Compound for forming metal-containing film, composition for forming metal-containing film, and patterning process

Abstract

To provide: a metal compound having better dry etching resistance than conventional organic underlayer film materials and also having high filling and planarizing properties; a composition for forming a metal-containing film employing the compound; and a patterning process in which the composition is used as a resist underlayer film material.SOLUTION: A compound for forming a metal-containing film is a reaction product between a compound having two or more diol structures per molecule and a Sn compound, and is a monomolecular compound containing two or more Sn atoms per molecule.SELECTED DRAWING: Figure 1

Description

[Technical field]

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

[0002] As LSIs become more highly integrated and faster, pattern rules are becoming finer at a rapid pace. As the most advanced fine-tuning technology, ArF immersion lithography is being applied to the mass production of devices at the 45nm node and beyond. In addition to ArF immersion exposure, double exposure (double patterning) processes have been put into practical use for the 28nm node and beyond generation, making it possible to form narrow-pitch patterns that exceed the optical limit.

[0003] Furthermore, for device manufacturing at the 20 nm node and below, multiple exposure (multi-patterning) processes are being considered, which create patterns with narrower pitches by repeating exposure and etching three or more times. However, the multiple exposure process increases the number of steps, which leads to longer manufacturing times and a higher frequency of defects, reducing productivity and resulting in a significant increase in costs.

[0004] In recent years, 13.5 nm wavelength vacuum ultraviolet (EUV) lithography has been attracting attention as a promising technology to replace the combined use of ArF immersion lithography and multiple exposure processes. Using this technology, it has become possible to form fine patterns with a half pitch of 25 nm or less in a single exposure.

[0005] On the other hand, in EUV lithography, there is a strong demand for high sensitivity in resist materials to compensate for the insufficient output of the light source. However, the increase in shot noise that accompanies high sensitivity leads to an increase in edge roughness (LER, LWR) of the line pattern, and therefore achieving both high sensitivity and low edge roughness is one of the important challenges in EUV lithography.

[0006] In recent years, the use of metal materials in resist materials has been considered as an attempt to increase the sensitivity of resists and reduce the effects of shot noise. Compounds containing metal elements such as barium, titanium, hafnium, zirconium, and tin have a higher absorbance to EUV light than organic materials that do not contain metals, and are expected to improve the photosensitivity of resists and suppress the effects of shot noise. In addition, metal-containing resist patterns can be combined with an underlayer film made of a non-metallic material to enable high-selectivity etching processing.

[0007] For example, resist materials containing metal salts or organometallic complexes as described in Patent Documents 1 and 2, and non-chemically amplified resist materials using metal oxide nanoparticles as described in Patent Documents 3 and 4 have been investigated.

[0008] Among them, molecules containing tin are being actively researched because they have excellent absorption of electron beams and extreme ultraviolet rays. In the case of organotin polymers, which are one of them, alkyl ligands are dissociated by light absorption or secondary electrons generated by it, and crosslinking with surrounding chains through oxo bonds enables negative tone patterning that is not removed by organic developers. Such organotin polymers can improve sensitivity while maintaining resolution and line edge roughness, but have not yet reached the level of commercialization (Patent Document 5). In addition, many issues remain, such as insufficient storage stability against changes in resist sensitivity.

[0009] In response to the above-mentioned problems, development of a resist underlayer film using a material containing metal elements such as titanium, hafnium, zirconium, and tin is also being considered. There is no need for performance improvements such as improving exposure sensitivity and suppressing sensitivity changes under storage environments, which are issues with metal-containing resist materials, and by including the above-mentioned metal elements, it is possible to provide a resist underlayer film with excellent dry etching resistance. Patent Document 7 reports that a material using a Ti compound exhibits excellent dry etching resistance against CHF3 / CF4-based gas and CO2 / N2-based gas.

[0010] On the other hand, one of the problems when using metal compounds for resist underlayer films is embeddability. For example, in compounds intended for use in photoresists such as Patent Document 6, heat resistance is not mentioned, but since baking at high temperatures is not assumed, heat resistance is insufficient, and embedding and film formation defects may occur. In addition, Patent Document 7 does not mention embeddability, but metal oxide compounds generally have large thermal shrinkage during baking, and after high-temperature baking, they induce significant deterioration of filling properties, so there is a concern that they are insufficient as resist underlayer film materials that require high level flattening properties, embedding properties, and heat resistance properties. Patent Document 8 reports that metal compounds modified with specific ligands have excellent embeddability, but the bake temperature for the embeddability evaluation that was carried out is as low as 150°C, and there is a concern that they are insufficient as resist underlayer films that require heat resistance (for example, properties against heat treatment that may be performed after the formation of the resist underlayer film). In Patent Document 9, a resist underlayer film material having excellent embedding properties after baking at 400°C is provided by mixing the metal compound reported in Patent Document 8 with an organic polymer having a specific structure. However, since the material is a mixed composition of an inorganic metal compound and an organic polymer, there are concerns about poor film formation, deterioration of storage stability, and deterioration of dry etching resistance caused by poor compatibility. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] Patent No. 5708521 [Patent Document 2] Patent No. 5708522 [Patent Document 3] U.S. Patent No. 9,310,684 [Patent Document 4] US Patent Application Publication No. 2017 / 0102612 [Patent Document 5] JP 2021-162865 A [Patent Document 6] Patent No. 7028940 [Patent Document 7] Patent No. 6189758 [Patent Document 8] Patent No. 7050137 [Patent Document 9] Special Publication No. 2022-521531 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 excellent dry etching resistance compared to conventional organic underlayer film materials and also has high-level filling / planarization properties, a composition for forming a metal-containing film using the compound, and a pattern formation method using the composition as a resist underlayer film material. [Means for solving the problem]

[0013] In order to solve the above problems, the present invention provides a compound for forming a metal-containing film, which is a reaction product of a compound having two or more diol structures in its molecule and a Sn compound, and is a monomolecular compound containing two or more Sn atoms in one molecule.

[0014] The compound for forming a metal-containing film of the present invention has excellent dry etching resistance compared to conventional organic underlayer film materials, and also has high-level filling / planarization properties, and it is possible to provide a composition for forming a metal-containing film using this metal compound, and a pattern formation method using the composition as a resist underlayer film material.

[0015] The metal-containing film-forming compound can be represented by the following general formula (M-1) or (M-2). [ka] (In the general formulae (M-1) to (M-2), R1 and R2 each independently represent a monovalent organic group or a halogen atom. X1 represents a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 70 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds (the alkyl group and the aliphatic unsaturated hydrocarbon group may have an ether group, a thioether group, an ester group, or an amide group), a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted triazine ring, a substituted or unsubstituted isocyanuric group, and an n1-valent organic group selected from substituted or unsubstituted glycoluril groups, where n1 is an integer of 2 to 6. R3 represents a substituent other than a hydrogen atom, each of which is independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a thiol group, a hydroxyl group, an amino group, a carboxy group, or a halogen atom, l is an integer of 0 to 1, and m1 is an integer of 0 to 5.X2 is a single bond or a linking moiety, the linking moiety being an n2-valent organic group selected from a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds (the alkyl group and the aliphatic unsaturated hydrocarbon group may have a ketone group, an ether group, an ester group, an amide group, an imine group, a lactone ring, and a sultone ring), a substituted or unsubstituted aryl group having 6 to 36 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 36 carbon atoms, and a substituted or unsubstituted triazine ring, or a 2×n2-valent organic group selected from a substituted or unsubstituted saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms forming a cyclic structure together with an aromatic ring (the hydrocarbon group may have an ether group), where n2 is an integer of 2 to 4. ).

[0016] Here, the heteroalkyl group refers to an alkyl group further containing one or more (e.g., 1, 2, 3, or 4) heteroatoms (e.g., oxygen, sulfur, nitrogen, boron, silicon, phosphorus) in its main chain. The heteroatoms may be inserted between adjacent carbon atoms in the parent carbon chain, or between a carbon atom and its parent molecule (i.e., between the bonding points). However, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms and substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms and having an ester group or amide group are excluded.

[0017] The structure represented by the above general formulas (M-1) to (M-2) can ensure a sufficient molecular weight, thereby suppressing sublimation of the molecules even at high temperatures, and therefore can provide a metal-containing film-forming composition that has excellent film-forming properties, filling properties, and planarization properties even after high-temperature baking.

[0018] In the above general formulas (M-1) to (M-2), R1 is preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds, 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.

[0019] In the above general formulas (M-1) to (M-2), if R1 is such a group, radical cleavage of the tin-carbon bond occurs during baking, generating radicals that initiate a crosslinking reaction, thereby enhancing the curability. A metal-containing film-forming compound having such a structure can achieve a high degree of both heat resistance and thermosetting properties, and when used in a metal-containing film-forming composition, a resist underlayer film material exhibiting superior embedding properties can be provided.

[0020] In the metal-containing film-forming compound of the present invention, R2 is preferably -OC(=O)R2' (R2' is a monovalent organic group).

[0021] In the above general formula (M), if R2 is -OC(=O)R2', the symmetry of the compound structure is lost, and a metal-containing film-forming composition with excellent solvent solubility can be provided. In addition, if R2' is -OC(=O)R2', R2' can be freely changed, so that further improvement in solubility and thermal fluidity can be expected by incorporating a bulky structure, and it is also possible to provide a crosslinked structure, so that sublimates can be suppressed and volume shrinkage that induces deterioration of embeddability can be suppressed. As a result, a metal-containing film-forming composition with excellent film-forming, embedding and flattening properties can be provided even after high-temperature baking.

[0022] In the present invention, the above R2' is preferably represented by the following general formulae (A-1) to (A-4), (2) or (3). [ka] (In the above general formulae (A-1) to (A-4), YA1 , Y A2 may be the same or different, and each represents a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms. A is a hydrogen atom, a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, R A1 is an organic group that generates one or more hydroxyl or carboxyl groups by elimination of a protecting group by the action of either or both of an acid and heat, as represented by the following general formula (1), and * represents a bond with a carbonyl group. [ka] (In the above general formula (1), R A2 is an organic group whose protecting group is removed by the action of either acid or heat, or both, and * is Y A1 Or Y A2 ) [ka] (In the general formula (2), X is a divalent organic group having 1 to 31 carbon atoms, B is the following general formula (B), and * represents a bond to a carbonyl group.) [ka] (In the above general formula (B), Y B represents a substituted or unsubstituted divalent saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms or an unsaturated divalent aliphatic hydrocarbon group having 2 to 20 carbon atoms, a substituted or unsubstituted divalent aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted divalent arylalkyl group having 7 to 31 carbon atoms, which may be bonded to an adjacent group via an oxygen atom or an NH group; R B is a hydroxyl group or any of the structures represented by the following general formulas (B-1) to (B-3). * represents the bond with the carbonyl group. [ka] (In the above general formulas (B-1) to (B-3), R B1 is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q is 0 or 1, * is Y B ) [ka] (In the general formula (3), X is a divalent organic group having 1 to 31 carbon atoms, C is any of the following general formulae (C-1) to (C-4), and * represents a bond to a carbonyl group.) [ka] (In the above general formulas (C-1) and (C-3), R C1 are each independently a hydrogen atom or a methyl group, and in the same formula, they may be the same or different. In (C-3) to (C-4), R C2 is a hydrogen atom, or a substituted or unsubstituted saturated or unsaturated monovalent aliphatic hydrocarbon 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. * represents the bond to the carbonyl group.)

[0023] If R2' is a structure represented by the above general formulas (A-1) to (A-4), the structure contains a bulky thermoacid labile group, and therefore the thermal fluidity can be improved. Furthermore, when this is used in a metal-containing film-forming composition, the thermoacid labile group is eliminated during baking, and a hydroxyl group or a carboxyl group is generated. The OH and α-hydrogen of the carboxylic acid thus generated are likely to react with radicals generated by the cleavage of the tin-carbon bond during baking, and a crosslinking reaction occurs, resulting in excellent thermosetting properties, which can suppress volume shrinkage that induces deterioration of flatness and embeddability, and a metal-containing film-forming composition having excellent film-forming properties and flattening / embedding properties even after high-temperature baking can be provided.

[0024] If R2' has the structure represented by the above general formula (2), it contains a hydroxyl group or a crosslinking group having any of the structures represented by the above general formulas (B-1) to (B-3) at its terminal. Therefore, when this is used in a metal-containing film-forming composition, it easily reacts with radicals generated by cleavage of tin-carbon bonds when baked, causing a crosslinking reaction. Furthermore, a crosslinking reaction occurs even with these crosslinking groups alone, so that the composition has excellent thermosetting properties and can suppress volume shrinkage that induces deterioration of flatness and fillability. Thus, a metal-containing film-forming composition having excellent film-forming properties and flattening properties / filling properties can be provided even after high-temperature baking.

[0025] If R2' has the structure represented by the above general formula (3), it contains the structures represented by (C-1) to (C-4), has a high crosslinking group density, and has excellent thermosetting properties. Therefore, when this is used in a composition for forming a metal-containing film, it is possible to provide a resist underlayer film material that has small volume shrinkage during baking and is excellent in film-forming properties and planarization properties / filling properties even after high-temperature baking.

[0026] Y in the above general formulas (A-1) to (A-4) A1 It is preferable that X in the general formula (2) or X in the general formula (3) is a substituted or unsubstituted unsaturated hydrocarbon having 2 to 20 carbon atoms.

[0027] Y in the above general formulas (A-1) to (A-4) A1 When X in the general formula (2) or X in the general formula (3) is an unsaturated hydrocarbon having 2 to 20 carbon atoms, the thermosetting property of the metal-containing film-forming compound can be further improved.

[0028] In addition, Y in the above general formulas (A-1) to (A-4) A1 X in the above general formula (2) or X in the above general formula (3) may be the following general formula (4). [ka] (In the general formula (4), R a , R b and R C is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and Ra and R b may be bonded to form a cyclic substituent. *1 and *2 each represent a bond to a carbonyl group, and the substitution positions of *1 and *2 may be reversed.)

[0029] Y in the above general formulas (A-1) to (A-4) A1 When X in the above general formula (2) or X in the above general formula (3) is the above general formula (4), it becomes possible to achieve a high compatibility between thermal fluidity and thermosetting property, and when this is used in a metal-containing film-forming composition, it is possible to provide a resist underlayer film material that exhibits superior planarization properties / filling properties.

[0030] In the above general formula (M-2), m1 is 0 or 1, and when m1=1, R3 is preferably a hydroxyl group.

[0031] In the above general formula (M-2), when m1 is 0 or 1, the tin content increases, so that excellent etching resistance can be expected, and when m1 is 1 and R3 is a hydroxyl group, radical cleavage of the tin-carbon bond occurs during baking, but the hydroxyl group easily reacts with radicals, so that curability can be improved. Therefore, a metal-containing film-forming composition that has excellent film-forming properties, filling properties, and etching resistance even after high-temperature baking can be provided.

[0032] The metal-containing film-forming compound is preferably characterized in that the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn in terms of polystyrene measured by gel permeation chromatography is 1.00≦Mw / Mn≦1.50.

[0033] A compound for forming a metal-containing film having a dispersity in such a range can be confirmed to be a monomolecular compound and further has better thermal fluidity. Therefore, when incorporated into a composition for forming a metal-containing film, it is not only possible to satisfactorily fill the fine structures formed on the substrate, but also to form a resist underlayer film that flattens the entire substrate.

[0034] The present invention also provides a composition for forming a metal-containing film that functions as a resist underlayer film material used in semiconductor manufacturing, the composition comprising (a) the compound for forming a metal-containing film and (b) an organic solvent.

[0035] Such a composition for forming a metal-containing film contains an organotin compound that has excellent solvent solubility, heat resistance, and thermal fluidity, and therefore can provide a resist underlayer film material that has excellent dry etching resistance compared to conventional organic underlayer film materials and also has advanced filling / planarization properties.

[0036] The above composition is a composition for forming a metal-containing film that can be used as a resist underlayer film in a multi-layer resist method, and can further contain one or more of (c) a crosslinking agent, (d) a surfactant, (e) a flowability promoter, and (f) an acid generator.

[0037] The (b) organic solvent is preferably a mixture of one or more organic solvents having a boiling point of less than 180°C and one or more organic solvents having a boiling point of 180°C or higher.

[0038] By imparting thermal fluidity to the above-mentioned metal-containing film-forming compound by adding a high-boiling point solvent, the resist underlayer film-forming composition also has high-level filling / planarizing properties.

[0039] The present invention also provides a method for forming a pattern on a workpiece substrate, comprising the steps of: (I-1) a step of applying the composition for forming a metal-containing film of the present invention onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (I-2) forming a resist top layer film on the metal-containing film using a photoresist material; (I-3) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (I-4) a step of transferring the pattern to the metal-containing film by dry etching using the resist top layer film on which the pattern is formed as a mask; and (I-5) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. The present invention provides a pattern forming method comprising the steps of:

[0040] By the pattern formation method using the two-layer resist process, a fine pattern can be formed on a workpiece (substrate).

[0041] The present invention also provides a method for forming a pattern on a workpiece substrate, comprising the steps of: (II-1) A step of applying the composition for forming a metal-containing film of the present invention onto a substrate to be processed and then heat-treating the composition to form a metal-containing film; (II-2) forming a resist intermediate film on the metal-containing film; (II-3) forming a resist upper layer film on the resist intermediate film using a photoresist material; (II-4) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (II-5) a step of transferring the pattern to the 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 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:

[0042] The pattern formation method using the three-layer resist process described above makes it possible to form fine patterns on a workpiece with high precision.

[0043] The present invention also provides a method for forming a pattern on a workpiece substrate, comprising the steps of: (III-1) A step of applying the composition for forming a metal-containing film of the present invention onto a substrate to be processed and then heat-treating the composition 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 resist underlayer 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 forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (III-6) a step of transferring a 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) A step of 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:

[0044] The pattern formation method using the four-layer resist process described above makes it possible to form fine patterns on a workpiece with high precision.

[0045] In this case, the inorganic hard mask is preferably formed by a CVD method or an ALD method.

[0046] When the inorganic hard mask is formed by a CVD method or an ALD method, a fine pattern can be formed on a workpiece with higher accuracy.

[0047] The present invention also provides a method for forming a pattern on a workpiece substrate, comprising the steps of: (IV-1) forming a resist underlayer film on a substrate to be processed; (IV-2) a step of applying the composition for forming a metal-containing film of the present invention onto the resist underlayer film, followed by heat treatment to form a metal-containing film; (IV-3) forming a resist upper layer film on the metal-containing film using a photoresist material, or forming an organic adhesion film on the metal-containing film by spin coating, and forming a resist upper layer film thereon using a photoresist material; (IV-4) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (IV-5) a step of transferring a pattern to the metal-containing film, or the organic adhesion film and the metal-containing film, by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (IV-6) a step of transferring a pattern to the resist underlayer film by dry etching using the metal-containing film to which the pattern has been transferred as a mask; and (IV-7) A step of processing the substrate to be processed using the resist underlayer film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. The present invention provides a pattern forming method comprising the steps of:

[0048] By using the pattern forming method using the multi-layer resist process, a fine pattern can be formed on a workpiece with high precision.

[0049] The present invention also provides a method for forming a pattern on a workpiece substrate, comprising the steps of: (V-1) a step of forming a resist underlayer film on a substrate to be processed; (V-2) a step of 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 on the resist intermediate film or on a combination of the inorganic hard mask intermediate film and an organic thin film using a photoresist material; (V-4) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (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 intermediate film or the inorganic hard mask intermediate 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 of the present invention onto the resist underlayer film on which the pattern has been formed, and then heat-treating the composition to form a metal-containing film, thereby 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 is formed by a chemical stripper or dry etching to expose an upper surface of the resist underlayer film on which the pattern is formed; (V-9) a step of removing the resist intermediate film or the 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 is formed as a mask to form a reverse pattern on the substrate to be processed. The present invention provides a pattern forming method comprising the steps of:

[0050] The above-described method for forming a pattern using a reversal process makes it possible to form a fine pattern on a workpiece with even greater precision.

[0051] In this case as well, the inorganic hard mask is preferably formed by a CVD method or an ALD method.

[0052] When the inorganic hard mask is formed by a CVD method or an ALD method, a fine pattern can be formed on a workpiece with higher accuracy. Effect of the Invention

[0053] As explained above, the compound for forming a metal-containing film of the present invention is a monomolecular compound containing two or more Sn atoms in one molecule, which is synthesized by reacting a compound having two or more diol structures (including a catechol structure) with a tin compound. Microscopically, the two hydroxyl groups of a diol such as catechol can bond with Sn, and two bond cleavage is required when the organic ligand sublimes, so that the tin-containing compound has better heat resistance than a normal monovalent ligand (monodentate ligand), and volume shrinkage that induces deterioration of embedding properties can be suppressed. Macroscopically, multiple Sn atoms can be introduced into one molecule, so molecular design is possible to increase the molecular weight while increasing the Sn content. Furthermore, since it contains two separate organic groups per Sn atom, it becomes a compound for forming a metal-containing film with excellent thermal fluidity, and the performance can be tuned by changing the structure of the organic group. Therefore, when this is used in a composition for forming a metal-containing film, volume shrinkage that induces deterioration of embedding properties can be suppressed, and a resist underlayer film material with excellent film forming properties and planarization properties / embedding properties can be provided even after high-temperature baking.

[0054] In particular, in fine patterning processes using multi-layer resist methods in semiconductor device manufacturing processes, it is possible to fill without causing defects such as voids or peeling, even on substrates having 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, since it has superior dry etching resistance compared to conventional coating-type organic resist underlayer film materials, it is possible to form fine patterns on the workpiece with even greater precision than with organic resist underlayer films.

[0055] In addition, the metal-containing film-forming composition containing the metal-containing film-forming compound of the present invention contains Sn atoms, which have high EUV light absorption, and therefore has a sensitizing effect due to secondary electrons generated from the Sn atoms during exposure. Furthermore, since Sn atoms have a large atomic weight, they are highly effective in suppressing acid diffusion from the upper resist layer into the resist underlayer film, and have the characteristic of being able to achieve high sensitivity while maintaining the LWR performance that the resist upper layer film originally has. [Brief description of the drawings]

[0056] [Figure 1] FIG. 2 is an explanatory diagram of an example (three-layer resist process) of the pattern forming method of the present invention. [Diagram 2] FIG. 2 is an explanatory diagram of an example of a tone reversal pattern formation method of the present invention (reversal of an SOC pattern in a three-layer resist process). [Diagram 3] FIG. 1 is an explanatory diagram of a method for evaluating embedding characteristics. [Figure 4] FIG. 1 is an explanatory diagram of a flattening characteristic evaluation method. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0057] As described above, in a fine patterning process using a multilayer resist method, there has been a demand for the development of a composition for forming a metal-containing film 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, and a compound for forming a metal-containing film that is useful for said composition.

[0058] The present inventors have focused on organotin compounds that are expected to play an active role in the EUV exposure generation and have conducted intensive research. As described above, tin atoms, which have a high EUV light absorption, have a sensitizing effect due to secondary electrons generated from them during exposure, and have the characteristic that the resist top layer film can be made highly sensitive while maintaining the inherent LWR performance. On the other hand, organotin compounds that have been considered as resist top layers have poor heat resistance and undergo rapid volume shrinkage during baking, making it difficult to fill in steps on the substrate to be processed and flatten it after high-temperature baking. The present inventors thought that if a diol / catechol-based compound can bond with divalent tin in one molecule, the bond is less likely to be broken when baked, and heat resistance can be improved. Furthermore, it is possible to increase the tin content while increasing the molecular weight by having multiple such structures in one molecule, and it has been found that a metal-containing film-forming composition that exhibits further improved heat resistance and excellent etching resistance can be obtained, and the present invention has been completed.

[0059] That is, the present invention relates to a compound for forming a metal-containing film, which is a reaction product of a compound having two or more diol structures in its molecule and a Sn compound, and is a monomolecular compound containing two or more Sn atoms in one molecule.

[0060] The present invention will be described in detail below, but the present invention is not limited thereto.

[0061] <Compounds for forming metal-containing films> The metal-containing film-forming compound of the present invention is a reaction product of a compound having two or more diol structures (including catechol structures) in a molecule and a Sn compound, and is a monomolecular compound containing two or more Sn atoms in a molecule. This compound can be used in a metal-containing film-forming composition that functions as a resist underlayer film material used in semiconductor manufacturing.

[0062] In the present invention, a compound having a diol structure refers to a compound (polyol) having two or more hydroxyl groups (-OH) in the molecule. Examples of such compounds include aliphatic diols having two hydroxyl groups in the molecule, aromatic diols, and triols and tetraols having three or more hydroxyl groups in the molecule. The substitution position of the hydroxyl group in the molecule of an aliphatic hydrocarbon (which may be linear, branched, or cyclic, and may be saturated or unsaturated), aromatic hydrocarbon (which may be substituted or unsubstituted and may have a heteroatom at any position), etc. is not particularly limited, but a compound having a structure of 1,2-diol having hydroxyl groups on two adjacent carbon atoms, or 1,3-diol having hydroxyl groups on one carbon atom and the carbon atom at the β-position of the carbon atom is preferred, and a compound having a 1,2-diol structure is more preferred. The above 1,2-diol structure also includes a structure having hydroxyl groups on two adjacent carbon atoms of an aromatic ring.

[0063] Examples of compounds having a 1,2-diol structure include alkanediols having 2 to 70 carbon atoms (having hydroxyl groups on two adjacent carbon atoms that constitute the ring) which may have a substituent, alicyclic diols having 3 to 70 carbon atoms (having hydroxyl groups on two adjacent carbon atoms that constitute the ring) which may have a substituent, catechol derivatives such as catechol, 3-methylcatechol, 4-methylcatechol, and pyrogallol, and heterocyclic compounds having hydroxyl groups on two adjacent carbon atoms that constitute the ring, such as N-benzoyl-3,4-dihydroxypyrrolidine. In addition, the compound having a diol structure may be a compound containing a hydroxyl group and a carboxyl group (COOH), such as α-hydroxycarboxylic acid, or a compound that has two or more hydroxyl groups in its limit structure, such as β-diketones such as acetylacetone. Examples of compounds having a 1,3-diol structure include alkanediols having 3 to 70 carbon atoms which may have a substituent, such as 1,3-propanediol. The compound having a diol structure of the present invention is a compound (complex) in which a diol is coordinated to a central metal Sn, and examples thereof include a compound in which a 1,2-diol (ligand) forms a five-membered ring with Sn. When an aromatic 1,2-diol such as catechol or 2,3-naphthalenediol is coordinated to Sn to form a five-membered ring, a rigid structure is formed.

[0064] In such a compound, two hydroxyl groups of catechol or diol can bond with tin at the micro level, and when the bond with the organic ligand is broken, two Sn-O bonds must be broken simultaneously, resulting in a tin-containing compound with better heat resistance than compounds with normal monovalent ligands, and since the volume shrinkage that induces deterioration of the embedding ability can be suppressed, even after high-temperature baking, a resist underlayer film material with excellent film-forming, embedding and planarization properties can be provided. In addition, since multiple Sn atoms can be introduced into one molecule at the macro level, it is possible to increase the tin content while increasing the molecular weight, and a resist underlayer film material with excellent heat resistance and etching resistance can be provided.

[0065] The metal-containing film-forming compound is preferably a compound represented by the following general formulas (M-1) to (M-2). [ka] (In the general formulae (M-1) to (M-2), R1 and R2 each independently represent a monovalent organic group or a halogen atom. X1 represents a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 70 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds (the alkyl group and the aliphatic unsaturated hydrocarbon group may have an ether group, a thioether group, an ester group, or an amide group), a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted triazine ring, a substituted or unsubstituted isocyanuric group, and an n1-valent organic group selected from substituted or unsubstituted glycoluril groups, where n1 is an integer of 2 to 6. R3 represents a substituent other than a hydrogen atom, each of which is independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a thiol group, a hydroxyl group, an amino group, a carboxy group, or a halogen atom, l is an integer of 0 to 1, and m1 is an integer of 0 to 5.X2 is a single bond or a linking moiety, the linking moiety being an n2-valent organic group selected from a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds (the alkyl group and the aliphatic unsaturated hydrocarbon group may have a ketone group, an ether group, an ester group, an amide group, an imine group, a lactone ring, and a sultone ring), a substituted or unsubstituted aryl group having 6 to 36 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 36 carbon atoms, and a substituted or unsubstituted triazine ring, or a 2×n2-valent organic group selected from a substituted or unsubstituted saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms forming a cyclic structure together with an aromatic ring (the hydrocarbon group may have an ether group), where n2 is an integer of 2 to 4. ).

[0066] The inventors have further conducted intensive research and have found that a compound for forming a metal-containing film represented by the above general formulas (M-1) to (M-2) can ensure a sufficient molecular weight, thereby suppressing rapid volumetric shrinkage during baking, and has excellent film-forming properties, filling characteristics, and planarization characteristics, and further can increase the tin content, resulting in a compound for forming a metal-containing film with excellent etching resistance.

[0067] The compounds for forming metal-containing films represented by the above general formulas (M-1) to (M-2) can ensure a sufficient molecular weight, thereby suppressing rapid volumetric shrinkage during baking, and are excellent in film-forming properties, filling properties, and flattening properties. Furthermore, the tin content can be increased, making them compounds for forming metal-containing films that provide metal-containing films with excellent etching resistance.

[0068] In the above general formulas (M-1) to (M-2), R1 and R2 are each independently a monovalent organic group or a halogen atom, and are preferably an alkyl group, an ester group, an alkoxy group, or a chloro group from the viewpoint of raw material availability and synthesis, and are preferably different structures in the same compound from the viewpoint of solvent solubility.Furthermore, in consideration of thermal fluidity, R1 and R2 are preferably a combination of an alkyl group and an ester group.

[0069] In the above general formula (M-1), X1 is an n1-valent organic group selected from a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 70 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds (the alkyl group and the aliphatic unsaturated hydrocarbon group may have an ether group, a thioether group, an ester group, or an amide group), a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted triazine ring, a substituted or unsubstituted isocyanuric group, and a substituted or unsubstituted glycoluril group, where n1 is an integer of 2 to 6. Specific examples of the above general formula (M-1) include, but are not limited to, the following.

[0070] [ka] (In the above formula, each n is independently an integer of 0 or more, and applies only to the above formula.)

[0071] [ka]

[0072] In the above general formula (M-2), specific examples of R3 include, but are not limited to, the following: In the following formula, * represents a bond to the aromatic ring. [ka]

[0073] In the above general formula (M-2), l is an integer of 0 to 1, and l is preferably 0 from the viewpoint of increasing the Sn content.

[0074] In the above general formula (M-2), X2 is a single bond or a linking moiety, and the linking moiety is a carbonyl group, an ether group, an ester group, or an amide group, or a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds (the alkyl group and the aliphatic unsaturated hydrocarbon group are a ketone group, an ether group, an ester group, an amide group, It is an n2-valent organic group selected from a substituted or unsubstituted aryl group having 6 to 36 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 36 carbon atoms, and a substituted or unsubstituted triazine ring, or a 2×n2-valent organic group selected from a substituted or unsubstituted saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms forming a cyclic structure together with an aromatic ring (the hydrocarbon group may have an ether group), where n2 is an integer of 2 to 4. Specific examples of the above general formula (M-2) include, but are not limited to, the following.

[0075] [ka]

[0076] In the above general formulas (M-1) to (M-2), R1 is preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds, 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, more preferably an unsubstituted alkyl group having 1 to 20 carbon atoms from the viewpoint of suppressing sublimates, and particularly preferably an n-butyl group from the viewpoint of easy availability of raw materials.

[0077] Such a compound for forming a metal-containing film contains a tin-alkyl bond, and therefore when baked, the bond is cleaved to generate radicals, which initiate a crosslinking reaction, resulting in excellent thermosetting properties, and therefore a resist underlayer film material that is excellent in film-forming properties, filling properties, and planarization properties can be provided, even after high-temperature baking.

[0078] Furthermore, in the above general formulae (M-1) to (M-2), it is preferable that R2 is --OC(.dbd.O)R2' (R2' is a monovalent organic group) from the viewpoint of solvent solubility.

[0079] Such a compound for forming a metal-containing film can provide a resist underlayer film with excellent planarization properties because the compound is asymmetric and has excellent solvent solubility and excellent thermal fluidity. In addition, in the case of -OC(=O)R2', R2' can be freely changed, so that further improvement in solubility and thermal fluidity can be expected by incorporating a bulky structure, and it is also possible to provide a crosslinked structure, so that sublimates can be suppressed and volume shrinkage that induces deterioration of embedding properties can be suppressed. As a result, a resist underlayer film material with excellent film forming properties, embedding properties and planarization properties can be provided even after high-temperature baking.

[0080] In the above R2, R2' is preferably represented by the following general formulae (A-1) to (A-4), (2) or (3). [ka] (In the above general formulas (A-1) to (A-4), Y A1 , Y A2 may be the same or different, and each represents a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms. A is a hydrogen atom, a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, R A1 is an organic group that generates one or more hydroxyl or carboxyl groups by elimination of a protecting group by the action of either or both of an acid and heat, as represented by the following general formula (1), and * represents a bond with a carbonyl group. [ka] (In the above general formula (1), R A2 is an organic group whose protecting group is removed by the action of either acid or heat, or both, and * is Y A1 Or Y A2 )

[0081] In the above general formulas (A-1) to (A-4), Y A1 , Y A2 may be the same or different, and each represents a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms. A is a hydrogen atom, a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, R A1is an organic group in which the protecting group is eliminated by the action of either or both of the acid represented by the above general formula (1) and heat to generate one or more hydroxyl groups or carboxyl groups. In consideration of thermal fluidity, (A-4) is preferable, and in terms of increasing the tin content, (A-1) is preferable.

[0082] In the above general formulas (A-1) to (A-4), Y A2 Preferred examples of the structure include, but are not limited to, the structures shown below. a is R A1 The joint with * b represents the other bond. [ka]

[0083] In the above general formula (A-3), R A represents a hydrogen atom, a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, and is preferably hydrogen from the viewpoints of suppressing sublimate formation and increasing the Sn content.

[0084] In the above general formula (1), R A2 represents an organic group from which a thermal acid labile group is eliminated by the action of either an acid or heat, or both, and is preferably a tertiary hydrocarbyl group or a group which forms an acetal structure together with the adjacent oxygen atom, and particularly preferably a tertiary hydrocarbyl group.

[0085] The tertiary hydrocarbyl group preferably has 4 to 20 carbon atoms, and is particularly preferably a tert-butyl group from the viewpoints of suppressing sublimates due to thermal decomposition products and easiness of raw material procurement. Specific examples include, but are not limited to, the following. In the following formula, * represents a bond to an oxygen atom. [ka]

[0086] [ka]

[0087] [ka]

[0088] [ka]

[0089] The group that forms the acetal structure is not particularly limited as long as it is an organic group in which an unstable group is eliminated or cleaved by the action of either or both of an acid and heat. Specific examples of the group that forms the acetal structure include, but are not limited to, the following. In the following formula, * represents a bond to an oxygen atom. [ka]

[0090] [ka]

[0091] [ka]

[0092] Such a compound for forming a metal-containing film has excellent solvent solubility and thermal fluidity. A1Since it contains thermoacid labile groups, when it is used in a composition for forming a metal-containing film, these groups are eliminated during baking, increasing the tin content and enabling the formation of a metal-containing film with excellent dry etching resistance. Furthermore, the hydroxyl and carboxyl groups generated by the elimination react easily with radicals generated by the cleavage of tin-carbon bonds during baking due to the presence of terminal OH and α-hydrogen, causing a crosslinking reaction, and since it has excellent thermosetting properties, it is possible to suppress volume shrinkage, and a composition for forming a metal-containing film with excellent film-forming properties and planarization / filling properties can be provided even after high-temperature baking.

[0093] In the metal-containing film formed using an organotin compound, the organic group bonded to the Sn atom via a C atom is dissociated during baking to generate radicals, and the generated radicals form -Sn-O-Sn- bonds, initiating a condensation polymerization reaction, thereby progressing the hardening of the metal-containing film. On the other hand, since the organic group is eliminated simultaneously with the above reaction, a large film shrinkage occurs during baking. However, the above compound has a thermoacid labile group at the end, and the thermoacid labile group is eliminated during baking to generate a hydroxyl group or a carboxyl group, and the OH or α-hydrogen at the end of the group easily reacts with the radical, causing a crosslinking reaction as shown in the following reaction formula. Since the compound has at least one such organic group, it is possible to suppress the entire organic group from thermally decomposing and sublimating, and since the composition has excellent thermal fluidity, it is possible to provide a composition for forming a metal-containing film with excellent embeddability. [ka]

[0094] [ka] (In the above general formula (2), X is a divalent organic group having 1 to 31 carbon atoms, B is the following general formula (B), and * represents a bond to the carbonyl.) [ka] (In the above general formula (B), Y Brepresents a substituted or unsubstituted divalent saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms or an unsaturated divalent aliphatic hydrocarbon group having 2 to 20 carbon atoms, a substituted or unsubstituted divalent aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted divalent arylalkyl group having 7 to 31 carbon atoms, which may be bonded to an adjacent group via an oxygen atom or an NH group; R B is a hydroxyl group or any of the structures represented by the following general formulas (B-1) to (B-3). * represents the bond with the carbonyl group. [ka] (In the above general formulas (B-1) to (B-3), R B1 is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q is 0 or 1, * is Y B )

[0095] In the above general formula (2), X is a divalent organic group having 1 to 31 carbon atoms, B is the above general formula (B), and * represents a bond to a carbonyl. B represents a substituted or unsubstituted divalent saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms or an unsaturated divalent aliphatic hydrocarbon group having 2 to 20 carbon atoms, a substituted or unsubstituted divalent aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted divalent arylalkyl group having 7 to 31 carbon atoms, which may be bonded to an adjacent group via an oxygen atom or an NH group; R B is preferably a hydroxyl group or any of the structures represented by the above general formulas (B-1) to (B-3). B1 is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and is preferably a hydrogen atom from the viewpoint of suppressing sublimate formation.

[0096] Preferred examples of the structure of the above general formula (B) include, but are not limited to, the structures shown below: In the following formula, * represents a bond to the carbonyl. [ka]

[0097] Such a compound for forming a metal-containing film has excellent solvent solubility and thermal fluidity. B Since these compounds contain hydroxyl groups or unsaturated bonds therein, when they are used in a composition for forming a metal-containing film, they undergo a crosslinking reaction upon baking, resulting in excellent thermosetting properties. Furthermore, the crosslinking reaction is accelerated by reacting with radicals generated by the cleavage of tin-carbon bonds, and the excellent thermosetting properties make it possible to suppress volumetric shrinkage, thereby providing a composition for forming a metal-containing film that has excellent film-forming properties and planarizing properties / filling properties even after high-temperature baking.

[0098] [ka] (In the above general formula (3), X is a divalent organic group having 1 to 31 carbon atoms, C is any of the following general formulae (C-1) to (C-4), and * represents a bond to a carbonyl group.) [ka] (In the above general formulas (C-1) and (C-3), R C1 are each independently a hydrogen atom or a methyl group, and in the same formula, they may be the same or different. In (C-3) to (C-4), R C2 is a hydrogen atom, or a substituted or unsubstituted saturated or unsaturated monovalent aliphatic hydrocarbon 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. * represents the bond to the carbonyl group.)

[0099] In the above general formula (3), X is a divalent organic group having 1 to 31 carbon atoms, and specific examples thereof include a substituted or unsubstituted saturated divalent hydrocarbon group having 1 to 20 carbon atoms or an unsaturated divalent hydrocarbon group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms. C is the above general formulas (C-1) to (C-4), and in (C-1) and (C-3), R C1From the viewpoint of thermal fluidity, R is preferably a methyl group, and from the viewpoint of curability, R is preferably a hydrogen atom. C2 is preferably a hydrogen atom from the viewpoint of suppressing sublimate, and is preferably a structure other than a hydrogen atom as described above from the viewpoint of thermal fluidity.

[0100] In the above general formulas (C-1) to (C-4), R C2 Preferred structures of the formula include, but are not limited to, the structures shown below: In the formula, * represents a bond to the nitrogen atom. [ka]

[0101] A compound for forming a metal-containing film having such a structure contains an organic group represented by the above general formula (3), and therefore is a compound for forming a metal-containing film with excellent solvent solubility and heat resistance. Furthermore, since it contains any of the structures represented by the above general formulas (C-1) to (C-4) at its end, it has a high crosslinking group density, can reduce rapid volumetric shrinkage during baking, and has good thermal fluidity, so that a composition for forming a metal-containing film with excellent filling / planarization properties can be provided.

[0102] Y in the above general formulas (A-1) to (A-4) A1 Preferred structures of X in the above general formula (2) or X in the above general formula (3) include, but are not limited to, the structures shown below. In the following formulas, * represents a bond to a carbon atom of a carbonyl group or * in formulas (A-1) to (A-4), (2) and (3). [ka]

[0103] Y in the above general formulas (A-1) to (A-4) A1 It is preferable that X in the above general formula (2) or X in the above general formula (3) is a substituted or unsubstituted unsaturated hydrocarbon having 2 to 20 carbon atoms.

[0104] Y in the above general formulas (A-1) to (A-4) A1 When X in the above general formula (2) or X in the above general formula (3) is such an unsaturated hydrocarbon, the thermosetting property of the above metal-containing film-forming compound can be further improved.

[0105] In addition, Y in the above general formulas (A-1) to (A-4) A1 X in the above general formula (2) or X in the above general formula (3) may be the following general formula (4). [ka] (In the above general formula (4), R a , R b and R C is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and R a and R b may be bonded to form a cyclic substituent. *1 and *2 each represent a bond to a carbonyl group, and the substitution positions of *1 and *2 may be reversed.)

[0106] Carboxylic acid raw materials containing the above general formula (4) can be synthesized by ring-opening an acid anhydride, but when an asymmetric carboxylic acid anhydride is ring-opened, it becomes a mixture of two types, resulting in the above-mentioned bond type. The presence of such an isomer can suppress crystallinity, and is expected to improve solvent solubility and thermal fluidity, thereby improving planarization characteristics. [ka]

[0107] In the above general formula (4), R a , R b and R C is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and R a and R b may be bonded to form a cyclic substituent, and is particularly preferably a hydrogen atom from the viewpoint of suppressing sublimate formation.

[0108] In the above general formula (M-2), m1 is preferably 0 or 1 from the viewpoint of increasing the tin content, and when m1 is 1, R3 is preferably a hydroxyl group from the viewpoint of curability.

[0109] In the above general formula (M-2), when m1 is 0 or 1, the tin content increases, so that excellent etching resistance can be expected, and when m1 is 1 and R3 is a hydroxyl group, radical cleavage of the tin-carbon bond occurs during baking, but the hydroxyl group easily reacts with radicals, so that curability can be improved. Therefore, a metal-containing film-forming composition that has excellent film-forming properties, filling properties, and etching resistance even after high-temperature baking can be provided.

[0110] The metal-containing film-forming compound is preferably characterized in that the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn in terms of polystyrene measured by gel permeation chromatography is 1.00≦Mw / Mn≦1.50.

[0111] By definition, if it is a monomolecular compound, Mw / Mn is 1.00, but due to the separation characteristics of gel permeation chromatography, the measured value may exceed 1.00. Generally, it is extremely difficult for a polymer having repeating units to approach Mw / Mn=1.00 unless a special polymerization method is used, and there is a distribution of Mw, resulting in a Mw / Mn value exceeding 1. In the present invention, 1.00≦Mw / Mn≦1.50 is defined as an index showing monomolecularity in order to distinguish between monomolecular compounds and polymers.

[0112] A compound for forming a metal-containing film having a dispersity in such a range can be confirmed to be a monomolecular compound and further has better thermal fluidity, so that when it is blended into a composition for forming a metal-containing film, not only can it satisfactorily fill the fine structures formed on the substrate, but it can also form a resist underlayer film that flattens the entire substrate.

[0113] <Metal-containing film forming composition> The present invention also provides a composition for forming a metal-containing film that functions as a resist underlayer film material used in semiconductor manufacturing, the composition comprising (a) the compound for forming a metal-containing film of the present invention and (b) an organic solvent.

[0114] Such a composition for forming a metal-containing film contains an organotin compound that has excellent heat resistance and thermal fluidity, and therefore can provide a resist underlayer film material that has excellent dry etching resistance compared to conventional organic underlayer film materials and also has advanced filling / planarization properties.

[0115] Hereinafter, components contained in the composition for forming a metal-containing film of the present invention other than the above (a) compound for forming a metal-containing film will be described.

[0116] <(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, (c) crosslinking agent, (d) surfactant, (e) flow promoter, (f) acid generator, and other additives.

[0117] Specifically, the organic solvents described in paragraphs

[0091] to

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

[0118] (High boiling point solvent) In the composition for forming a resist underlayer film of the present invention, the (b) organic solvent may be used as a mixture of one or more organic solvents having a boiling point (value at 1 atmospheric pressure (1013 hPa)) of less than 180°C and one or more organic solvents (high boiling point solvents) having a boiling point of 180°C or higher.

[0119] The 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, chlorine-based solvents, etc., but specific examples include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-Hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, n-nonyl acetate, monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol-n-butyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, propylene glycol diacetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,Examples of the diethyl ester include 6-hexanediol diacetate, triethylene glycol diacetate, γ-butyrolactone, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, and dibutyl adipate. These may be used alone or in combination.

[0120] The high boiling point solvent may be appropriately selected from the above-mentioned solvents according to the temperature at which the resist underlayer film forming composition of the present invention is heat-treated. The boiling point of the high boiling point solvent is preferably 180°C to 300°C, more preferably 200°C to 300°C. If the solvent has such a boiling point, there is no risk of the solvent volatilizing too quickly during baking (heat treatment), so that sufficient thermal fluidity can be obtained during film formation, and it is believed that a resist underlayer film having excellent filling / flattening properties can be formed. In addition, if the solvent has such a boiling point, the solvent does not volatilize and remains in the film after baking, so there is no risk of adversely affecting the film properties such as etching resistance.

[0121] The amount of the organic solvent to be added is preferably in the range of 200 to 10,000 parts, more preferably 250 to 5,000 parts, based on 100 parts by mass of the (a) compound for forming a metal-containing film.

[0122] When a high boiling point solvent is used, the blending amount is preferably 1 to 30 parts by mass per 100 parts by mass of an organic solvent having a boiling point of less than 180° C. Such a blending amount is preferable because it can impart sufficient thermal fluidity during baking and does not remain in the film, leading to deterioration of film properties such as etching resistance.

[0123] <Composition for forming resist underlayer film> The composition is a composition for forming a metal-containing film that can be used as a resist underlayer film in a multi-layer resist method, and can further contain one or more of (c) a crosslinking agent, (d) a surfactant, (e) a flowability promoter, and (f) an acid generator. Hereinafter, components contained in the composition for forming a resist underlayer film of the present invention other than (a) the compound for forming a metal-containing film and (b) the organic solvent will be described.

[0124] [(c) Crosslinking agent] The resist underlayer film forming composition of the present invention may further contain (c) a crosslinking agent in order to increase the denseness of the film and further suppress intermixing with the resist upper layer film. The crosslinking agent is not particularly limited, and various known crosslinking agents can be widely used. Examples include melamine-based crosslinking agents, acrylate-based crosslinking agents, glycoluril-based crosslinking agents, benzoguanamine-based crosslinking agents, urea-based crosslinking agents, β-hydroxyalkylamide-based crosslinking agents, isocyanurate-based crosslinking agents, aziridine-based crosslinking agents, oxazoline-based crosslinking agents, phenol-based crosslinking agents (e.g., methylol or alkoxymethyl-type crosslinking agents of polynuclear phenols), epoxy-based crosslinking agents, and oxetane-based crosslinking agents. The content of the (c) crosslinking agent is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, based on 100 parts by mass of the (a) metal-containing film forming compound.

[0125] 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 the urea-based crosslinking agent include dimethoxymethylated dimethoxyethyleneurea, its alkoxy and / or hydroxyl 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 crosslinking agent include 2,2'-isopropylidenebis(4-benzyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2-oxazoline), 2,2'-methylenebis-4,5-diphenyl-2-oxazoline, 2,2'-methylenebis-4-phenyl-2-oxazoline, 2,2'-methylenebis-4-tertbutyl-2-oxazoline, 2,2'-bis(2-oxazoline), 1,3-phenylenebis(2-oxazoline), 1,4-phenylenebis(2-oxazoline), and 2-isopropenyloxazoline copolymer.

[0126] Specific examples of polynuclear phenol-based crosslinking agents include compounds represented by the following general formula (XL-1). [ka] (In the formula, S is a single bond or a hydrocarbon group having 1 to 20 carbon atoms and a valence of s. R6 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. s is an integer of 1 to 5.)

[0127] S is a single bond or a hydrocarbon group having 1 to 20 carbon atoms and a valence of s. s is an integer of 1 to 5, and is more preferably 2 or 3. Specific examples of S include groups obtained by removing s hydrogen atoms from methane, ethane, propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, methylpentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylisopropylbenzene, diisopropylbenzene, methylnaphthalene, ethylnaphthalene, and eicosane. R6 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, an octyl group, an ethylhexyl group, a decyl group, and an eicosanyl group, and a hydrogen atom or a methyl group is preferable.

[0128] Specific examples of the compound represented by the above general formula (XL-1) include the following compounds. Among these, from the viewpoint of improving the curability and thickness uniformity of the organic film, hexamethoxymethylated triphenolmethane, triphenolethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene are preferred. R6 is the same as above. [ka]

[0129] [ka]

[0130] The epoxy-based crosslinking agent and the oxetane-based crosslinking agent may be of a monomolecular type or a polymer type. Specific examples of the monomolecular type include, but are not limited to, those shown below. [ka]

[0131] The above compounds are commercially available, but the epoxy-based crosslinking agent and the oxetane-based crosslinking agent can also be obtained by reacting a hydroxyl group with epibromohydrin, 3-bromomethyloxetane, or the like, as shown in the following formula. In the following formula, R is 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 alkyl group having 7 to 31 carbon atoms. All the hydroxyl groups can be left unreacted. In this case, it is preferable that the number of epoxy + oxetane is greater than the number of hydroxyl groups, and more preferably, the number of epoxy + oxetane is greater than the number of hydroxyl groups*2. The content of these compounds is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the (a) metal-containing film-forming compound. [ka]

[0132] Specific examples of compounds having a hydroxyl group that can be used in the above reaction include, but are not limited to, the following: [ka]

[0133] As the polymer type, specifically, there can be mentioned polymers in which the molar fraction of the repeating units represented by the following general formulae (XL-2) and (XL-3) is 20% or more. When the molar fraction of the structural units represented by the general formulae (XL-2) and (XL-3) does not total 100%, other structural units include α,β-unsaturated carboxylic acid esters such as other acrylic acid esters, other methacrylic acid esters, other acrylic acid amides, other methacrylic acid amides, crotonates, maleates, and itaconic acid esters; α,β-unsaturated carboxylic acids such as methacrylic acid, acrylic acid, maleic acid, and itaconic acid; acrylonitrile; methacrylonitrile; α,β-unsaturated lactones such as 5,5-dimethyl-3-methylene-2-oxotetrahydrofuran; norbornene derivatives, tetracyclo[4.4.0.1 2,5 .1 7,10 Any structural unit derived from cyclic olefins such as dodecene derivatives; α,β-unsaturated carboxylic anhydrides such as maleic anhydride and itaconic anhydride; allyl ethers; vinyl ethers; vinyl esters; and vinyl silanes can be used in combination. These polymers preferably have a weight average molecular weight of 1,000 to 20,000 and a GPC dispersion degree of 2.0 or less. The content of these compounds is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the (A) compound for forming a metal-containing film.

[0134] [ka] (In the formula, R7 is a hydrogen atom or a methyl group, R8 is a hydrogen atom or a group selected from the following formulae (2-1) to (2-3), and L1 is a divalent organic group containing a single bond, -C(=O)O-, -C(=O)NH-, or -C(=O)NCH3-.)

[0135] In the above general formula (XL-2), from the viewpoint of curability, it is preferable that R8 satisfy the relationship: epoxy + number of oxetane > number of hydroxyl groups, and more preferably epoxy + number of oxetane > number of hydroxyl groups * 2. [ka] (In the formula, R7 is a hydrogen atom or a methyl group, and R9 is a group selected from the following formulae (2-1) to (2-3).) [ka] (In the above formula, the dashed lines represent bonds.)

[0136] <(d) Surfactant> To the resist underlayer film forming composition of the present invention, a surfactant (d) can be added to improve the coating property in spin coating. For example, the surfactants described in

[0142] to

[0147] of JP-A-2009-269953 can be used. When the surfactant is added, the amount of the surfactant is preferably 0.01 to 10 parts, more preferably 0.05 to 5 parts, based on 100 parts by mass of the above-mentioned (a) compound for forming a metal-containing film.

[0137] <(e) Flow enhancers> The resist underlayer film forming composition of the present invention can also be blended with other compounds or polymers. The flow promoter is mixed with the metal-containing film forming compound of the present invention to improve the film forming properties of spin coating and the embedding properties of a substrate having a step. The flow promoter is preferably a material having a high carbon atom density and high etching resistance.

[0138] Such materials include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 3,5- Diphenylphenol, 2-naphthylphenol, 3-naphthylphenol, 4-naphthylphenol, 4-tritylphenol, resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, catechol, 4-tert-butylcatechol, 2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 2-methoxy-5-methylphenol, 2-tert-Butyl-5-methylphenol, pyrogallol, thymol, isothymol, 4,4'-(9H-fluoren-9-ylidene)bisphenol, 2,2'dimethyl-4,4'-(9H-fluoren-9-ylidene)bisphenol, 2,2'diallyl-4,4'-(9H-fluoren-9-ylidene)bisphenol, 2,2'difluoro-4,4'-(9H-fluoren-9-ylidene)bisphenol, 2,2'diphenyl-4,4'-(9H-fluoren-9-ylidene)bisphenol, 2,2'dimethoxy-4,4'-(9H- fluoren-9-ylidene) bisphenol, 2,3,2',3'-tetrahydro-(1,1')-spirobiindene-6,6'-diol, 3,3,3',3'-tetramethyl-2,3,2',3'-tetrahydro-(1,1')-spirobiindene-6,6'-diol, 3,3,3',3',4,4'-hexamethyl-2,3,2',3'-tetrahydro-(1,1')-spirobiindene-6,6'-diol, 2,3,2',3'-tetrahydro-(1,1')-spirobiindene-5,5'-diol, 5,5'-dimethyl-3,3,3',3'-tetramethyl-2,3,2',3'-tetrahydro-(1,1')-spirobiindene-6,6'-diol, 1-naphthol, 2-naphthol, 2-methyl-1-naphthol, 4-methoxy-1-naphthol, 7-methoxy-2-naphthol, dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene, 3-hydroxynaphthalene-2-methyl carboxylate, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, and biphenyl. Examples of the novolak resins include bisphenol, trisphenol, dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborn-2-ene, α-pinene, β-pinene, and limonene; polyhydroxystyrene, polystyrene, polyvinylnaphthalene, polyvinylanthracene, polyvinylcarbazole, polyindene, polyacenaphthylene, polynorbornene, polycyclodecene, polytetracyclododecene, polynortricyclene, poly(meth)acrylate, and copolymers thereof. In addition, naphthol dicyclopentadiene copolymers described in JP 2004-205685 A, fluorene bisphenol novolac resins described in JP 2005-128509 A, acenaphthylene copolymers described in JP 2005-250434 A, fullerenes having phenol groups described in JP 2006-227391 A, bisphenol compounds and novolac resins described in JP 2006-293298 A, novolac resins of adamantanephenol compounds described in JP 2006-285095 A, bisnaphthol compounds and novolac resins described in JP 2010-122656 A, fluorene compounds described in JP 2017-119671 A, and fullerene resin compounds described in JP 2008-158002 A can also be blended. The blending amount of the flow promoter is preferably 0.001 to 100 parts by mass, more preferably 0.01 to 50 parts by mass, based on 100 parts by mass of the compound for forming a metal-containing film of the present invention.

[0139] In addition, in the composition for forming a resist underlayer film of the present invention, as an additive for imparting filling / flattening properties, for example, a liquid additive having a polyethylene glycol or polypropylene glycol structure, or a thermally decomposable polymer 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 is preferably used. This thermally decomposable polymer preferably contains a repeating unit having an acetal structure represented by the following general formula (DP1) or (DP1a).

[0140] [ka] (In the formula, R 10 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.

[0141] [ka] (In the formula, R 10a 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.

[0142] <(f) Acid generator> The resist underlayer film forming composition of the present invention may contain (f) an acid generator to further promote the elimination reaction. The acid generator (f) may be one that generates an acid by thermal decomposition or one that generates an acid by light irradiation, and any of these may be added. Specifically, the materials described in paragraphs

[0061] to

[0085] of JP-A-2007-199653 may be added, but are not limited thereto.

[0143] The acid generators can be used alone or in combination of two or more. When an acid generator is added, the amount of the acid generator is preferably 0.05 to 50 parts, more preferably 0.1 to 10 parts, based on 100 parts by mass of the (a) compound for forming a metal-containing film.

[0144] <Method for forming resist underlayer film> The present invention provides a method for forming a filling film that functions as a resist underlayer film of a multi-layer resist film used in lithography or a planarizing film for semiconductor manufacturing, using the above-mentioned metal-containing film-forming composition.

[0145] In the method for forming a resist underlayer film using the composition for forming a metal-containing film of the present invention, the composition for forming a metal-containing film is coated on a substrate to be processed by spin coating or the like. By using the spin coating or the like, good embedding properties can be obtained. After spin coating, the solvent is evaporated, and baking (heat treatment) is performed to promote a crosslinking reaction in order to prevent mixing with the resist upper layer film or the resist intermediate film. The baking is preferably performed at 100°C or higher and 600°C or lower for 10 to 600 seconds, more preferably at 200°C or higher and 500°C or lower for 10 to 300 seconds. Considering the influence on device damage and wafer deformation, the upper limit of the heating temperature in the wafer process of lithography is preferably 600°C or lower, more preferably 500°C or lower.

[0146] In addition, in a method for forming a resist underlayer film using the composition for forming a metal-containing film of the present invention, the composition for forming a metal-containing film of the present invention can be coated on a substrate to be processed by a spin coating method or the like as described above, and the composition for forming a metal-containing film can be baked and cured in an atmosphere having an oxygen concentration of 0.1 vol.% or more and 21 vol.% or less to form a metal-containing film.

[0147] 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 the atmosphere during baking may be air, it is preferable to seal in an inert gas such as N2, Ar, or He to reduce oxygen in order to prevent oxidation of the metal-containing film. In order to prevent oxidation, it is necessary to control the oxygen concentration, which is preferably 1000 ppm or less, more preferably 100 ppm or less (volume basis). Preventing oxidation of the metal-containing film during baking is preferable because it does not increase absorption or reduce etching resistance.

[0148] <Pattern Forming Method Using Composition for Forming Resist Underlayer Film> The present invention also provides a pattern formation method by a two-layer resist process using the above-mentioned metal-containing film-forming composition, which comprises forming a metal-containing film on a substrate to be processed using the above-mentioned metal-containing film-forming composition, forming a resist upper layer film on the metal-containing film using a photoresist material, exposing the resist upper layer film to light and then developing the resist upper layer film with a developer to form a pattern in the resist upper layer film, transferring the pattern to the metal-containing film by dry etching using the resist upper layer film with the pattern formed as a mask, and processing the substrate to be processed using the metal-containing film with the pattern formed as a mask to form a pattern on the substrate to be processed.

[0149] Since the resist top layer film in the two-layer resist process exhibits etching resistance to chlorine-based gases, it is preferable that the dry etching of the metal-containing film in the two-layer resist process is performed using the resist top layer film as a mask with an etching gas mainly containing a chlorine-based gas.

[0150] In addition, the present invention provides a pattern formation method by a three-layer resist process using such a metal-containing film-forming composition, which includes forming a metal-containing film on a substrate to be processed using the above-mentioned metal-containing film-forming composition, forming a silicon-containing resist intermediate film on the metal-containing film using a silicon-containing resist intermediate film material, forming a resist upper layer film on the resist intermediate film using a photoresist material, exposing the resist upper layer film to a pattern, and developing the resist upper layer film with a developer to form a pattern on the resist upper layer film. Using the resist upper layer film with the pattern formed as a mask, transfer the pattern to the resist intermediate film by dry etching. Using the resist intermediate film with the pattern transferred as a mask, transfer the pattern to the metal-containing film by dry etching. Using the metal-containing film with the pattern formed as a mask, the substrate to be processed is processed. A pattern formation method is provided, which is characterized by the above-mentioned.

[0151] An example of a three-layer resist process is specifically shown below with reference to Figure 1. In the case of the three-layer resist process, as shown in Figure 1(A), a metal-containing film (metal-containing resist underlayer film) 3 is formed on a processable layer 2 laminated on a processable substrate 1 using the metal-containing film-forming composition of the present invention, and then a silicon-containing resist intermediate film 4 is formed, and a resist upper layer film 5 is formed thereon.

[0152] Next, as shown in FIG. 1(B), a desired portion (exposed portion) 6 of the resist upper layer film 5 is exposed, and PEB and development are performed to form a resist upper layer film pattern 5a (FIG. 1(C)). Using the obtained resist upper layer film pattern 5a as a mask, the silicon-containing resist intermediate film 4 is etched using a CF-based gas to form a silicon-containing resist intermediate film pattern 4a (FIG. 1(D)). After removing the resist upper layer film pattern 5a, the metal-containing film 3 is chlorine plasma etched using the obtained silicon-containing resist intermediate film pattern 4a as a mask to form a metal-containing film pattern (metal-containing resist underlayer film pattern) 3a (FIG. 1(E)). Furthermore, after removing the silicon-containing resist intermediate film pattern 4a, the processed layer 2 is etched using the metal-containing film pattern 3a as a mask to form a pattern 2a in the processed layer (FIG. 1(F)).

[0153] The silicon-containing resist intermediate film in the above three-layer resist process exhibits etching resistance to chlorine-based gas and hydrogen-based gas, so in the above 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 composed of a chlorine-based gas or a hydrogen-based gas.

[0154] As the silicon-containing resist intermediate film in the above three-layer resist process, a polysiloxane-based intermediate film is also preferably used. By imparting an anti-reflection effect to the silicon-containing resist intermediate film, reflection can be suppressed. In particular, for 193 nm exposure, if a material containing many aromatic groups and having high etching selectivity with the substrate is used as the organic film, the k value becomes high and the substrate reflection becomes high, but by imparting absorption to the silicon-containing resist intermediate film to obtain an appropriate k value, it becomes possible to suppress reflection, and the substrate reflection can be reduced to 0.5% or less. As the silicon-containing resist intermediate film having an anti-reflection effect, anthracene is preferably used for 248 nm and 157 nm exposure, and polysiloxane with a pendant light-absorbing group having a phenyl group or a silicon-silicon bond and crosslinked by acid or heat is preferably used for 193 nm exposure.

[0155] In addition, the present invention provides a pattern formation method by a four-layer resist process using such a metal-containing film-forming composition, which includes forming a metal-containing film on a substrate to be processed using the above-mentioned metal-containing film-forming composition, forming a silicon-containing resist intermediate film on the resist underlayer 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 upper layer film on the BARC using a photoresist material, exposing the resist upper layer film to a pattern, and developing the resist upper layer film 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, a pattern is transferred to the BARC or adhesion film and the silicon-containing resist intermediate film by dry etching. Using the silicon-containing resist intermediate film on which the pattern has been transferred as a mask, a pattern is transferred to the metal-containing film by dry etching. The pattern formation method is characterized by having the steps 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.

[0156] Alternatively, an inorganic hard mask may be formed instead of the silicon-containing resist underlayer film. In this case, at least a metal-containing film is formed on a workpiece using the metal-containing film-forming composition of the present invention, an inorganic hard mask selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film is formed on the metal-containing film, a resist upper layer film is formed on the inorganic hard mask using a photoresist composition to form a circuit pattern on the resist upper layer film, the inorganic hard mask is etched using the resist upper layer film on which the pattern has been formed as a mask, the metal-containing film is etched using the inorganic hard mask on which the pattern has been formed as a mask, and the workpiece is etched using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the workpiece, thereby forming a semiconductor device circuit pattern on the substrate.

[0157] As described above, when an inorganic hard mask is formed on a metal-containing film, a silicon oxide film, a silicon nitride film, and a silicon oxide nitride 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-A-2002-334869 and WO-A-2004 / 066377. The thickness of the inorganic hard mask is preferably 5 to 200 nm, more preferably 10 to 100 nm. In addition, a SiON film, which has a high effect as an anti-reflective film, is most preferably used as the inorganic hard mask. Since the substrate temperature when forming the SiON film is 300 to 500° C., the metal-containing film needs to withstand a temperature 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., so that it is possible to combine an inorganic hard mask formed by a CVD method or an ALD method with a metal-containing film formed by a spin coating method.

[0158] As described above, a photoresist film may be formed on the inorganic hard mask as a resist top layer, but an organic anti-reflective coating (BARC) or adhesion film may be formed on the inorganic hard mask by spin coating, and a photoresist film may be formed on top of that. In particular, when a SiON film is used as the inorganic hard mask, the two-layer anti-reflective coating of the SiON film and the BARC makes it possible to suppress reflection even in immersion exposure with a high NA exceeding 1.0. Another advantage of forming the BARC is that it has the effect of reducing the tailing of the photoresist pattern directly above the SiON film.

[0159] In addition, in the present invention, as a pattern formation method by a multilayer resist process using such a metal-containing film-forming composition, a resist underlayer film is formed on a substrate to be processed, the metal-containing film-forming composition of the present invention is applied on the resist underlayer, and then a metal-containing film is formed by heat treatment. A resist upperlayer film is formed on the metal-containing film using a photoresist material, the resist upperlayer film is pattern-exposed and then developed with a developer to form a pattern in the resist upperlayer film, and the resist upperlayer film on which the pattern has been formed is used as a mask to transfer the pattern to the metal-containing film by dry etching. Using the metal-containing film on which the pattern has been transferred as a mask, a pattern is transferred to the resist underlayer film by dry etching. Furthermore, the resist underlayer film on which the pattern has been formed is used as a mask to process the substrate to form a pattern on the substrate to be processed, thereby forming a semiconductor device circuit pattern on the substrate.

[0160] As described above, a photoresist film may be formed on the metal-containing film as a resist upper layer film, but an organic adhesive film may be formed on the metal-containing film by spin coating, and a photoresist film may be formed thereon.

[0161] 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 organic underlayer film material, a CVD method, an ALD method, etc. Coating type organic underlayer film materials are disclosed in JP2012-001687A, JP2012-077295A, JP2004-264710A, JP2005-043471A, JP2005-250434A, JP2007-293294A, JP2008-065303A, and the like. No. 2004-205685, No. 2007-171895, No. 2009-014816, No. 2007-199653, No. 2008-274250, No. 2010-122656, No. 2012-214720, No. 2014-0 Examples of resins and compositions disclosed in JP-A-2005-128509, JP-A-2006-259249, JP-A-2006-259482, JP-A-2006-293298, JP-A-2007-316282, JP-A-2012-145897, JP-A-2017-119671, JP-A-2019-044022, and the like can be mentioned.

[0162] The resist upper layer film in the above multi-layer resist process may be either positive or negative, and may be the same as a commonly used photoresist composition. After spin-coating the photoresist composition, pre-baking is performed, preferably at 60 to 180°C for 10 to 300 seconds. Thereafter, exposure is performed according to a conventional method, followed by post-exposure baking (PEB) and development to obtain a resist pattern. The thickness of the resist upper layer film is not particularly limited, but is preferably 30 to 500 nm, and more preferably 50 to 400 nm.

[0163] Examples of the 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.

[0164] The method for forming the pattern on the resist upper layer film is preferably photolithography with a wavelength of 5 nm or more and 300 nm or less, direct drawing with an electron beam, nanoimprinting, or a combination of these.

[0165] In the pattern forming method, the development method is preferably alkaline development or development using an organic solvent.

[0166] 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 and the inorganic hard mask is performed using a fluorocarbon-based gas as a mask for the upper resist pattern. This forms a silicon-containing resist intermediate film pattern and an inorganic hard mask pattern.

[0167] Next, the metal-containing film is etched using the silicon-containing resist intermediate film pattern or the inorganic hard mask pattern as a mask. The etching of the metal-containing film is preferably performed using an etching gas mainly containing a chlorine-based gas.

[0168] The next etching of the workpiece can also be done by a normal method, for example, if the workpiece is SiO2, SiN, or a silica-based low dielectric constant insulating film, etching is done mainly with 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.

[0169] The metal-containing film obtained by using the metal-containing film-forming composition of the present invention is characterized by excellent etching resistance when etching the workpiece.

[0170] 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 on which a workpiece layer is formed. As the workpiece layer, various low-k films such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, or Al-Si and their stopper films are used, and may be formed to a thickness of usually 50 to 10,000 nm, particularly 100 to 5,000 nm. When forming a workpiece layer, the substrate and the workpiece layer are made of different materials.

[0171] In the pattern forming method using the metal-containing film forming composition of the present invention, it is preferable to use a substrate to be processed having a structure or step having a height of 30 nm or more. As described above, since the metal-containing film forming composition of the present invention has excellent filling / flattening properties, even if the substrate to be processed has a structure or step (unevenness) having a height of 30 nm or more, a flat cured film can be formed. The height of the structure or step of the substrate to be processed is preferably 30 nm or more, more preferably 50 nm or more, and more preferably 100 nm or more. In the method for processing a stepped substrate having a pattern of the above height, the metal-containing film forming composition of the present invention is formed into a film and filled / flattened, thereby making it possible to uniformize the film thickness of the resist intermediate film and resist top layer film to be formed thereafter, which is very preferable, since it is easy to ensure the exposure depth margin (DOF) during photolithography.

[0172] <Method of forming a tone-reversal pattern using a composition for forming a metal-containing film> Further, in the present invention, a tone-reversal pattern formation method using such a metal-containing film-forming composition includes forming a resist underlayer film on a substrate to be processed, 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, 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, exposing the resist upper layer film to a pattern and developing it with a developer to form a pattern on the resist upper layer film, transferring the 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, and then performing dry etching on the resist intermediate film or the inorganic hard mask intermediate film on which the pattern has been transferred by using the resist intermediate film or the inorganic hard mask intermediate film as a mask. a metal-containing film covering the resist underlayer film on which the pattern has been formed, using the metal-containing film-forming composition to form a metal-containing film, filling spaces between the resist underlayer film patterns with the metal-containing film, etching back the metal-containing film covering the resist underlayer film on which the pattern has been formed by using a chemical stripper or dry etching to expose an upper surface of the resist underlayer film on which the pattern has been formed, removing the resist intermediate film or hard mask intermediate film remaining on the upper surface of the resist underlayer film by dry etching, removing the resist underlayer film on which the pattern has been formed and its surface exposed by dry etching, forming a reverse pattern of the original pattern on the metal-containing film, and processing the workpiece substrate using the metal-containing film on which the reverse pattern has been formed as a mask to form a reverse pattern on the workpiece substrate.

[0173] An example of the formation of a tone reversal pattern is specifically shown below with reference to Fig. 2. As shown in Fig. 2(G), a resist underlayer film 7 made of a coating type organic underlayer film material is formed on a processable layer 2 laminated on a processable substrate 1, and then a silicon-containing resist intermediate film 4 is formed, and a resist upper layer film 5 is formed thereon.

[0174] Next, as shown in Fig. 2(H), a desired portion (exposed portion) 6 of the resist upper layer film 5 is exposed, and PEB and development are performed to form a resist upper layer film pattern 5a (Fig. 2(I)). Using the obtained resist upper layer film pattern 5a as a mask, the silicon-containing resist intermediate film 4 is etched using a CF-based gas to form a silicon-containing resist intermediate film pattern 4a (Fig. 2(J)). After removing the resist upper layer film pattern 5a, the resist underlayer film 7 made of a coating type organic underlayer film material is oxygen plasma etched using the obtained silicon-containing resist intermediate film pattern 4a as a mask to form a resist underlayer film pattern 7a made of a coating type organic underlayer film material (Fig. 2(K)).

[0175] The metal-containing film-forming composition of the present invention is applied onto the resist underlayer film pattern 7a made of a coating type organic underlayer film material, and then heat-treated to cover the metal-containing film 8, and the metal-containing film fills the gaps between the resist underlayer film patterns 7a made of the coating type organic underlayer film material (FIG. 2(L)). Next, the metal-containing film 8 covering the resist underlayer film pattern 7a made of the coating type organic underlayer film material is etched back by a chemical stripper or dry etching to expose the upper surface of the resist underlayer film pattern 7a made of the coating type organic underlayer film material (FIG. 2(M)). Furthermore, the silicon-containing resist intermediate film pattern 4a remaining on the upper surface of the resist underlayer film pattern 7a made of the coating type organic underlayer film material is removed by dry etching (FIG. 2(N)). Next, the resist underlayer film pattern 7a made of the coating-type organic underlayer film material is removed by dry etching, and an inverted pattern of the original pattern is formed on the metal-containing film (a metal-containing film pattern 8a which is an inverted version of the resist underlayer film pattern) (FIG. 2(O)). After that, the workpiece substrate is processed using the metal-containing film pattern 8a which is an inverted version of the resist underlayer film pattern as a mask to form a tone-reversed pattern on the workpiece substrate (FIG. 2(P)).

[0176] 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 organic underlayer film material, a CVD method, an ALD method, etc. Coating type organic underlayer film materials are disclosed in JP2012-1687A, JP2012-77295A, JP2004-264710A, JP2005-043471A, JP2005-250434A, JP2007-293294A, JP2008-65303A, JP2009-100111A, and JP2006-2009-2010. JP 2004-205685 A, JP 2007-171895 A, JP 2009-14816 A, JP 2007-199653 A, JP 2008-274250 A, JP 2010-122656 A, JP 2012-214720 A, JP 2014-29435 A, Examples of the resins and compositions disclosed in International Publication WO2012 / 077640, International Publication WO2010 / 147155, International Publication WO2012 / 077640, International Publication WO2010 / 147155, International Publication WO2012 / 176767, JP 2005-128509 A, JP 2006-259249 A, JP 2006-259482 A, JP 2006-293298 A, JP 2007-316282 A, JP 2012-145897 A, JP 2017-119671 A, JP 2019-44022 A, and the like can be mentioned.

[0177] In the above-mentioned tone reversal pattern forming method, it is preferable to coat the obtained resist underlayer film pattern with a metal-containing film forming composition, and then remove the metal-containing film using a dry etching gas mainly composed of a chlorine-based gas to expose the upper surface of the resist underlayer film pattern. Then, the resist intermediate film or hard mask intermediate film remaining on the resist underlayer film is removed by dry etching with a fluorocarbon-based gas, and the resist underlayer film pattern with the exposed surface is removed by dry etching with an oxygen-based gas to form a metal-containing film pattern.

[0178] In the tone reversal patterning method, the resist underlayer film pattern preferably has a structure or step having a height of 30 nm or more. As described above, the metal-containing film-forming composition of the present invention has excellent filling / flattening properties, so that even if the processed film has a structure or step (unevenness) having a height of 30 nm or more, a flat cured film can be formed. The height of the structure or step of the resist underlayer film pattern is preferably 30 nm or more, more preferably 50 nm or more, and more preferably 100 nm or more. In the method for reversing a resist underlayer film pattern having a pattern of the above height, the metal-containing film-forming composition of the present invention is formed into a film and filled / flattened, so that the reversal / transfer of the pattern can be performed with high accuracy, which is very preferable. Compared to the resist underlayer film using a conventional coating-type organic underlayer film material, the composition has excellent resistance to dry etching using a fluorocarbon-based gas, so that the resist underlayer film pattern can be reversed with the metal-containing film-forming composition to form a desired resist pattern on the processed film with high accuracy. EXAMPLES

[0179] The present invention will be described in more detail below with reference to Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited thereto. Note that, as for the molecular weight and dispersity, the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene were determined by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent, and the dispersity (Mw / Mn) was determined.

[0180] [Synthesis example] In the following synthesis examples and comparative examples, the following tin compounds Sn: (Sn-1) to (Sn-5), raw material group X: (X-1) to (X-12), and raw material group G: (G-1) to (G-7) were used. Each raw material group is shown below.

[0181] Tin compounds (Sn): [ka]

[0182] Raw material group X: [ka]

[0183] Raw material group G: [ka]

[0184] [Synthesis Example 1] Synthesis of metal-containing film-forming compound (A-1) 5.0 g of tin compound (Sn-4), 1.9 g of raw material (X-1) and 100 g of toluene were added and reacted for 7 hours at 130° C. while removing water. After the reaction, the solvent was removed under reduced pressure to obtain compound (A-1). (A-1): Mw = 554, Mw / Mn = 1.04

[0185] [Synthesis Example 2] Synthesis of metal-containing film-forming compound (A-2) 5.0 g of tin compound (Sn-1), 1.6 g of raw material (X-2) and 100 g of toluene were added and reacted for 7 hours at 100°C while removing tert-butyl alcohol. After the reaction, the solvent was removed under reduced pressure to obtain compound (A-2). (A-2): Mw = 890, Mw / Mn = 1.09

[0186] [Synthesis Example 4] Synthesis of metal-containing film-forming compound (A-4) 5.0 g of tin compound (Sn-5), 4.7 g of raw material (X-4) and 100 g of toluene were added and reacted for 7 hours at 100° C. After the reaction, the solvent was removed under reduced pressure to obtain compound (A-4). (A-4): Mw = 1530, Mw / Mn = 1.26

[0187] [Synthesis Examples 3, 5-8] Synthesis of metal-containing film-forming compounds (A-3), (A-5) to (A-8) Except for using the tin compound Sn and the above-mentioned raw material group X in the amounts shown in Tables 1-1 and 1-2, (A-3) and (A-5) to (A-8) were obtained under the same reaction conditions as in Synthesis Example 1. The weight average molecular weight (Mw) and dispersity (Mw / Mn) of these compounds were determined. The results are shown in Table 2.

[0188] [Synthesis Examples 9-14] Synthesis of metal-containing film-forming compounds (A-9)-(A-14) Except for using the raw material group X and raw material group G in the amounts shown in Table 1-2, (A-9) to (A-14) were obtained under the same reaction conditions as in Synthesis Example 4. The weight average molecular weight (Mw) and dispersity (Mw / Mn) of these compounds were determined. The results are shown in Table 2.

[0189] [Table 1-1]

[0190] [Table 1-2]

[0191] [Synthesis of Comparative Metal-containing Film-forming Compound (R-1)] 5.0 g of tin compound (Sn-2), 11.4 g of raw material group G (G-7), and 100 g of toluene were added and reacted for 7 hours at 130° C. while removing water. After the reaction, the solvent was removed under reduced pressure to obtain (R-1). [ka]

[0192] [Synthesis of Comparative Metal-containing Film-forming Compound (R-2)] 5.0 g of tin compound (Sn-2), 6.8 g of raw material group X (X-12), and 50 g of toluene were added and reacted for 7 hours at 130°C while removing water. After the reaction, the solvent was removed under reduced pressure to obtain (R-2). [ka]

[0193] The weight average molecular weight (Mw) and dispersity (Mw / Mn) of these compounds were determined, and the results are shown in Table 2.

[0194] [Table 2]

[0195] [Synthesis of Comparative Metal-containing Film-forming Compound (R-3)] As a metal-containing compound intended for use in photoresists, a tin compound reported in [Synthesis Example 8] of Japanese Patent No. 7028940 was synthesized. 3 g of isopropyltriphenyltin, 1.4 g of succinic acid, and 20 ml of acetonitrile were dissolved in acetonitrile and refluxed for 24 hours. After the reaction, the solvent was removed under reduced pressure to obtain a tin-containing compound (R-3). [ka]

[0196] [Synthesis of Comparative Metal-containing Film-forming Compound (R-4)] 10g of catechol, 6.6g of formaldehyde, and 30g of PGME (propylene glycol monomethyl ether) were added and homogenized at an internal temperature of 100℃. Then, a mixture of 0.2g of paratoluenesulfonic acid monohydrate and 3.0g of PGME, which had been mixed and homogenized in advance, was slowly dropped and reacted at an internal temperature of 120℃ for 8 hours. After the reaction was completed, 300ml of MIBK was added, and the mixture was washed four times with 200ml of pure water, and the organic layer was dried under reduced pressure. Then, 22g of tin raw material (Sn-2) and 300g of toluene were added and stirred at 130℃ for 8 hours. After the reaction, the solvent was removed under reduced pressure to obtain (R-4). [ka]

[0197] [Synthesis of Comparative Metal-containing Film-forming Compound (R-5)] As a compound having a metal different from the compound for forming a metal-containing film of the present invention, a titanium compound reported in [Synthesis Example A-II] of Japanese Patent No. 6189758 was synthesized. A solution of 27 g of deionized water and 500 g of IPA was dropped into a solution of 284 g of titanium tetraisopropoxide (Tokyo Chemical Industry Co., Ltd.) in 500 g of IPA while stirring at room temperature for 2 hours. 120 g of 2-methyl-2,4-pentanediol was added to the obtained solution and stirred at room temperature for 30 minutes. After concentrating this solution at 30°C under reduced pressure, it was further heated to 60°C and continued to be heated under reduced pressure until no distillate was produced. When no distillate was observed, 1,200 g of PGMEA was added and heated at 40°C under reduced pressure until no IPA was produced, obtaining 1,000 g of a PGMEA solution of titanium-containing compound (R-5) (compound concentration 20% by mass). The molecular weight of this product in terms of polystyrene was measured and found to be Mw=1,100.

[0198] [Synthesis of Comparative Organic Film-Forming Resin (R-6)] In a nitrogen atmosphere, 160.2g of 1,5-dihydroxynaphthalene, 56.8g of formaldehyde, and 300g of PGME (propylene glycol monomethyl ether) were added and homogenized at an internal temperature of 100℃. Then, a mixture of 8.0g of paratoluenesulfonic acid monohydrate and 8.0g of PGME, which had been mixed and homogenized in advance, was slowly dropped and reacted at an internal temperature of 80℃ for 8 hours. After the reaction was completed, the mixture was cooled to room temperature, 2,000ml of MIBK was added, and the mixture was washed six times with 500ml of pure water, and the organic layer was dried under reduced pressure. 300g of THF was added to the residue to make a homogenous solution, and then crystallized in 2,000g of hexane. The precipitated crystals were separated by filtration, washed twice with 500g of hexane, and collected. The collected crystals were dried in a vacuum at 70℃ to obtain resin (R-6). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the results were as follows: (R-6): Mw = 3,300, Mw / Mn = 2.54 [ka]

[0199] [Metal-containing film forming composition UDL-1] The metal-containing film-forming compound (A-1) was dissolved in a solvent of propylene glycol monomethyl ether acetate (PGMEA) or cyclohexanone (CyHO) containing 0.5 mass% of a surfactant FC-4430 (manufactured by Sumitomo 3M Limited) in the ratio shown in Table 3, and the solution was filtered through a 0.2 μm membrane filter to prepare a metal-containing film-forming composition (UDL-1).

[0200] [Preparation of metal-containing film-forming compositions (UDL-2 to 18) and comparative metal-containing film-forming compositions (Comparative UDL-1 to 6)] Each chemical solution was prepared in the same manner as UDL-1, except that the type and content of each component were as shown in Table 3. In Table 3, "-" indicates that the corresponding component was not used. The crosslinking agent used was the formula (C-1) below, the high boiling point solvent (D-1) was 1,6-diacetoxyhexane (boiling point 260°C), the flow promoter polymer (F-1) was used, and the thermal acid generator (TAG) used was the formula (TAG-1) below.

[0201] [Crosslinking agent] The crosslinking agent (C-1) used in the metal-containing film-forming composition is shown below. [ka]

[0202] [Example of synthesis of polymer for fluidity promoter] Synthesis of polymer for fluidity promoter (F-1) Under a nitrogen atmosphere, 20.0 g of cresol novolak, 27.6 g of potassium carbonate, and 100 g of DMF were added to obtain a uniform dispersion at an internal temperature of 50°C. 11.9 g of propargyl bromide was slowly added, and the reaction was carried out for 24 hours at an internal temperature of 50°C. 300 ml of methyl isobutyl ketone and 300 g of pure water were added to the reaction solution to dissolve the precipitated salt, and then the separated aqueous layer was 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 the organic layer was dried under reduced pressure to obtain resin (F-1). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the results were as follows: (F-1): Mw = 8,500, Mw / Mn = 3.46 [ka]

[0203] [Thermal acid generator] The thermal acid generator (TAG-1) used in the metal-containing film-forming composition is shown below. [ka]

[0204] [Table 3]

[0205] As shown in Table 3, it was confirmed that the metal-containing film-forming compositions UDL-1 to 7 of the present invention can be prepared as solutions in cyclohexanone and have sufficient solubility. In addition, UDL-8 and UDL-9 to 14, which are also used in the reaction and have significantly broken molecular symmetry, can be prepared in PGMEA and have excellent solvent solubility. In addition, the comparative compound (R-4), which is a polymeric compound into which multiple tin atoms can be introduced, is not a monomolecular compound and does not dissolve at all in PGMEA or CyHO, so a solution could not be prepared.

[0206] [Heat resistance evaluation and solvent resistance evaluation] The metal-containing film-forming compositions (UDL-1 to 18, Comparative Examples UDL-1 to 3, 5) prepared above were applied onto silicon substrates, baked at 100° C. for 60 seconds, and the film thickness (a [nm]) was measured. Then, after baking for 60 seconds at each baking temperature shown in Table 4, the film thickness (b [nm]) was measured, and the film thickness difference before and after the additional baking process (residual film ratio: (b / a)×100) was calculated. Furthermore, PGMEA solvent was dispensed on it, left for 30 seconds, spin-dried, and baked at 100°C for 60 seconds to evaporate the PGMEA, and the film thickness (c [nm]) was measured. The difference in film thickness before and after PGMEA treatment (residual film ratio: (c / b) x 100) was calculated. The results are shown in Table 4 below.

[0207] [Table 4]

[0208] As shown in Table 4, the metal-containing film-forming composition of the present invention (Examples 1-1 to 1-18) had a film remaining ratio ((b / a)×100) of 65% or more after a high-temperature additional bake treatment at 250°C, and was found to have the high-temperature bake resistance required for a resist underlayer film. On the other hand, Comparative UDL-1 to Comparative UDL-2, which used a similar tin compound, had a film remaining ratio ((b / a)×100) of 43% and 61%, respectively, after a high-temperature additional bake treatment at 250°C, and the compound of the present invention was found to have better heat resistance. In addition, when Examples 1-19 to 1-21 and Comparative Examples 1-4 to 1-5, which were subjected to a high-temperature additional bake treatment at 350°C, were compared, the film remaining ratio ((b / a)×100) of Examples 1-19 to 1-21 was 48% or more, while the film remaining ratio ((b / a)×100) of Comparative Examples 1-4 to 1-5 was 8% and 35%, respectively, and it was confirmed that the compound of the present invention exhibited excellent heat resistance even in a 350°C bake. This is believed to be because the compound of the present invention has an organic ligand bonded to tin at two places like a chelate, making it difficult for the tin and the organic group of the mother nucleus to be cut off, and because the molecular weight increases by introducing multiple tin atoms into one molecule, suppressing sublimation. In addition, the film that was subjected to high-temperature additional baking treatment had a remaining film rate ((c / b) x 100) of 98% or more after PGMEA rinsing treatment, which indicates that a crosslinking reaction occurs and sufficient solvent resistance is exhibited. Furthermore, in UDL10 to 14, which used raw material group G that generates carboxylic acid by unsaturated bonds or thermal acid elimination in the reaction, the remaining film rate ((c / b) x 100) after PGMEA rinsing treatment was 99.5% or more, which indicates that the crosslinking reaction is further promoted and sufficient solvent resistance is exhibited.

[0209] In addition, the residual film rate after baking of UDL-15, which contains a crosslinking agent (C-1), increased from 91% to 93% compared to UDL-8, which does not contain the crosslinking agent. This is believed to be the result of efficient crosslinking caused by the crosslinking agent, and the suppression of sublimate formation. In addition, when comparing UDL-13 and UDL-17, which contains a thermal acid generator (TAG-1), the residual film rate ((c / b) x 100) after PGMEA rinsing treatment after baking at 250°C for UDL-13 was 99.6%, while the residual film rate ((c / b) x 100) after PGMEA rinsing treatment after baking at 200°C for UDL-17 was 100%, resulting in increased curing properties. This is believed to be the result of the efficient elimination of leaving groups and the resulting crosslinking reaction occurring by the addition of a thermal acid generator.

[0210] In addition, Comparative Example 1-3, which uses a tin compound reported in [Synthesis Example 8] of Japanese Patent No. 7028940 as a tin compound having a different use from the present invention, and Comparative Example 1-6, which uses a titanium compound reported in [Synthesis Example A-II] of Japanese Patent No. 6189758 as a compound having a metal different from the compound for forming a metal-containing film of the present invention, showed sufficient solvent resistance, but the difference in film thickness before and after high-temperature additional baking was large, and it was found that the volume shrinkage due to high-temperature baking was large compared to the compound for forming a metal-containing film of the present invention. Regarding Comparative Example 1-3, as in the present invention, it has two tin atoms in one molecule, but since the two tin atoms are bonded by a linear divalent organic group, the Sn-O bond itself connecting the two tins is easily bonded and is easily broken, and further, it has a ring structure as in the present invention, but it is a seven-membered ring, and it is considered that the heat resistance is insufficient because of two reasons that the thermal stability is poor and there is a lot of sublimate.

[0211] [Evaluation of embedding characteristics] The metal-containing film-forming compositions (UDL-1 to 18) that showed good film-forming properties after additional baking in the above solvent resistance evaluation, and the comparative examples UDL-1 to 3 and 5 that showed good or possible film formation, were each applied onto a SiO2 wafer substrate having a dense line & space pattern (line width 40 nm, line depth 120 nm, distance between the centers of two adjacent lines 80 nm), and heated for 60 seconds using a hot plate at the temperature shown in Table 5 to form a metal-containing film with a thickness of 100 nm. The substrate used was a base substrate 9 (SiO2 wafer substrate) having a dense line & space pattern as shown in Figure 3 (Q) (bird's-eye view) and (R) (cross-sectional view). The cross-sectional shape of each of the obtained wafer substrates was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd., and whether or not the stepped substrate could be filled was confirmed. The results are shown in Table 5. When a metal-containing film-forming composition with poor filling properties was used, the stepped substrate could not be filled well in this evaluation. When a metal-containing film-forming composition with good filling properties is used, in this evaluation, the spaces between the lines of an underlying substrate 9 having a dense line and space pattern can be filled without gaps with the metal-containing resist underlayer film 10, as shown in Figure 3(S). ◯ indicates that filling is possible without large voids, △ indicates that there are visible voids, and × indicates that filling is not possible.

[0212] [Table 5]

[0213] As shown in Table 5, Comparative Examples 2-1 to 2-3 using a tin compound similar to Examples 2-1 to 2-15 using the resist metal-containing film forming composition of the present invention were able to fill dense line & space patterns without generating voids when baked at 250 ° C., and were confirmed to have good filling properties. In addition, when comparing Examples 2-16 to 2-18 baked at 350 ° C. with Comparative Examples 2-4 and 2-5, it was found that Examples 2-16 to 2-18 using the compound of the present invention were able to fill dense line & space patterns without generating voids, while Comparative Examples 2-4 and 2-5 were unable to fill or generated voids. In addition, in Comparative Example 2-3 using a tin compound reported in [Synthesis Example 8] of Japanese Patent No. 7028940 as a tin compound having a different use from the present invention, and Comparative Example 2-6 using a titanium compound reported in [Synthesis Example A-II] of Japanese Patent No. 6189758, voids were observed at the bottom of the pattern. This is presumably because, as observed in the above-mentioned solvent resistance evaluation, the compounds of the present invention have small volumetric shrinkage upon high-temperature baking, and therefore no voids are generated and filling is possible, whereas the comparative compounds have large volumetric shrinkage, and therefore, voids are generated or filling is not possible.

[0214] [Flattening characteristics evaluation] 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 obtained in the above-mentioned filling property evaluation 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 part and the non-line pattern forming part of the filling film (metal-containing resist underlayer film 12) was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd. The results are shown in Table 6. In this evaluation, it can be said that the smaller the step, the better the planarization property. [Table 6]

[0215] As shown in Table 6, it was confirmed that Examples 3-1 to 3-18 using the resist metal-containing film-forming composition of the present invention (UDL-1 to 18) showed superior flatness compared to Comparative Example 3-3 using a titanium compound reported in [Synthesis Example A-II] of Japanese Patent No. 6189758 and Comparative Example 3-4, which is an organic resist underlayer film. This is believed to be because the compound of the present invention has a long alkyl chain or an asymmetric structure, which gives it excellent thermal fluidity. In addition, it was confirmed that the same flatness was shown even when baked at 350°C, as in Examples 3-16 to 3-18. In addition, Examples 3-13 and 3-15, which contained the high boiling point solvent (D-1) and the flow promoter (F-1), showed superior planarization characteristics compared to Examples 3-15 and 3-17, which did not contain the high boiling point solvent (D-1) and the flow promoter (F-1). It can be seen that the use of the high boiling point solvent (D-1) and the flow promoter (F-1) can further improve the thermal flowability of the metal-containing film-forming compound.

[0216] [Etching resistance evaluation] The metal-containing film-forming compositions (UDL-2, UDL-4, UDL-8, and UDL-11) and Comparative Examples UDL-1 to UDL-2 and Comparative Examples UDL-5 to 6, which had good film-forming properties after additional baking in the above solvent resistance evaluation, were applied to a silicon substrate, heated for 60 seconds at the temperatures shown in Table 7 using a hot plate to form a metal-containing film with a thickness of 200 nm, and an etching test was performed using a CF-based gas and an O2-based gas under the following conditions to determine the difference in thickness of the organic film before and after etching. The results are shown in Table 7. A dry etching device TE-8500 manufactured by Tokyo Electron Limited was used for etching.

[0217] The CF4-based gas etching conditions are as follows: Chamber pressure 200mT RF power 300W CF4 gas flow rate: 100sccm Time 20sec

[0218] The O2-based gas etching conditions are as follows: Chamber pressure 500mT RF power 100W O2 gas flow rate: 30sccm N2 gas flow rate: 270sscm Time 20sec

[0219] [Table 7]

[0220] As shown in Table 7, Examples 4-1 to 4-4 using the resist metal-containing film-forming composition of the present invention, Comparative Examples 4-1 to 4-2 using a similar metal-containing film-forming composition, and Comparative Example 4-3 using a titanium compound reported in [Synthesis Example A-II] of Japanese Patent No. 6189758, showed superior etching resistance to CF-based gases compared to Comparative Example 4-4 using an organic resist underlayer film material, and O2 etching resistance was found to be even better. In particular, Example 4-1 showed superior etching resistance, which is believed to be due to the high tin content.

[0221] [Pattern Forming Method (Examples 5-1 to 5-4, Comparative Examples 5-1 to 5-2)] The metal-containing film-forming compositions (UDL-2, UDL-4, UDL-8 and UDL-11) and comparative examples UDL-5 to 6, which had good film-forming properties after additional baking in the above solvent resistance evaluation, were applied to a SiO2 wafer substrate having a trench pattern (trench width 10 μm, trench depth 0.10 μm), and baked in air at 250 ° C for 60 seconds to form a metal-containing film with a thickness of 100 nm. A silicon atom-containing resist intermediate layer material (SOG-1) was applied thereon and baked at 220 ° C for 60 seconds to form a resist intermediate layer film with a thickness of 30 nm, and a single layer resist for ArF of the resist upper layer film material was applied thereon and baked at 105 ° C for 60 seconds to form a photoresist film with a thickness of 100 nm. An immersion protective film material (TC-1) was applied on the photoresist film and baked at 90 ° C for 60 seconds to form a protective film with a thickness of 50 nm.

[0222] The silicon-containing resist intermediate layer material (SOG-1) was prepared by dissolving the polymer represented by ArF silicon-containing intermediate film polymer (SiP1) and the crosslinking catalyst (CAT1) in an organic solvent containing 0.1 mass % of FC-4430 (manufactured by Sumitomo 3M) in the ratios shown in Table 8, and filtering the solution through a fluorine resin filter having a pore size of 0.1 μm.

[0223] [Table 8]

[0224] The structural formulae of the ArF silicon-containing intermediate film polymer (SiP1) and crosslinking catalyst (CAT1) used are shown below. [ka]

[0225] The resist top layer film material (ArF single layer resist) was prepared by dissolving a polymer (RP1), an acid generator (PAG1), and a basic compound (Amine1) in a solvent containing 0.1 mass % of a surfactant FC-4430 (Sumitomo 3M Limited) in the ratios shown in Table 9, and filtering the solution through a 0.1 μm fluorine resin filter.

[0226] [Table 9]

[0227] 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]

[0228] 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 10 and filtering through a 0.1 μm fluorine resin filter.

[0229] [Table 10]

[0230] The polymer (PP1) used in the immersion protective film material (TC-1) is shown below. [ka]

[0231] Next, the resist was exposed using an ArF immersion exposure tool (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 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds to obtain a 55 nm 1:1 positive line and space pattern (resist pattern).

[0232] Next, the silicon-containing resist intermediate layer material (SOG-1) was etched by dry etching using the resist pattern as a mask to form a hard mask pattern, the metal oxide film was etched using the obtained hard mask pattern as a mask to form a metal oxide film pattern, and the SiO2 film was etched using the obtained metal oxide film pattern as a mask. The etching equipment used was ULVAC CE-3001, and the etching conditions were as follows:

[0233] Transfer conditions of resist pattern to silicon-containing resist intermediate layer material (SOG-1). Dry etching conditions with CF4 gas Pressure: 1Pa Antenna RF power: 100W Bias RF power: 15W CF4 gas flow rate: 15sccm Time: 60sec

[0234] Transfer conditions of SOG-1 hard mask pattern to metal-containing film. Pressure: 1Pa Antenna RF power: 320W Bias RF power: 30W Cl2 gas flow rate: 25sccm Time (Examples 5-1 to 5-4): 15 sec Time (Comparative Example 5-1 and Comparative Example 5-2): 60 sec

[0235] Transfer conditions of 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

[0236] The cross section of the pattern was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd. The results are shown in Table 11.

[0237] [Table 11]

[0238] As shown in Table 11, in Examples 5-1 to 5-4 in which the metal oxide film-forming composition of the present invention was used, the resist upper layer film pattern was finally transferred to the substrate well in all cases, and it was confirmed that the metal oxide film-forming composition of the present invention is suitably used for fine processing by the multilayer resist method. On the other hand, in Comparative Example 5-1 in which insufficient performance was confirmed in the embedding characteristic evaluation and the planarization characteristic evaluation, pattern collapse occurred during pattern processing, and ultimately, a good pattern could not be obtained. In addition, although there were no problems in the embedding characteristic and planarization characteristic evaluations, in Comparative Example 5-2 in which insufficient performance was confirmed in the dry etching resistance evaluation, distortion of the pattern shape occurred during pattern processing, and ultimately, a good pattern could not be obtained.

[0239] From the above, since the compound for forming a metal oxide film of the present invention is an organotin compound that highly balances thermal fluidity and thermosetting properties, a composition for forming a metal-containing film using this compound has excellent dry etching resistance compared to conventional organic underlayer film materials, and can provide a composition for forming a metal-containing film that also has high filling / planarization properties, and is 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.

[0240] The present specification includes the following aspects. [1]: A compound for forming a metal-containing film, which is a reaction product of a compound having two or more diol structures in its molecule and a Sn compound, and is a monomolecular compound containing two or more Sn atoms in one molecule. [2]: The compound for forming a metal-containing film according to [1], characterized in that the compound for forming a metal-containing film is represented by the following general formula (M-1) or (M-2): [ka] (In the general formulae (M-1) to (M-2), R1 and R2 each independently represent a monovalent organic group or a halogen atom. X1 represents a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 70 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds (the alkyl group and the aliphatic unsaturated hydrocarbon group may have an ether group, a thioether group, an ester group, or an amide group), a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted triazine ring, a substituted or unsubstituted isocyanuric group, and an n1-valent organic group selected from substituted or unsubstituted glycoluril groups, where n1 is an integer of 2 to 6. R3 represents a substituent other than a hydrogen atom, each of which is independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a thiol group, a hydroxyl group, an amino group, a carboxy group, or a halogen atom, l is an integer of 0 to 1, and m1 is an integer of 0 to 5.X2 is a single bond or a linking moiety, the linking moiety being an n2-valent organic group selected from a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds (the alkyl group and the aliphatic unsaturated hydrocarbon group may have a ketone group, an ether group, an ester group, an amide group, an imine group, a lactone ring, and a sultone ring), a substituted or unsubstituted aryl group having 6 to 36 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 36 carbon atoms, and a substituted or unsubstituted triazine ring, or a 2×n2-valent organic group selected from a substituted or unsubstituted saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms forming a cyclic structure together with an aromatic ring (the hydrocarbon group may have an ether group), where n2 is an integer of 2 to 4. ). [3]: The compound for forming a metal-containing film according to [2], characterized in that in the general formulae (M-1) to (M-2), R1 is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds, 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. [4]: The compound for forming a metal-containing film according to [2] or [3], wherein R2 is -OC(=O)R2' (R2' is a monovalent organic group). [5]: The compound for forming a metal-containing film according to [4], wherein R2' is any one of the following general formulae (A-1) to (A-4), (2) and (3): [ka] (In the above general formulae (A-1) to (A-4), Y A1 , Y A2may be the same or different, and each represents a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms. A is a hydrogen atom, a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, R A1 is an organic group that generates one or more hydroxyl or carboxyl groups by elimination of a protecting group by the action of either or both of an acid and heat, as represented by the following general formula (1), and * represents a bond with a carbonyl group. [ka] (In the above general formula (1), R A2 is an organic group whose protecting group is removed by the action of either acid or heat, or both, and * is Y A1 Or Y A2 ) [ka] (In the general formula (2), X is a divalent organic group having 1 to 31 carbon atoms, B is the following general formula (B), and * represents a bond to a carbonyl group.) [ka] (In the above general formula (B), Y B represents a substituted or unsubstituted divalent saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms or an unsaturated divalent aliphatic hydrocarbon group having 2 to 20 carbon atoms, a substituted or unsubstituted divalent aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted divalent arylalkyl group having 7 to 31 carbon atoms, which may be bonded to an adjacent group via an oxygen atom or an NH group; R B is a hydroxyl group or any of the structures represented by the following general formulas (B-1) to (B-3). * represents the bond with the carbonyl group. [ka] (In the above general formulas (B-1) to (B-3), R B1 is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q is 0 or 1, * is Y B ) [ka] (In the general formula (3), X is a divalent organic group having 1 to 31 carbon atoms, C is any of the following general formulae (C-1) to (C-4), and * represents a bond to a carbonyl group.) [ka] (In the above general formulas (C-1) and (C-3), R C1 are each independently a hydrogen atom or a methyl group, and in the same formula, they may be the same or different. In (C-3) to (C-4), R C2 is a hydrogen atom, or a substituted or unsubstituted saturated or unsaturated monovalent aliphatic hydrocarbon 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. * represents the bond to the carbonyl group.) [6]: Y in the general formulae (A-1) to (A-4) A1 The compound for forming a metal-containing film according to [5], wherein X in the general formula (2) or X in the general formula (3) is a substituted or unsubstituted unsaturated hydrocarbon having 2 to 20 carbon atoms. [7]: Y in the general formulae (A-1) to (A-4) A1 The compound for forming a metal-containing film according to [5] or [6], wherein X in the general formula (2) or X in the general formula (3) is represented by the following general formula (4): [ka] (In the general formula (4), R a , R b and R C is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and R a and R bmay be bonded to form a cyclic substituent. *1 and *2 each represent a bond to a carbonyl group, and the substitution positions of *1 and *2 may be reversed.) [8]: A compound for forming a metal-containing film according to any one of [2] to [7], characterized in that in the general formula (M-2), m1 is 0 or 1, and when m1=1, R3 is a hydroxyl group. [9]: The compound for forming a metal-containing film according to any one of [1] to [8], characterized in that the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn of the compound for forming a metal-containing film, as calculated using polystyrene standards, measured by a gel permeation chromatography method, is 1.00≦Mw / Mn≦1.50.

[10] : A composition for forming a metal-containing film, which functions as a resist underlayer film material 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 [9] and (b) an organic solvent.

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

[10] , which is usable as a resist underlayer film in a multi-layer resist method, and further contains one or more of (c) a crosslinking agent, (d) a surfactant, (e) a flowability promoter, and (f) an acid generator.

[12] : The composition for forming a metal-containing film according to

[10] or

[11] , characterized in that the (b) organic solvent is a mixture of one or more organic solvents having a boiling point of less than 180°C and one or more organic solvents having a boiling point of 180°C or higher.

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

[10] to

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

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

[10] to

[12] onto a substrate to be processed, and then performing a heat treatment to form a metal-containing film; (II-2) forming a resist intermediate film on the metal-containing film; (II-3) forming a resist upper layer film on the resist intermediate film using a photoresist material; (II-4) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (II-5) a step of transferring the pattern to the 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 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:

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

[10] to

[12] onto a substrate to be processed, and then performing a 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 resist underlayer 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 forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (III-6) a step of transferring a 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) A step of 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:

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

[10] to

[12] onto the resist underlayer film, and then subjecting the composition to a heat treatment to form a metal-containing film; (IV-3) forming a resist upper layer film on the metal-containing film using a photoresist material, or forming an organic adhesion film on the metal-containing film by spin coating, and then forming a resist upper layer film thereon using a photoresist material; (IV-4) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (IV-5) a step of transferring a pattern to the metal-containing film, or the organic adhesion film and the metal-containing film, by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (IV-6) a step of transferring a pattern to the resist underlayer film by dry etching using the metal-containing film to which the pattern has been transferred as a mask; and (IV-7) A step of processing the substrate to be processed using the resist underlayer film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. A pattern forming method comprising the steps of:

[17] : 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) a step of 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 on the resist intermediate film or on a combination of the inorganic hard mask intermediate film and an organic thin film using a photoresist material; (V-4) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (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 intermediate film or the inorganic hard mask intermediate 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

[10] to

[12] onto the resist underlayer film on which the pattern has been formed, and then heat-treating the composition to form a metal-containing film, thereby 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 is formed by a chemical stripper or dry etching to expose an upper surface of the resist underlayer film on which the pattern is formed; (V-9) a step of removing the resist intermediate film or the 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 is formed as a mask to form a reverse pattern on the substrate to be processed. A pattern forming method comprising the steps of:

[18] The pattern formation method according to

[15] or

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

[0241] The present invention is not limited to the above-described embodiment. The above-described embodiment is merely an example, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included in the technical scope of the present invention. [Explanation of symbols]

[0242] 1... substrate to be processed, 2... layer to be processed, 2a... pattern (pattern to be formed on layer to be processed), 3...metal-containing resist underlayer film, 3a...metal-containing resist underlayer film pattern, 4...silicon-containing resist intermediate film, 4a...silicon-containing resist intermediate film pattern, 5...resist upper layer film, 5a...resist upper layer film pattern, 6...exposed portion, 7 ... a resist underlayer film made of a coating type organic underlayer film material; 7a ... a resist underlayer film pattern made of a coating type organic underlayer film material; 8...metal-containing film, 8a...metal-containing film pattern obtained by inverting the resist underlayer film pattern, 9... Base substrate having dense lines and spaces; 10... Metal-containing resist underlayer film; 11... base substrate having dense lines and spaces; 12... metal-containing resist underlayer film; Delta12: Step difference between the patterned portion and the non-patterned portion of the metal-containing resist underlayer film 12.

Claims

1. A compound for forming a metal-containing film, which is a reaction product of a compound having two or more diol structures in its molecule and a Sn compound, and is a monomolecular compound containing two or more Sn atoms in one molecule.

2. The compound for forming a metal-containing film according to claim 1, characterized in that the compound for forming a metal-containing film is represented by the following general formula (M-1) or (M-2): 【Chemistry 1】 (In the general formulas (M-1) to (M-2), R １ , R ２ Each of X is independently a monovalent organic group or a halogen atom. １ is selected from a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 70 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds (the alkyl group and the aliphatic unsaturated hydrocarbon group may have an ether group, a thioether group, an ester group, or an amide group), a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted triazine ring, a substituted or unsubstituted isocyanuric group, and a substituted or unsubstituted glycoluril group. １ is an n-valent organic group; １ is an integer from 2 to 6. ３ represents a substituent other than a hydrogen atom, and each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a thiol group, a hydroxyl group, an amino group, a carboxy group, or a halogen atom; l is an integer of 0 to 1; １ is an integer from 0 to 5. ２ is a single bond or a linking moiety, and n is selected from a carbonyl group, an ether group, an ester group, or an amide group, or a substituted or unsubstituted linear alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted branched or cyclic alkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms containing one or more double bonds or triple bonds (the alkyl group and the aliphatic unsaturated hydrocarbon group may have a ketone group, an ether group, an ester group, an amide group, an imine group, a lactone ring, and a sultone ring), a substituted or unsubstituted aryl group having 6 to 36 carbon atoms, a substituted or unsubstituted arylalkyl group having 6 to 36 carbon atoms, and a substituted or unsubstituted triazine ring. ２ or a substituted or unsubstituted, saturated or unsaturated hydrocarbon group having 2 to 20 carbon atoms which forms a cyclic structure together with an aromatic ring (the hydrocarbon group may have an ether group). ２ is an n-valent organic group; ２ is an integer from 2 to 4.)

3. In the general formulas (M-1) to (M-2), R １ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms and containing one or more double bonds or triple bonds, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms.

4. The R ２ -OC(=O)R ２ '(R ２ 3. The compound for forming a metal-containing film according to claim 2, wherein R′ is a monovalent organic group.

5. The R ２ The compound for forming a metal-containing film according to claim 4, characterized in that ' is represented by the following general formula (A-1) to (A-4), or the following general formula (2), or the following general formula (3). 【Chemistry 2】 (In the above general formulae (A-1) to (A-4), Y Ａ１ , Y Ａ２ may be the same or different, and each represents a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms. Ａ is a hydrogen atom, a substituted or unsubstituted saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms; R Ａ１ is an organic group represented by the following general formula (1) in which a protecting group is eliminated by the action of either an acid or heat, or both, to generate one or more hydroxyl groups or carboxyl groups, and * represents a bond with a carbonyl group. 【Chemistry 3】 (In the general formula (1), R Ａ２ represents an organic group whose protecting group is removed by the action of either acid or heat, or both, and * represents Y Ａ１ Or Y Ａ２ It represents the bond with 【Chemistry 4】 (In the general formula (2), X is a divalent organic group having 1 to 31 carbon atoms, B is the following general formula (B), and * represents a bond to a carbonyl group.) 【Chemistry 5】 (In the above general formula (B), Y Ｂ represents a substituted or unsubstituted divalent saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms or an unsaturated divalent aliphatic hydrocarbon group having 2 to 20 carbon atoms, a substituted or unsubstituted divalent aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted divalent arylalkyl group having 7 to 31 carbon atoms, which may be bonded to an adjacent group via an oxygen atom or an NH group; R Ｂ is a hydroxyl group or any of the structures represented by the following general formulas (B-1) to (B-3). * represents the bond with the carbonyl group. 【Chemistry 6】 (In the above general formulas (B-1) to (B-3), R Ｂ１ is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, q represents 0 or 1, * represents Y Ｂ It represents the bond with 【Chemistry 7】 (In the general formula (3), X is a divalent organic group having 1 to 31 carbon atoms, C is one of the following general formulas (C-1) to (C-4), and * represents a bond to a carbonyl group.) 【Chemistry 8】 (In the general formulas (C-1) and (C-3), R Ｃ１ are each independently a hydrogen atom or a methyl group, and in the same formula, they may be the same or different. Ｃ２ is a hydrogen atom, or a substituted or unsubstituted saturated or unsaturated monovalent aliphatic hydrocarbon 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. * represents the bond to the carbonyl group.)

6. Y in the general formulae (A-1) to (A-4) Ａ１ 6. The compound for forming a metal-containing film according to claim 5, wherein X in the general formula (2) or X in the general formula (3) is a substituted or unsubstituted unsaturated hydrocarbon having 2 to 20 carbon atoms.

7. Y in the general formulae (A-1) to (A-4) Ａ１ 6. The compound for forming a metal-containing film according to claim 5, wherein X in the general formula (2) or X in the general formula (3) is the following general formula (4): 【Chemistry 9】 (In the general formula (4), R ａ , R ｂ and R Ｃ is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, R ａ and R ｂ may be bonded to form a cyclic substituent. *1 and *2 each represent a bond to a carbonyl group, and the substitution positions of *1 and *2 may be reversed.)

8. In the general formula (M-2), m １ is 0 or 1, m １ R when = 1 ３ The compound for forming a metal-containing film according to claim 2, characterized in that is a hydroxyl group.

9. The compound for forming a metal-containing film according to claim 1, characterized in that the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn of the compound for forming a metal-containing film in terms of polystyrene measured by a gel permeation chromatography method is 1.00≦Mw / Mn≦1.

50.

10. A composition for forming a metal-containing film, which functions as a resist underlayer film material used in semiconductor manufacturing, comprising (a) the compound for forming a metal-containing film according to any one of claims 1 to 9 and (b) an organic solvent.

11. The composition for forming a metal-containing film according to claim 10, which is a composition for forming a metal-containing film that can be used as a resist underlayer film used in a multi-layer resist method, and further contains one or more of (c) a crosslinking agent, (d) a surfactant, (e) a flowability promoter, and (f) an acid generator.

12. The metal-containing film-forming composition according to claim 10, characterized in that the (b) organic solvent is a mixture of one or more organic solvents having a boiling point of less than 180°C and one or more organic solvents having a boiling point of 180°C or more.

13. A method for forming a pattern on a workpiece substrate, comprising the steps of: (I-1) A step of forming a metal-containing film by applying the composition for forming a metal-containing film according to claim 10 onto a substrate to be processed and then subjecting the substrate to a heat treatment; (I-2) forming a resist top layer film on the metal-containing film using a photoresist material; (I-3) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a pattern on the resist upper layer film; (I-4) a step of transferring a pattern to the metal-containing film by dry etching using the resist top layer film on which the pattern is formed as a mask; and (I-5) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. A pattern forming method comprising the steps of:

14. A method for forming a pattern on a workpiece substrate, comprising the steps of: (II-1) A step of forming a metal-containing film by applying the composition for forming a metal-containing film according to claim 10 onto a substrate to be processed and then subjecting the composition to a heat treatment; (II-2) forming a resist intermediate film on the metal-containing film; (II-3) forming a resist upper layer film on the resist intermediate film using a photoresist material; (II-4) a step of forming a pattern on the resist upper layer film by pattern-exposing the resist upper layer film and then developing the resist upper layer film with a developer; (II-5) a step of transferring a pattern to the 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 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:

15. A method for forming a pattern on a workpiece substrate, comprising the steps of: (III-1) A step of forming a metal-containing film by applying the composition for forming a metal-containing film according to claim 10 onto a substrate to be processed and then heat-treating the composition; (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 resist underlayer 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 the same with a developer to form a pattern on the resist upper layer film; (III-6) a step of transferring a 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) A step of 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:

16. A method for forming a pattern on a workpiece substrate, comprising the steps of: (IV-1) A step of forming a resist underlayer film on a substrate to be processed; (IV-2) A step of forming a metal-containing film by applying the composition for forming a metal-containing film according to claim 10 onto the resist underlayer film and then heat-treating the composition; (IV-3) forming a resist upper layer film on the metal-containing film using a photoresist material, or forming an organic adhesion film on the metal-containing film by spin coating, and forming a resist upper layer film thereon using a photoresist material; (IV-4) a step of pattern-exposing the resist upper layer film and then developing the same with a developer to form a pattern on the resist upper layer film; (IV-5) a step of transferring a pattern to the metal-containing film, or the organic adhesion film and the metal-containing film, by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (IV-6) a step of transferring a pattern to the resist underlayer film by dry etching using the metal-containing film to which the pattern has been transferred as a mask; and (IV-7) A step of processing the substrate to be processed using the resist underlayer film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. A pattern forming method comprising the steps of:

17. A method for forming a pattern on a workpiece substrate, comprising the steps of: (V-1) A step of forming a resist underlayer film on a substrate to be processed; (V-2) a step of 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 on the resist intermediate film or the combination of the inorganic hard mask intermediate film and the organic thin film using a photoresist material; (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 intermediate film or the inorganic hard mask intermediate 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 10 onto the resist underlayer film on which the pattern has been formed, and then heat-treating the composition to cover the 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 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 having the pattern formed thereon and having an exposed surface by dry etching to form a reverse pattern of the original pattern in 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 is formed as a mask to form a reverse pattern on the substrate to be processed. A pattern forming method comprising the steps of:

18. 16. The pattern formation method according to claim 15, wherein the inorganic hard mask intermediate film is formed by a CVD method or an ALD method.

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

Images