples, examples, and comparative examples, but the present invention is not limited to these.

[0193] [Synthesis example] In the following synthesis examples, the following organic group raw materials G: (G1) to (G18) and silicon-containing organic group raw materials H: (H1) to (H5) were used. The organic group raw materials G: (G1) to (G18) are shown below. [ka]

[0194] The silicon-containing organic group raw materials H: (H1) to (H5) are shown below. [ka]

[0195] As the metal raw material M, the following metal compounds were used. (M1): Titanium tetraisopropoxide (Sigma-Aldrich Corp, 377996) (M2): Titanium butoxide tetramer (Fujifilm Wako Pure Chemical Industries, Ltd.) (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(IV) diisopropoxybis(2,4-pentanedionate) (75% by mass solution in isopropyl alcohol) (Tokyo Chemical Industry Co., Ltd., B3395)

[0196] [Synthesis Example 1] Synthesis of metal-containing film-forming compound (A-1) Under a nitrogen atmosphere, a solution of 1.6 g of deionized water and 24.2 g of IPA was added dropwise to 12.1 g of an IPA solution containing 33.4 g of titanium tetraisopropoxide (M1) over 2 hours at room temperature while stirring. To the resulting solution, 16.6 g of organic group raw material group (G1) was added and stirred at room temperature for 30 minutes. This solution was concentrated under reduced pressure at 30°C and then further heated to 60°C and continued to be heated under reduced pressure until no more distillate was produced. When no more distillate was observed, 69.0 g of a PGMEA / PGME (70 / 30 mass ratio) solution was added and heated under reduced pressure at 40°C until no more IPA was produced, yielding a PGMEA / PGME solution of the metal-containing film-forming compound (A-1). The concentration of components other than the solvent in the solution was 20% by mass.

[0197] [Synthesis Examples 2 to 4] Synthesis of metal-containing film-forming compounds (A-2) to (A-4) The metal-containing film-forming compounds (A-2) to (A-4) shown in Table 1 were obtained under the same reaction conditions as in Synthesis Example 1, except that the metal raw material M and the organic group raw material group G were used in the amounts shown in Table 1. [Table 1]

[0198] [Synthesis Example 5] Synthesis of metal-containing film-forming compound (A-5) Under a nitrogen atmosphere, 11.8 g of tetrabutyl orthotitanate (M5) was dissolved in 20.6 g of a PGMEA / PGME (70 / 30 mass ratio) solution. The reaction temperature was raised to 50°C while stirring, and 6.5 g of silicon-containing organic group raw material group (H1) was added dropwise to the solution. After the dropwise addition, the reaction temperature was raised to 60°C and stirring was continued for 2 hours. Next, a mixture prepared by suspending 4.8 g of organic group raw material group (G5) in 8.6 g of a PGMEA / PGME (70 / 30 mass ratio) solution was added to the reaction system, and stirring was continued for 1 hour while maintaining 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 the metal-containing film-forming compound (A-5). The concentration of components other than the solvent in the solution was 23% by mass.

[0199] [Synthesis Examples 6 to 20] Synthesis of metal-containing film-forming compounds (A-6) to (A-20) The metal-containing film-forming compounds (A-6) to (A-20) shown in Table 2 were obtained under the same reaction conditions as in Synthesis Example 5, except that the metal raw material M, the organic group raw material group G, and the silicon-containing organic group raw material group H were used in the amounts shown in Table 2. [Table 2]

[0200] [Comparative example metal-containing film forming compound (R-1)] Titanium(IV) diisopropoxybis(2,4-pentanedionate) (75% by mass solution in isopropyl alcohol) was used as the comparative metal-containing film-forming compound (R-1).

[0201] [Comparative Synthesis Example 1] Synthesis of a metal-containing film-forming compound (R-2) for comparison The titanium compound reported in Example 1 of Japanese Patent Publication No. 6323456 was synthesized. Under a nitrogen atmosphere, 20 g of pure water was added dropwise to 180 g of a propylene glycol monoethyl ether solution containing 51 g of a 75% by weight solution of titanium(IV) diisopropoxybis(2,4-pentanedionate) (M6) in isopropyl alcohol over 10 minutes while stirring. The mixture was then allowed to react at 60°C for 2 hours, cooled to room temperature, and 250 g of propylene glycol monoethyl ether was added. The IPA was then removed by vacuum concentration using a rotary evaporator, yielding a propylene glycol monoethyl ether solution of a comparative metal-containing film-forming compound (R-2). The concentration of components other than the solvent in the solution was 12% by weight.

[0202] [Comparative Synthesis Example 2] Synthesis of a metal-containing film-forming compound (R-3) for comparison The titanium compound reported in Example 1 of Japanese Patent No. 6578092 was synthesized. Under a nitrogen atmosphere, 0.33 equivalents of tris(2-hydroxyethyl)isocyanurate (Tokyo Chemical Industry Co., Ltd., T0674) was added to 100 g of a 75% by mass solution of titanium(IV) diisopropoxybis(2,4-pentanedionate) (M6) in isopropyl alcohol, and the mixture was stirred at 120°C for 1 day. The solution was then concentrated under reduced pressure, and the solid crystallized in 500 g of heptane was vacuum-dried to obtain a comparative metal-containing film-forming compound (R-3).

[0203] Comparative Synthesis Example 3: Synthesis of a metal-containing film-forming compound (R-4) for comparison The titanium compound reported in [Synthesis Example A-II] of Japanese Patent No. 6189758 was synthesized. Under a nitrogen atmosphere, a solution of 284 g of titanium tetraisopropoxide (M1) in 500 g of IPA was added dropwise over 2 hours at room temperature while stirring. 120 g of 2-methyl-2,4-pentanediol was added to the resulting solution and stirred at room temperature for 30 minutes. The solution was concentrated under reduced pressure at 30°C and then further heated to 60°C and continued to be heated under reduced pressure until no more distillate was produced. When no more distillate was observed, 1,200 g of PGMEA was added, and the mixture was heated at 40°C under reduced pressure until no more IPA was produced, yielding 1,000 g of a PGMEA solution of the metal-containing film-forming compound (R-4) for comparison (compound concentration: 20% by mass).

[0204] Comparative Synthesis Example 4: Synthesis of a comparative metal-containing film-forming compound (R-5) The zirconium compound reported in [Synthesis Example 1-1] of WO 2020 / 241712 was synthesized. Under a nitrogen atmosphere, diethanolamine (molar ratio 2) was added dropwise to zirconium (IV) tetrabutoxide (80% by mass 1-butanol solution) (M3) (molar ratio 1) at room temperature over 30 minutes while stirring, and the mixture was stirred at 60 ° C for 2 hours. The reaction solution was then cooled to room temperature and diluted with 1-butanol (900 parts by mass). Water (molar ratio 0.75) was added dropwise to the cooled reaction solution at room temperature over 10 minutes while stirring. A hydrolysis condensation reaction was then carried out at 60 ° C for 2 hours. After the reaction was completed, the resulting reaction solution was cooled to room temperature, propylene glycol monoethyl ether (1,000 parts by mass) was added, and the water and 1-butanol were removed using an evaporator to obtain a PGEE solution of the comparative metal-containing film-forming compound (R-5) (compound concentration 8.1% by mass).

[0205] [Comparative Synthesis Example 5] Synthesis of a metal-containing film-forming compound (R-6) for comparison The zirconium compound reported in [Synthesis Example 4] of Japanese Patent No. 6311702 was synthesized. In a nitrogen atmosphere, 38 g of zirconium(IV) tetrabutoxide (80% by mass solution in 1-butanol) (M3) and 50 g of propylene glycol monomethyl ether were mixed and stirred at room temperature for 10 minutes. Then, 9.2 g of glycerin was added and heated and stirred at 100°C for 4 hours. After the reaction was completed, the mixture was cooled to room temperature, and 20 g of 1,3-acetonedicarboxylate diethyl carboxylate and 200 g of γ-butyrolactone were added. Low-boiling points were then removed using an evaporator to obtain a GBL solution of the metal-containing film-forming compound (R-6) for comparison (compound concentration 9.8% by mass).

[0206] [Comparative Synthesis Example 6] Synthesis of Comparative Organic Film-Forming Resin (R-7) Under a nitrogen atmosphere, 160.2 g of 1,5-dihydroxynaphthalene, 56.8 g of formaldehyde, and 300 g of PGME (propylene glycol monomethyl ether) were added and homogenized at an internal temperature of 100°C. A pre-mixed mixture of 8.0 g of paratoluenesulfonic acid monohydrate and 8.0 g of PGME was then slowly added dropwise, and the reaction was carried out at an internal temperature of 80°C for 8 hours. After the reaction was completed, the mixture was cooled to room temperature, 2,000 ml of MIBK was added, and the mixture was washed six times with 500 ml of purified water. The organic layer was evaporated to dryness under reduced pressure. 300 g of THF was added to the residue to form a homogenous solution, which was then crystallized in 2,000 g of hexane. The precipitated crystals were separated by filtration, washed twice with 500 g of hexane, and then recovered. The recovered crystals were dried in vacuo at 70°C to obtain a comparative organic film-forming resin (R-7). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent, and the following results were obtained. (R-7): Mw = 3,300, Mw / Mn = 2.54 [ka]

[0207] (Synthesis of Flow Promoters) The flow promoter was synthesized using the organic group raw material group G: (G19) to (G21) and modifying agent K: (K1) to (K2) shown below. The organic group raw materials G: (G19) to (G21) are shown below. [ka]

[0208] The modifying agents K: (K1) to (K2) are shown below. [ka]

[0209] [Synthesis of flow promoter (BPA-1)] Under a nitrogen atmosphere, 45.5 g of organic group raw material group (G19), 9.8 g of potassium carbonate, and 150 g of DMF were added and a uniform dispersion was obtained at an internal temperature of 50°C. 17.6 g of modifying agent (K1) was slowly added, and the reaction was carried out at an internal temperature of 50°C for 24 hours. 300 ml of methyl isobutyl ketone and 300 g of pure water were added to the reaction solution to dissolve the precipitated salt, and the separated aqueous layer was then removed. The organic layer was further washed six times with 100 g of 3% aqueous nitric acid solution and 100 g of pure water, and then evaporated to dryness under reduced pressure to obtain flow promoter (BPA-1). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (BPA-1): Mw = 965, Mw / Mn = 1.08 [ka]

[0210] [Synthesis of flow promoter (BPA-2)] 80.0 g of organic group raw material group (G20), 51.0 g of modifying agent (K2), and 600 g of 2-methoxy-1-propanol were mixed under a nitrogen atmosphere at an internal temperature of 100°C to form a homogeneous solution, and then 5.7 g of benzyltriethylammonium chloride was added and stirred at an internal temperature of 120°C for 12 hours. After cooling to room temperature, 1,500 g of methyl isobutyl ketone was added, and the organic layer was washed five times with 300 g of pure water. The organic layer was evaporated to dryness under reduced pressure to obtain a flow promoter (BPA-2). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (BPA-2): Mw=900, Mw / Mn=1.04 [ka]

[0211] [Synthesis of flow promoter (BPA-3)] Under a nitrogen atmosphere, 20.0 g of organic group raw material group (G21), 34.5 g of potassium carbonate, and 100 g of DMF were added and a uniform dispersion was obtained at an internal temperature of 50°C. 23.8 g of modifying agent (K1) was slowly added, and the reaction was carried out at an internal temperature of 50°C for 24 hours. 300 ml of methyl isobutyl ketone and 300 g of pure water were added to the reaction solution to dissolve the precipitated salt, and the separated aqueous layer was then removed. The organic layer was further washed six times with 100 g of 3% aqueous nitric acid solution and 100 g of pure water, and then evaporated to dryness under reduced pressure to obtain a flow promoter (BPA-3). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (BPA-3): Mw = 9,400, Mw / Mn = 3.59 [ka]

[0212] [Preparation of Metal-Containing Film-Forming Composition (UDL-1)] The metal-containing film-forming compound (A-1) was dissolved in a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) containing 0.5 mass% of surfactant FC-4430 (manufactured by Sumitomo 3M Limited) in the proportions shown in Table 3, and the solution was filtered through a 0.02 μm membrane filter to prepare a metal-containing film-forming composition (UDL-1).

[0213] [Preparation of Metal-Containing Film-Forming Compositions (UDL-2 to 24) and Comparative Metal-Containing Film-Forming Compositions (Comparative UDL-1 to 7)] Each composition was prepared in the same manner as UDL-1, except that the type and content of each component were as shown in Table 3. In Table 3, "-" indicates that the corresponding component was not used. The crosslinking agent used was the formula (C-1) below, the acid generator (TAG) used was the formula (F-1) below, the high-boiling point solvent (B-1) used was ethylene glycol dibenzyl ether (boiling point 364°C), and the metal nanoparticles (G-1) used were ZrO2 nanoparticles (5 nm core, 915505 Sigma-Aldrich Corp).

[0214] [Crosslinking agent, acid generator] The crosslinking agent (C-1) and the acid generator (F-1) used in the metal-containing film-forming composition are shown below. [ka] [ka]

[0215] [Table 3]

[0216] [Evaluation of Filling Characteristics (Examples 1-1 to 1-24, Comparative Examples 1-1 to 1-7)] Each of the compositions (UDL-1 to 24 and Comparative Examples UDL-1 to 7) prepared above was applied to a SiO2 wafer substrate with a dense line and space pattern (line width 60 nm, line depth 100 nm, center-to-center distance 120 nm) and heated at 350 °C for 60 seconds using a hot plate to form a metal-containing film with a thickness of 80 nm. The substrate used was a base substrate 9 (SiO2 wafer substrate) with a dense line and space pattern as shown in Figure 3(Q) (overhead view) and (R) (cross-sectional view). The cross-sectional shape of each wafer substrate obtained in the filling evaluation was observed using an electron microscope (S-4700, manufactured by Hitachi, Ltd.) to confirm the presence of voids (air gaps) within the metal-containing film filling the gaps between the lines. The results are shown in Table 4. When a metal-containing film-forming composition with poor filling properties was used, voids were generated within the metal-containing film filling the gaps between the lines in this evaluation. When a metal-containing film-forming composition with good filling properties is used, in this evaluation, a void-free metal-containing film 10 is filled inside the metal-containing film that fills the spaces between the lines of a base substrate 9 having a dense line-and-space pattern, as shown in Figure 3(S).

[0217] [Table 4]

[0218] As shown in Table 4, in Examples 1-1 to 1-24, which used the metal-containing film-forming compositions (UDL-1 to UDL-24) of the present invention, dense line and space patterns could be filled without voids even after baking at 350°C, confirming that the compositions have good filling properties even under high-temperature baking conditions. On the other hand, in Comparative Examples 1-1 to 1-6, which used Comparative Examples UDL-1 to UDL-6, which used metal compounds that, unlike the metal-containing film-forming compounds of the present invention, do not contain any of the crosslinking groups represented by general formulas (a-1) to (a-4) or (b-1) to (b-4), voids were observed at the bottom of the patterns after baking at 350°C. It is presumed that these voids were generated because the organic ligands coordinated to the metal had low heat resistance, resulting in large volume shrinkage upon high-temperature baking.

[0219] [Evaluation of Planarization Characteristics (Examples 2-1 to 2-24, Comparative Example 2-1)] For the base substrate 11 (SiO2 wafer substrate) having a dense line and space pattern as shown in Figure 4(T), the cross-sectional shape of each wafer substrate in which no voids were observed in the above-mentioned filling evaluation after baking at 350°C as shown in Figure 4(U) was observed using a scanning electron microscope (SEM), and the step (Delta 12 in Figure 4(U)) between the dense line pattern area and the non-line pattern area of ​​the filling film 12 was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd. The results are shown in Table 5. In this evaluation, the smaller the step, the better the planarization characteristics. [Table 5]

[0220] As shown in Table 5, Examples 2-1 to 2-24, which used the metal-containing film-forming compositions of the present invention (UDL-1 to 24), exhibited small film step differences between patterned and non-patterned areas, demonstrating comparable planarization performance to Comparative Example 2-1, which used an organic resist underlayer film material (Comparative Example UDL-7). Comparing UDL-5 to 7, which varied in the content of crosslinkable organic ligand, the higher the crosslinkable organic ligand content, the better the planarization performance. Furthermore, UDL-3, 4, 6, 7, 8, 9, 13, 14, and 15, which contain aromatic ring-containing ligands, exhibited excellent planarization, likely due to their superior heat resistance. Furthermore, UDL-21, which contained a high-boiling point solvent (B-1), and UDL-22 to 24, which contained flow promoters (BPA-1 to 3), exhibited superior planarization performance compared to the unadded compositions. It is believed that the addition of additives further improved the thermal flowability of the metal-containing film-forming compositions.

[0221] [Etching Resistance Evaluation (Examples 3-1 to 3-24, Comparative Example 3-1)] The metal-containing film-forming compositions (UDL-1 to 24, and comparative example UDL-7) were applied to silicon substrates and heated at 350°C for 60 seconds using a hot plate to form metal-containing films with a thickness of 80 nm, and the film thickness a was measured. Next, etching was performed using CF4 gas under the following conditions using a ULVAC etching system CE-300I, and the film thickness b was measured. The etching rate (nm / min) was calculated as the film thickness etched per minute from the film thickness etched over the specified time (film thickness a - film thickness b). The results are shown in Table 6.

[0222] Dry etching conditions with CF4 gas Pressure: 1Pa Antenna RF power: 100W Bias RF power: 15W CF4 gas flow rate: 15sccm Time: 30sec [Table 6]

[0223] As shown in Table 6, Examples 3-1 to 3-24, which used the metal-containing film-forming compositions of the present invention (UDL-1 to 24), were found to exhibit extremely excellent etching resistance to CF4 gas compared to Comparative Example 3-1, which used an organic resist underlayer film material (Comparative Example UDL-7).

[0224] [Pattern Forming Method (Examples 4-1 to 4-24, Comparative Example 4-1)] The above metal-containing film-forming compositions (UDL-1 to 24, Comparative Example UDL-7) were each applied to a SiO2 wafer substrate with a trench pattern (trench width 10 μm, trench depth 0.10 μm) and baked in air at 350 °C for 60 seconds to form an 80 nm thick metal-containing film. A silicon-containing resist interlayer material (SOG-1) was applied on top of the substrate and baked at 220 °C for 60 seconds to form a 50 nm thick resist interlayer. An ArF single-layer resist top layer material was then applied on top of that and baked at 105 °C for 60 seconds to form a 100 nm thick photoresist film. An immersion protective film material (TC-1) was applied on top of the photoresist film and baked at 90 °C for 60 seconds to form a 50 nm thick protective film.

[0225] The silicon-containing resist interlayer material (SOG-1) was prepared by dissolving a polymer designated as ArF silicon-containing interlayer polymer (SiP1) and a thermal crosslinking catalyst (CAT1) in an organic solvent containing 0.1 mass% of FC-4430 (manufactured by Sumitomo 3M) in the proportions shown in Table 7, and filtering the solution through a fluororesin filter with a pore size of 0.1 μm.

[0226] [Table 7]

[0227] The structural formulae of the ArF silicon-containing intermediate film polymer (SiP1) and thermal crosslinking catalyst (CAT1) used are shown below. [ka]

[0228] The resist top layer material (ArF single-layer resist) was prepared by dissolving a polymer (RP1), an acid generator (PAG1), and a basic compound (Amine1) in the proportions shown in Table 8 in a solvent containing 0.1 mass% of surfactant FC-4430 (Sumitomo 3M Limited), and filtering the solution through a 0.1 μm fluororesin filter.

[0229] [Table 8]

[0230] 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]

[0231] 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 the solution through a 0.1 μm fluororesin filter.

[0232] [Table 9]

[0233] The protective film polymer (PP1) used in the immersion protective film material (TC-1) is shown below. [ka]

[0234] The resist was then exposed using an ArF immersion exposure system (Nikon Corporation; NSR-S610C, NA 1.30, σ 0.98 / 0.65, 35-degree dipole s-polarized illumination, 6% halftone phase-shift mask), baked at 100°C for 60 seconds (PEB), and developed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds to obtain a 55 nm 1:1 positive line-and-space pattern (resist upper layer film pattern).

[0235] Next, the resist intermediate film was dry-etched using the resist upper layer film pattern as a mask to form a hard mask pattern, the metal-containing film was etched using the resulting hard mask pattern as a mask to form a metal-containing film pattern, and the SiO2 film was etched using the resulting metal-containing film pattern as a mask. The etching conditions are as follows:

[0236] Conditions for transferring the resist upper layer film pattern to the resist intermediate film. Dry etching conditions with CF4 gas Pressure: 1Pa Antenna RF power: 100W Bias RF power: 15W CF4 gas flow rate: 15sccm Time: 60sec

[0237] Conditions for transferring hard mask patterns to metal-containing films. Dry etching conditions using Cl2 gas Pressure: 1Pa Antenna RF power: 320W Bias RF power: 30W Cl2 gas flow rate: 25sccm Time: 45 seconds

[0238] Transfer conditions for metal-containing film pattern onto SiO2 film. Dry etching conditions with CF4 gas Pressure: 1Pa Antenna RF power: 100W Bias RF power: 15W CF4 gas flow rate: 15sccm Time: 60sec

[0239] The cross section of the pattern was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd. The results are shown in Table 10. [Table 10]

[0240] As shown in Table 10, in Examples 4-1 to 4-24, in which the metal-containing film-forming compositions (UDL-1 to 24) of the present invention were used, the resist upper layer film pattern was ultimately transferred successfully to the substrate, confirming that the metal-containing film-forming compositions of the present invention are suitable for use in microfabrication using the multilayer resist method. On the other hand, in Comparative Example 4-1, in which an organic resist underlayer film material (Comparative Example UDL-7) was used that was confirmed to have insufficient performance in the dry etching resistance evaluation, distortion of the pattern shape occurred during pattern processing, and ultimately a good pattern could not be obtained.

[0241] [SOC Pattern Inversion Method (Examples 5-1 to 5-24, Comparative Examples 5-1 to 5-8)] A silicon wafer substrate with a 300 nm SiO2 film was coated with a resist underlayer material (SOC-1) and baked at 350°C for 60 seconds to form an 80 nm thick resist underlayer film. A silicon-containing resist interlayer material (SOG-1) was then coated on top of that and baked at 220°C for 60 seconds to form a 40 nm thick resist interlayer film. A single-layer ArF resist toplayer material was then coated on top of that and baked at 105°C for 60 seconds to form a 100 nm thick photoresist film. An immersion protective film material (TC-1) was then coated on top of the photoresist film and baked at 90°C for 60 seconds to form a 50 nm thick protective film.

[0242] The silicon-containing resist intermediate film material (SOG-1), resist top layer film material (ArF single layer resist), and immersion protective film material (TC-1) on the photoresist film were the same materials as those used in the pattern formation method described above (Example 4).

[0243] A coating-type resist underlayer film material (SOC-1) was prepared by dissolving a polymer indicated as a resist underlayer film polymer (SOP1) and 0.1 mass % of FC-4430 (manufactured by Sumitomo 3M Limited) in an organic solvent in the proportions shown in Table 11, and filtering the resulting solution through a fluororesin filter with a pore size of 0.2 μm.

[0244] [Table 11]

[0245] The structural formula of the resist underlayer film polymer (SOP1) used is shown in Table 12. [Table 12]

[0246] The resist was then exposed using an ArF immersion exposure system (Nikon Corporation; NSR-S610C, NA 1.30, σ 0.98 / 0.65, 35-degree dipole s-polarized illumination, 6% halftone phase-shift mask), baked at 100°C for 60 seconds (PEB), and developed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds to obtain a 55 nm 1:1 positive line-and-space pattern (resist upper layer film pattern).

[0247] Next, the resist intermediate film was dry-etched using a Tokyo Electron etching system, Telius, with the resist upper layer film pattern as a mask to form a hard mask pattern, and the resist lower layer film (SOC-1) was etched using the resulting hard mask pattern as a mask to form a SOC-1 film pattern. The etching conditions are as follows:

[0248] Conditions for transferring the resist upper layer film pattern to the resist intermediate film. Chamber pressure: 50mT RF power (top): 500W RF power (bottom): 300W CF4 gas flow rate: 150sccm CHF3 gas flow rate: 50sccm Time: 20sec

[0249] Conditions for transferring the hard mask pattern to the resist underlayer film. Chamber pressure: 10mT RF power (top): 1,000W RF power (bottom): 300W CO2 gas flow rate: 150sccm CO gas flow rate: 50 sccm N2 gas flow rate: 50sccm H2 gas flow rate: 150sccm Time: 60sec

[0250] Next, the above-mentioned metal-containing film-forming compositions (UDL-1 to 24, Comparative Examples UDL-1 to 7) were applied to the obtained SOC-1 film pattern and baked in air at 350°C for 60 seconds to form a metal-containing film with a thickness of 80 nm. The metal-containing film covering the SOC-1 film pattern was then etched to expose the top surface of the SOC-1 film pattern. The resist intermediate film remaining on the exposed top surface of the SOC-1 film pattern was then removed by etching, and the exposed SOC-1 film pattern was then removed by etching to invert the above pattern onto the metal-containing film. The resulting metal-containing film pattern was used as a mask to etch the SiO2 film. As comparative examples, SiO2 film etching was also performed using the SOC-1 film pattern as a mask without using the metal-containing film-forming composition (Comparative Examples 5 to 8). The etching conditions are as shown below.

[0251] Conditions for etching back the metal-containing film (exposing the SOC-1 film pattern). Pressure: 1Pa Antenna RF power: 320W Bias RF power: 30W Cl2 gas flow rate: 25sccm Time: 15sec

[0252] Removal of the resist intermediate film remaining on the SOC-1 film pattern. Dry etching conditions with CF4 gas Pressure: 1Pa Antenna RF power: 100W Bias RF power: 15W CF4 gas flow rate: 15sccm Time: 45 seconds

[0253] Removal of SOC-1 membrane pattern. Dry etching conditions with O2 gas Pressure: 1Pa Antenna RF power: 300W Bias RF power: 0W O2 gas flow rate: 25sccm Time: 30sec

[0254] Transfer conditions for metal-containing film pattern onto SiO2 film. Dry etching conditions with CF4 gas Pressure: 1Pa Antenna RF power: 100W Bias RF power: 15W CF4 gas flow rate: 15sccm Time: 60sec

[0255] Comparative Example 5-8: Conditions for transferring the SOC-1 film pattern to the SiO2 film. Dry etching conditions with CF4 gas Pressure: 1Pa Antenna RF power: 100W Bias RF power: 15W CF4 gas flow rate: 15sccm Time: 60sec

[0256] The cross section of the pattern was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd. The results are shown in Table 13. [Table 13]

[0257] As shown in Table 13, in Examples 5-1 to 5-24, in which the metal-containing film-forming compositions (UDL-1 to UDL-24) of the present invention were used, the SOC-1 film pattern was accurately reversed in all cases, and the reversed pattern was successfully transferred to the final substrate without pattern collapse. This confirms that the metal-containing film-forming compositions of the present invention are suitable for use in microfabrication using a tone-reversal etching method in a multilayer resist process. On the other hand, in Comparative Example 5-8, in which the SOC-1 film pattern was directly transferred to an SiO2 film, pattern distortion was observed due to insufficient etching resistance of the SOC-1 film. Furthermore, in Comparative Examples 5-1 to 5-6, in which comparative UDL-1 to UDL-6, which were confirmed to have insufficient performance in the filling characteristic evaluation, the metal-containing film did not reach the bottom between the SOC-1 film patterns, making it impossible to reverse the pattern and ultimately failing to obtain a satisfactory reversed pattern. On the other hand, in Comparative Example 5-7, in which comparative UDL-7, which was confirmed to have insufficient performance in the dry etching resistance evaluation, pattern distortion occurred during pattern reversal processing, and ultimately failing to obtain a satisfactory reversed pattern.

[0258] From the above, it has become clear that a metal-containing film-forming composition containing the metal-containing film-forming compound of the present invention has both high filling / planarization properties and dry etching resistance, and is therefore extremely useful as a resist underlayer film material used in a multilayer resist method and as a reversal agent used in a tone reversal etching method, and that the pattern formation method of the present invention using this composition can form fine patterns with high precision even if the workpiece is a substrate having steps.

[0259] The present specification includes the following aspects. [1]: A metal-containing film-forming compound used in a metal-containing film-forming composition, The compound for forming a metal-containing film is characterized in that it contains at least one metal atom selected from the group consisting of Ti, Zr, and Hf and one or more ligands derived from compounds represented by the following general formulas (1-A) to (1-D): [ka] (In the general formulas (1-A) to (1-D), R1 to R3 are hydrogen atoms or monovalent organic groups having 1 to 20 carbon atoms which may contain a crosslinking group represented by the following general formulas (a-1) to (a-4) and (b-1) to (b-4); R4 to R5 are hydrogen atoms or monovalent organic groups having 1 to 20 carbon atoms which may contain a crosslinking group represented by the following general formulas (a-1) to (a-4); R6 to R9 are hydrogen atoms or monovalent organic groups having 1 to 20 carbon atoms which may contain a crosslinking group represented by the following general formulas (a-1) to (a-4) and (b-1) to (b-4); R 10 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and Y is a divalent organic group having 1 to 10 carbon atoms. The compounds of general formulas (1-A) to (1-D) contain one or more bridging groups represented by general formulas (a-1) to (a-4) and (b-1) to (b-4). In general formula (1-B), R4 and R5 may be bonded to each other to form an unsaturated or saturated ring structure. [ka] (In general formulas (a-1) to (a-4), Ra represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.) [ka] (In general formulas (b-1) to (b-4), R' b is a hydrogen atom or a methyl group, and in the same formula, they may be the same or different from each other; R' c represents a hydrogen atom, 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. [2]: The compound for forming a metal-containing film according to [1] above, characterized in that the ligand derived from the compound represented by any one of the general formulae (1-A) to (1-D) contains one or more structures selected from an aromatic ring, a heteroaromatic ring, and an alicyclic structure. [3]: The compound for forming a metal-containing film according to [1] or [2] above, characterized in that the compound for forming a metal-containing film further contains a ligand derived from a silicon compound represented by the following general formula (2): [ka] (In general formula (2), R 3A , R 3B and R 3C is any organic group selected from an organic group having 1 to 30 carbon atoms and a crosslinking group having any of the structures represented by the following general formulas (c-1) to (c-3), a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. [ka] (In general formulas (c-1) to (c-3), R'3 represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.) [4]: A composition for forming a metal-containing film used in semiconductor manufacturing, characterized in that it contains (A) a compound for forming a metal-containing film according to any one of [1] to [3] above, and (B) an organic solvent. [5]: The composition for forming a metal-containing film according to [4] above, further comprising one or more of (C) a crosslinking agent, (E) a surfactant, and (F) an acid generator. [6]: The metal-containing film-forming composition according to [4] or [5], wherein the (B) organic solvent contains one or more organic solvents having a boiling point of 180°C or higher as (B1) high-boiling-point solvents. [7]: The composition for forming a metal-containing film according to any one of [4] to [6] above, characterized in that the composition for forming a metal-containing film further contains (G) metal oxide nanoparticles having an average primary particle size of 100 nm or less. [8]: The metal-containing film-forming composition according to [7] above, wherein the (G) metal oxide nanoparticles are selected from the group consisting of zirconium oxide nanoparticles, hafnium oxide nanoparticles, titanium oxide nanoparticles, tin oxide nanoparticles, and tungsten oxide nanoparticles. [9]: The composition for forming a metal-containing film according to any one of [4] to [8] above, characterized in that the composition for forming a metal-containing film further contains a flowability promoter (BP) having an organic group and an aromatic ring represented by the following general formula (3): [ka] (In the general formula (3), * represents a bonding site to an oxygen atom, and R B is a divalent organic group having 1 to 10 carbon atoms, R A is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.

[10] : The metal-containing film-forming composition according to [9] above, characterized in that the flow promoter (BP) has at least one structural unit represented by the following general formulas (BP-1), (BP-2), (BP-3), (BP-4) and (BP-5): [ka] In general formulas (BP-1) and (BP-2), W1 and W2 each independently represent a benzene ring or a naphthalene ring, and the hydrogen atoms in the benzene ring and the naphthalene ring may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. R a is a group represented by the following formula (4). Y' is a group represented by the following formula (5). n1 is 0 or 1, n2 is 1 or 2, and each V independently represents a hydrogen atom or a linking moiety. [ka] (In general formula (BP-3), Z1 is a group represented by the following general formula (6), and R a is a group represented by the following formula (4), where n4 is 0 or 1, n5 is 1 or 2, and each V independently represents a hydrogen atom or a linking moiety. [ka] (In formula (4), * represents a bond to an oxygen atom.) [ka] (In formula (5), * represents a bond.) [ka] (In the general formula (6), W1, W2, Y', and n1 are the same as above.) [ka] In general formula (BP-4), m3 and m4 represent 1 or 2, and Z represents a single bond or a structure represented by the following general formula (7). R x is any of the structures represented by the following general formula (8). [ka] (In the general formula (7), * represents a bond, 1 represents an integer of 0 to 3, and R a ~R f each independently represents a hydrogen atom, an optionally fluorine-substituted alkyl group having 1 to 10 carbon atoms, a phenyl group, or a phenylethyl group; R a and R b may be bonded to form a cyclic compound.) [ka] (In general formula (8), * represents a bonding site to the aromatic ring, and Q1 is a linear saturated hydrocarbon group having 1 to 30 carbon atoms, or a structure represented by the following general formula (9).) [ka] (In the general formula (9), * represents a bonding site to a carbonyl group, and R i is a group represented by the formula (4). jrepresents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. n3 and n4 represent the number of substituents on the aromatic ring, and each represents an integer of 0 to 7, provided that n3 + n4 is 0 or more and 7 or less. n5 represents 0 to 2. [ka] (In general formula (BP-5), R 1 is a saturated monovalent organic group having 1 to 30 carbon atoms or an unsaturated monovalent organic group having 2 to 30 carbon atoms, X is a divalent organic group having 1 to 30 carbon atoms, and R a is a group represented by the formula (4), where p is an integer of 0 to 5, q1 is an integer of 1 to 6, p+q1 is an integer of 1 or more and 6 or less, and q2 is 0 or 1.

[11] : A method for forming a pattern on a workpiece substrate, (I-1) A step of applying any one of the compositions for forming a metal-containing film according to [4] to

[10] above 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 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 the pattern to the metal-containing film by dry etching using the resist upper layer film on which the pattern has been 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:

[12] : A method for forming a pattern on a workpiece substrate, (II-1) A step of applying any one of the compositions for forming a metal-containing film according to [4] to

[10] above onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (II-2) forming a silicon-containing resist intermediate film on the metal-containing film; (II-3) forming a resist upper layer film on the silicon-containing resist intermediate film using a photoresist material; (II-4) 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; (II-5) a step of transferring the pattern to the silicon-containing resist intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (II-6) a step of transferring a pattern to the metal-containing film by dry etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; and (II-7) 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, (III-1) A step of applying any one of the compositions for forming a metal-containing film according to [4] to

[10] above onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (III-2) forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the metal-containing film; (III-3) forming an organic thin film on the inorganic hard mask intermediate film; (III-4) forming a resist top layer film on the organic thin film using a photoresist material; (III-5) 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; (III-6) a step of transferring the pattern to the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (III-7) transferring a pattern to the metal-containing film by dry etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; and (III-8) 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:

[14] : The pattern forming method according to

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

[15] : A method for forming a pattern on a workpiece substrate, (IV-1) A step of applying any one of the compositions for forming a metal-containing film according to [4] to

[10] above onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (IV-2) forming a resist underlayer film on the metal-containing film; (IV-3) forming a silicon-containing resist intermediate film or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film on the resist underlayer film; (IV-4) forming a resist upper layer film on the silicon-containing resist intermediate film or the organic thin film using a photoresist material; (IV-5) 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; (IV-6) a step of transferring a pattern to the silicon-containing resist intermediate film or the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (IV-7) a step of transferring a pattern to the resist underlayer film by dry etching using the silicon-containing resist interlayer film or inorganic hard mask interlayer film to which the pattern has been transferred as a mask; (IV-8) a step of transferring a pattern to the metal-containing film by dry etching using the resist underlayer film to which the pattern has been transferred as a mask; and (IV-9) 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:

[16] : A method for forming a pattern on a workpiece substrate, comprising: (V-1) forming a resist underlayer film on a substrate to be processed; (V-2) forming a resist intermediate film or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film on the resist underlayer film; (V-3) forming a resist upper layer film using a photoresist material on the resist intermediate film or the combination of the inorganic hard mask intermediate film and the organic thin film; (V-4) 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; (V-5) a step of transferring a pattern to the resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film, by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (V-6) a step of transferring a pattern to the resist underlayer film by dry etching using the resist interlayer film or inorganic hard mask interlayer film to which the pattern has been transferred as a mask; (V-7) a step of applying a composition for forming a metal-containing film according to any one of [4] to

[10] above onto the resist underlayer film on which the pattern has been formed, followed by heat treatment to coat the resist underlayer film with a metal-containing film and fill spaces between the resist underlayer film patterns with the metal-containing film; (V-8) a step of etching back the metal-containing film covering the resist underlayer film on which the pattern has been formed by a chemical stripper or dry etching to expose the upper surface of the resist underlayer film on which the pattern has been formed; (V-9) a step of removing the resist intermediate film or the inorganic hard mask intermediate film remaining on the upper surface of the resist underlayer film by dry etching; (V-10) a step of removing the resist underlayer film on which the pattern is formed and the surface is exposed by dry etching, thereby forming a reverse pattern of the original pattern on the metal-containing film; (V-11) A step of processing the substrate to be processed using the metal-containing film on which the reverse pattern has been formed as a mask to form a reverse pattern on the substrate to be processed. A tone-reversal pattern forming method comprising:

[0260] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention. [Explanation of symbols]

[0261] 1...Substrate to be processed, 2...Layer to be processed, 2a...pattern (pattern formed on the processing layer), 2b...reverse pattern (reverse pattern formed on the processing layer), 3...metal-containing film, 3a...metal-containing film pattern, 4...resist intermediate film, 4a...resist intermediate film pattern, 5...resist upper layer film, 5a...resist upper layer film pattern, 6...exposed portion, 7...resist lower layer film, 7a...resist underlayer film pattern, 8...metal-containing film, 8a...Inverted metal-containing film pattern, 9...Base substrate having dense line and space pattern, 10...Metal-containing film, 11... base substrate having dense line and space pattern; 12... filling film; Delta 12: Step difference between the filling film in the dense line pattern area and the non-line pattern area.

Claims

1. A metal-containing film-forming compound used in a metal-containing film-forming composition, The compound for forming a metal-containing film is characterized in that it contains at least one metal atom selected from the group consisting of Ti, Zr, and Hf and one or more ligands derived from compounds represented by the following general formulas (1-B) to (1-D): 【Chemistry 1】 (In general formulas (1-B) to (1-D), R ４ ~R ５ is a hydrogen atom or any one of an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms, which may contain a crosslinking group represented by the following general formulas (a-1) to (a-4), and may contain one or more atoms selected from an oxygen atom and a nitrogen atom; R ６ ~R ９ is a hydrogen atom or any one of an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms, which may contain a crosslinking group represented by the following general formulas (a-1) to (a-4) and (b-1) to (b-4), and which may contain one or more atoms selected from an oxygen atom and a nitrogen atom; R １０ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and Y is an alkylene group having 1 to 10 carbon atoms. The compounds of general formulas (1-B) to (1-D) contain one or more crosslinking groups represented by general formulas (a-1) to (a-4) and (b-1) to (b-4). In general formula (1-B), R ４ and R ５ may be bonded to each other to form an unsaturated or saturated ring structure. 【Chemistry 2】 (In general formulas (a-1) to (a-4), Ra represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bonding site.) 【Transformation 3】 (In general formulas (b-1) to (b-4), R' ｂ is a hydrogen atom or a methyl group, and in the same formula, they may be the same or different from each other; R' ｃ represents a hydrogen atom, a substituted or unsubstituted saturated or unsaturated alkyl 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.

2. The compound for forming a metal-containing film according to claim 1, wherein the ligand derived from the compound represented by any one of the general formulas (1-B) to (1-D) contains one or more structures selected from an aromatic ring, a heteroaromatic ring, and an alicyclic structure.

3. The compound for forming a metal-containing film according to claim 1, further comprising a ligand derived from a silicon compound represented by the following general formula (2): 【Chemistry 4】 (In general formula (2), R ３Ａ , R ３Ｂ and R ３Ｃ is any group selected from an alkyl group having 1 to 30 carbon atoms and having a crosslinking group of any of the structures represented by the following general formulas (c-1) to (c-3), a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. 【Transformation 5】 (In general formulas (c-1) to (c-3), R' ３ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, q represents 0 or 1, and * represents a bond.

4. A composition for forming a metal-containing film used in semiconductor manufacturing, comprising (A) the compound for forming a metal-containing film according to any one of claims 1 to 3 and (B) an organic solvent.

5. 5. The metal-containing film-forming composition according to claim 4, further comprising one or more of (C) a crosslinking agent, (E) a surfactant, and (F) an acid generator.

6. 5. The metal-containing film-forming composition according to claim 4, wherein the (B) organic solvent contains one or more organic solvents having a boiling point of 180° C. or higher as (B1) a high-boiling-point solvent.

7. The metal-containing film-forming composition according to claim 4 , further comprising (G) metal oxide nanoparticles having an average primary particle size of 100 nm or less.

8. 8. The metal-containing film-forming composition according to claim 7, wherein the (G) metal oxide nanoparticles are selected from the group consisting of zirconium oxide nanoparticles, hafnium oxide nanoparticles, titanium oxide nanoparticles, tin oxide nanoparticles, and tungsten oxide nanoparticles.

9. The composition for forming a metal-containing film according to claim 4, further comprising a flowability promoter (BP) having a group represented by the following general formula (3) and an aromatic ring: 【Transformation 6】 (In general formula (3), * represents a bonding site to an oxygen atom, and R Ｂ is an alkylene group having 1 to 10 carbon atoms, R Ａ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

10. The metal-containing film-forming composition according to claim 9, wherein the flow promoter (BP) has at least one structural unit represented by the following general formulas (BP-1), (BP-2), (BP-3), (BP-4), and (BP-5): 【Transformation 7】 (In general formulas (BP-1) and (BP-2), W １ and W ２ are each independently a benzene ring or a naphthalene ring, and the hydrogen atoms in the benzene ring and the naphthalene ring may be substituted with a hydrocarbon group having 1 to 6 carbon atoms. ａ is a group represented by the following formula (4). Y' is a group represented by the following formula (5). n1 is 0 or 1, n2 is 1 or 2, and each V independently represents a hydrogen atom or a linking moiety. 【Transformation 8】 (In general formula (BP-3), Z １ is a group represented by the following general formula (6), and R ａ is a group represented by the following formula (4), n4 is 0 or 1, n5 is 1 or 2, and each V independently represents a hydrogen atom or a linking moiety. 【Chemistry 9】 (In formula (4), * represents a bond to an oxygen atom.) 【Chemistry 10】 (In formula (5), * represents a bond.) 【Chemistry 11】 (In general formula (6), W １ , W ２ , Y', and n1 are the same as above.) 【Chemistry 12】 (In general formula (BP-4), m3 and m4 represent 1 or 2, and Z is either a single bond or a structure represented by the following general formula (7). R ｘ is any of the structures represented by the following general formula (8): 【Chemistry 13】 (In general formula (7), * represents a bond, 1 represents an integer of 0 to 3, and R ａ ~R ｆ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted with fluorine, a phenyl group, or a phenylethyl group; R ａ and R ｂ may be bonded to form a cyclic compound.) 【Chemistry 14】 (In general formula (8), * represents a bonding site to the aromatic ring, and Q １ is a linear saturated hydrocarbon group having 1 to 30 carbon atoms, or a structure represented by the following general formula (9): 【Chemistry 15】 (In general formula (9), * represents the bonding site to the carbonyl group, and R ｉ is a group represented by the formula (4). ｊ represents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 1 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms. n3 and n4 represent the number of substituents on the aromatic ring, and each represents an integer of 0 to 7. However, n3 + n4 is 0 to 7. n5 represents 0 to 2. 【Chemistry 16】 (In general formula (BP-5), R １ is a saturated alkyl group having 1 to 30 carbon atoms or an unsaturated alkyl group having 2 to 30 carbon atoms, X is any one of an alkanediyl group having 1 to 30 carbon atoms, a cycloalkanediyl group having 3 to 30 carbon atoms, an alkanediyloxy group having 1 to 30 carbon atoms, a cycloalkanediyloxy group having 3 to 30 carbon atoms, and an arenediyl group having 6 to 30 carbon atoms, and R ａ is a group represented by the formula (4), p is an integer of 0 to 5, q １ is an integer from 1 to 6, p+q １ is an integer of 1 to 6, and q ２ is 0 or 1.)

11. A method for forming a pattern on a workpiece substrate, comprising: (I-1) A step of applying the metal-containing film-forming composition according to claim 4 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 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 the pattern to the metal-containing film by dry etching using the resist upper layer film on which the pattern has been 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:

12. A method for forming a pattern on a workpiece substrate, comprising: (II-1) A step of applying the metal-containing film-forming composition according to claim 4 onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (II-2) forming a silicon-containing resist intermediate film on the metal-containing film; (II-3) forming a resist upper layer film on the silicon-containing resist intermediate film using a photoresist material; (II-4) 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; (II-5) a step of transferring the pattern to the silicon-containing resist intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (II-6) A step of transferring a pattern to the metal-containing film by dry etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; and (II-7) 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: (III-1) A step of applying the metal-containing film-forming composition according to claim 4 onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (III-2) forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the metal-containing film; (III-3) forming an organic thin film on the inorganic hard mask intermediate film; (III-4) forming a resist top layer film on the organic thin film using a photoresist material; (III-5) 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; (III-6) a step of transferring the pattern to the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (III-7) transferring the pattern to the metal-containing film by dry etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; and (III-8) 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:

14. 14. The pattern formation method according to claim 13, wherein the inorganic hard mask intermediate film is formed by a CVD method or an ALD method.

15. A method for forming a pattern on a workpiece substrate, comprising: (IV-1) A step of applying the metal-containing film-forming composition according to claim 4 onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (IV-2) forming a resist underlayer film on the metal-containing film; (IV-3) forming a silicon-containing resist intermediate film or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film on the resist underlayer film; (IV-4) forming a resist upper layer film on the silicon-containing resist intermediate film or the organic thin film using a photoresist material; (IV-5) 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; (IV-6) A step of transferring a pattern to the silicon-containing resist intermediate film or the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (IV-7) A step of transferring a pattern to the resist underlayer film by dry etching using the silicon-containing resist interlayer film or inorganic hard mask interlayer film to which the pattern has been transferred as a mask; (IV-8) a step of transferring a pattern to the metal-containing film by dry etching using the resist underlayer film to which the pattern has been transferred as a mask; and (IV-9) 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:

16. A method for forming a pattern on a workpiece substrate, comprising: (V-1) A step of forming a resist underlayer film on a substrate to be processed; (V-2) forming a resist intermediate film or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film on the resist underlayer film; (V-3) forming a resist upper layer film using a photoresist material on the resist intermediate film or the combination of the inorganic hard mask intermediate film and the organic thin film; (V-4) 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; (V-5) a step of transferring a pattern to the resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film, by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (V-6) a step of transferring a pattern to the resist underlayer film by dry etching using the resist interlayer film or inorganic hard mask interlayer film to which the pattern has been transferred as a mask; (V-7) a step of applying the composition for forming a metal-containing film according to claim 4 onto the resist underlayer film on which the pattern has been formed, followed by heat treatment to cover the resist underlayer film with a metal-containing film and fill spaces between the resist underlayer film patterns with the metal-containing film; (V-8) a step of etching back the metal-containing film covering the resist underlayer film on which the pattern has been formed by a chemical stripper or dry etching to expose the upper surface of the resist underlayer film on which the pattern has been formed; (V-9) a step of removing the resist intermediate film or the inorganic hard mask intermediate film remaining on the upper surface of the resist underlayer film by dry etching; (V-10) a step of removing the resist underlayer film, on which the pattern is formed and the surface is exposed, by dry etching to form a reverse pattern of the original pattern on the metal-containing film; (V-11) A step of processing the substrate to be processed using the metal-containing film on which the reverse pattern has been formed as a mask to form a reverse pattern on the substrate to be processed. A tone-reversal pattern forming method comprising:

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