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

Abstract

To provide a compound for forming a metal-containing film having better dry etching resistance than conventional resist underlayer film materials and also having high filling and planarizing properties, a composition for forming the metal-containing film containing the compound, and a patterning process in which the composition is used.SOLUTION: The present invention provides a compound for forming a metal-containing film to be contained in a composition for forming the metal-containing film, where the compound is represented by the following general formula (M).SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

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

[0003] Furthermore, for device manufacturing at the 20nm node and beyond, 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 an increased frequency of defects, resulting in reduced productivity and a significant increase in costs.

[0004] In recent years, vacuum ultraviolet (EUV) lithography with a wavelength of 13.5 nm has been attracting attention as a promising alternative to the combined use of ArF immersion lithography and multiple exposure processes. This technology has made it 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, high sensitivity is strongly required for 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 line edge roughness (LER, LWR) of the line pattern, and achieving both high sensitivity and low edge roughness has been cited as one of the important challenges in EUV lithography.

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

[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 are being investigated.

[0008] In particular, tin-containing molecules have been the subject of active research due to their excellent absorption of electron beams and extreme ultraviolet rays. In the case of organotin polymers, one such polymer, alkyl ligands are dissociated by light absorption or the secondary electrons generated by the absorption, and crosslinking with surrounding chains via oxo bonds enables negative-tone patterning that is resistant to removal by organic developers. While such organotin polymers can improve sensitivity while maintaining resolution and line edge roughness, they have yet to reach a commercial level (Patent Document 5). Furthermore, many issues remain, such as insufficient storage stability to prevent changes in resist sensitivity.

[0009] To address the above issues, development of resist underlayer films using materials containing metal elements such as titanium, hafnium, zirconium, and tin is also being considered. Performance improvements such as improving exposure sensitivity and suppressing sensitivity changes under storage conditions, which are issues with metal-containing resist materials, are not required, and the inclusion of these metal elements may make it possible to provide resist underlayer films with excellent dry etching resistance. Patent Document 6 reports that materials using Ti compounds exhibit excellent dry etching resistance to CHF3 / CF4-based gases and CO2 / N2-based gases.

[0010] On the other hand, one issue when using metal compounds in resist underlayer films is their embeddability. While Patent Document 6 does not mention embeddability, metal compounds generally exhibit significant thermal shrinkage during baking, leading to significant deterioration of their embedding ability after high-temperature baking. This raises concerns that they may be insufficient as resist underlayer film materials, which require high levels of planarization, embedding, and heat resistance. Patent Document 7 reports that metal compounds modified with specific ligands exhibit excellent embeddability, but the bake temperature used for embeddability evaluation was as low as 150°C, raising concerns that they may be insufficient as resist underlayer films that require heat resistance (e.g., resistance to heat treatments that may be performed after resist underlayer film formation). Patent Document 8 provides a resist underlayer film material that exhibits excellent embeddability after baking at 400°C by blending the metal compound reported in Patent Document 7 with an organic polymer of a specific structure. However, because the material is a mixed composition of an inorganic metal compound and an organic polymer, concerns exist regarding poor compatibility, such as poor film formation, deterioration in storage stability, and deterioration in dry etching resistance. [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] Patent Publication No. 2021-162865 [Patent Document 6] Patent No. 6189758 [Patent Document 7] Patent No. 7050137 [Patent Document 8] 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 an object of the present invention is to provide a compound for forming a metal-containing film that has superior dry etching resistance compared to conventional resist 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. [Means for solving the problem]

[0013] In order to solve the above problems, the present invention provides a metal-containing film-forming compound used in a metal-containing film-forming composition, the compound being represented by the following general formula (M): [ka] In the general formula (M), T is a group represented by the following general formula (1) or a group represented by the following general formula (1'), at least one of which is a group represented by the following general formula (1), and one or more of these may be used in combination; Q is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted Carbon number a cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated organic group having 2 to 20 carbon atoms and containing one or more double or triple bonds, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, or a combination thereof, wherein m and n are any integers and satisfy the relationships m+n=4, m≧1, and n≧2. [ka] (In general formula (1), X represents a divalent organic group having 1 to 31 carbon atoms, W represents a group represented by the following general formulas (W-1) to (W-4), * represents a bond to the Sn atom, and in general formula (1'), R represents an optional substituent, * represents a bond to the Sn atom.) [ka] (In general formulas (W-1) and (W-3), R1 represents a hydrogen atom or a methyl group, which may be the same or different; in (W-3) and (W-4), R2 represents a hydrogen atom, a substituted or unsubstituted saturated monovalent organic group having 1 to 20 carbon atoms or an unsaturated monovalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms; and * represents the bond to the carbonyl.)

[0014] Such tetravalent metal-containing film-forming compounds are tin-containing compounds with excellent solvent solubility, contain structures represented by (W-1) to (W-4) in the above general formula (1), have a high crosslinking group density, and exhibit excellent thermosetting properties. Therefore, when used in a metal-containing film-forming composition, the compound has excellent dry etching resistance and exhibits small volume shrinkage during baking. Unlike the tin-containing compounds for forming resist top layer films as reported in Patent Document 5, a resist material can be provided that has excellent film-forming properties and planarization / filling properties even after high-temperature baking.

[0015] In the general formula (1), X is preferably an unsaturated hydrocarbon group having 2 to 20 carbon atoms.

[0016] In the general formula (1), if X is an unsaturated hydrocarbon group having 2 to 20 carbon atoms, the thermosetting property of the metal-containing film-forming compound can be further improved.

[0017] In addition, in the general formula (1), X is preferably a group represented by the following general formula (2). [ka] (In general formula (2), R a , and R b is a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and R c is a hydrogen atom or a monovalent organic group having 1 to 17 carbon atoms, and R a and R b The total number of carbon atoms is 0 to 18, and R a and Rb may be bonded to form a cyclic substituent, and *1 and *2 each represent the bonding site with the carbonyl group, and *1 and *2 may be reversed.)

[0018] A metal-containing film-forming compound having such a structure can achieve a high degree of both thermal fluidity and thermosetting property, and when used in a metal-containing film-forming composition, it can provide a resist material that exhibits superior planarization properties / filling properties.

[0019] The ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn in terms of polystyrene as determined by gel permeation chromatography of the metal-containing film-forming compound is preferably 1.00≦Mw / Mn≦1.50.

[0020] A metal-containing film-forming compound having a dispersity within this range has even better thermal fluidity, and therefore, when incorporated into a metal-containing film-forming composition, it is possible to not only satisfactorily fill the microstructures formed on the substrate, but also to form a resist film that flattens the entire substrate.

[0021] The present invention also provides a metal-containing film-forming composition used in semiconductor manufacturing, the metal-containing film-forming composition comprising the above-described (A) metal-containing film-forming compound and (B) an organic solvent.

[0022] 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 material that has excellent dry etching resistance compared to conventional resist underlayer film materials and also has advanced filling / planarization properties.

[0023] The composition may further contain one or more of (C) a crosslinking agent, (E) a surfactant, (F) a flow promoter, and (G) an acid generator.

[0024] A metal-containing film-forming composition containing the above additives will have better coatability, dry etching resistance, and filling / planarization properties.

[0025] Furthermore, it is preferable that the (B) organic solvent contains one or more organic solvents having a boiling point of 180° C. or higher as (B1) high boiling point solvents.

[0026] By adding a high-boiling point solvent to the metal-containing film-forming composition, thermal fluidity is imparted to the metal-containing film-forming composition, and the metal-containing film-forming composition also has higher filling / planarizing properties.

[0027] The present invention also provides a method for forming a pattern on a substrate to be processed, comprising the steps of: (I-1) a step of applying the above-described composition for forming a metal-containing film onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (I-2) forming a resist top layer film on the metal-containing film using a photoresist material; (I-3) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a pattern on the resist upper layer film; (I-4) a step of transferring the pattern to the metal-containing film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; and (I-5) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. The present invention provides a pattern forming method comprising the steps of:

[0028] By using the pattern forming method using the two-layer resist process, a fine pattern can be formed on a workpiece (substrate).

[0029] The present invention also provides a method for forming a pattern on a substrate to be processed, comprising the steps of: (II-1) A step of applying the above-described composition for forming a metal-containing film onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (II-2) forming a silicon-containing resist intermediate film on the metal-containing film; (II-3) forming a resist upper layer film on the silicon-containing resist intermediate film using a photoresist material; (II-4) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a pattern on the resist upper layer film; (II-5) a step of transferring the pattern to the silicon-containing resist intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (II-6) a step of transferring a pattern to the metal-containing film by dry etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; and (II-7) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. The present invention provides a pattern forming method comprising the steps of:

[0030] The pattern formation method using the three-layer resist process described above makes it possible to form a fine pattern on a workpiece with high precision.

[0031] The present invention also provides a method for forming a pattern on a substrate to be processed, comprising the steps of: (III-1) A step of applying the above-described composition for forming a metal-containing film onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (III-2) The above Contains metal forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the film; (III-3) forming an organic thin film on the inorganic hard mask intermediate film; (III-4) forming a resist top layer film on the organic thin film using a photoresist material; (III-5) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a pattern on the resist upper layer film; (III-6) a step of transferring the pattern to the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (III-7) transferring a pattern to the metal-containing film by dry etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; and (III-8) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. The present invention provides a pattern forming method comprising the steps of:

[0032] The pattern formation method using the four-layer resist process described above makes it possible to form a fine pattern on a workpiece with high precision.

[0033] In this case, the inorganic hard mask intermediate film is preferably formed by a CVD method or an ALD method.

[0034] When the inorganic hard mask intermediate film is formed by a CVD method or an ALD method, a fine pattern can be formed on a workpiece with higher precision.

[0035] The present invention also provides a method for forming a pattern on a substrate to be processed, comprising the steps of: (IV-1) forming a resist underlayer film on a substrate to be processed; (IV-2) a step of applying the above-described composition for forming a metal-containing film 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 then 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 it with a developer to form a pattern on the resist upper layer film; (IV-5) a step of transferring a pattern to the organic adhesion film and the metal-containing film, or to 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) 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:

[0036] By using the pattern forming method using the multilayer resist process, a fine pattern can be formed on a workpiece with high precision.

[0037] The present invention also provides a method for forming a pattern on a substrate to be processed, comprising the steps of: (V-1) forming a resist underlayer film on a substrate to be processed; (V-2) forming a resist intermediate film or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film on the resist underlayer film; (V-3) forming a resist upper layer film using a photoresist material on the resist intermediate film or the combination of the inorganic hard mask intermediate film and an organic thin film; (V-4) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a pattern on the resist upper layer film; (V-5) a step of transferring a pattern to the resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film, by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (V-6) a step of transferring a pattern to the resist underlayer film by dry etching using the resist interlayer film or inorganic hard mask interlayer film to which the pattern has been transferred as a mask; (V-7) a step of applying the above-described composition for forming a metal-containing film onto the resist underlayer film on which the pattern has been formed, followed by heat treatment to cover the resist underlayer film with a metal-containing film and filling spaces between the resist underlayer film patterns with the metal-containing film; (V-8) a step of etching back the metal-containing film covering the resist underlayer film on which the pattern has been formed by a chemical stripper or dry etching to expose the upper surface of the resist underlayer film on which the pattern has been formed; (V-9) a step of removing the resist intermediate film or the inorganic hard mask intermediate film remaining on the upper surface of the resist underlayer film by dry etching; (V-10) a step of removing the resist underlayer film on which the pattern is formed and the surface is exposed by dry etching, thereby forming a reverse pattern of the original pattern on the metal-containing film; (V-11) A step of processing the substrate to be processed using the metal-containing film on which the reverse pattern has been formed as a mask to form a reverse pattern on the substrate to be processed. The present invention provides a tone-reversal pattern formation method having the steps of:

[0038] The pattern forming method using the above-described reversal process makes it possible to form a fine pattern on a workpiece with even higher precision. [Effects of the Invention]

[0039] As described above, the metal-containing film-forming compound of the present invention is a tetravalent metal-containing film-forming compound as represented by the general formula (M), resulting in a tin-containing compound with excellent solvent solubility. Since it contains the structures represented by (W-1) to (W-4) in the general formula (1), it has a high crosslinking group density and excellent thermosetting properties. Therefore, when the compound is used in a metal-containing film-forming composition, it can provide a resist material that exhibits small volume shrinkage during baking and has excellent film-forming properties and planarization / filling properties even after high-temperature baking.

[0040] In particular, in fine patterning processes using multilayer resist methods in semiconductor device manufacturing processes, this material can be filled without causing defects such as voids or peeling, even on substrates that have areas that are difficult to fill / planarize, such as dense areas of high-aspect ratio fine pattern structures such as those in DRAM memories, which are becoming increasingly miniaturized.In addition, it has superior dry etching resistance compared to conventional coating-type resist underlayer film materials, making it possible to form fine patterns on the workpiece with even greater precision than with resist underlayer films.

[0041] Furthermore, the metal-containing film-forming composition containing the metal-containing film-forming compound of the present invention contains tin atoms, which have high light absorption, and therefore has a sensitizing effect due to secondary electrons generated from the tin atoms during exposure. Furthermore, since tin atoms have a large atomic weight, they are highly effective in suppressing acid diffusion from the resist top layer film into the resist bottom layer film, and are therefore characterized by being able to achieve high sensitivity while maintaining the LWR performance that the resist top layer film originally has. [Brief explanation of the drawings]

[0042] [Figure 1] FIG. 1 is an explanatory diagram of an example of the pattern forming method of the present invention (three-layer resist process). [Figure 2] FIG. 2 is an explanatory diagram of an example of the tone reversal pattern forming method of the present invention (reversal of the SOC pattern in a three-layer resist process). [Figure 3] FIG. 3 is an explanatory diagram of the embedding characteristic evaluation method. [Figure 4] FIG. 4 is an explanatory diagram of a method for evaluating flattening characteristics. DETAILED DESCRIPTION OF THE INVENTION

[0043] As described above, there has been a need for the development of a metal-containing film-forming composition that has excellent embedding ability and flatness and that can be used to form a resist underlayer film that can transfer a resist pattern to a substrate to be processed with higher precision in a fine patterning process using a multilayer resist method, as well as a metal-containing film-forming compound that is useful for the composition.

[0044] The present inventors have focused on organotin compounds, which are expected to be useful in the EUV exposure generation, and have conducted extensive research. As described above, tin atoms, which have high light absorption, have a sensitizing effect due to the secondary electrons generated during exposure. This has the advantage of enabling resist top layer films to have high sensitivity while maintaining the inherent LWR performance. On the other hand, organotin compounds considered for use as resist underlayer films have poor heat resistance and undergo rapid volumetric shrinkage during baking, making it difficult to fill and planarize uneven surfaces on the substrate after high-temperature baking. The present inventors believed that compounds containing organic groups with excellent heat resistance could reduce rapid volumetric shrinkage during baking and improve thermal fluidity, thereby enabling the filling of uneven surfaces on the substrate without generating voids even after high-temperature baking. Furthermore, they hypothesized that a structure containing a crosslinking group at the terminal would provide excellent thermosetting properties during baking, resulting in a compound for forming a metal-containing film with even better heat resistance.

[0045] As a result of further intensive research, the present inventors have found that a compound for forming a metal-containing film containing at least one organic group represented by the above general formula (1) has excellent thermosetting properties, thereby reducing rapid volume shrinkage during baking, and has good thermal fluidity, thereby achieving advanced filling / planarization properties. Furthermore, by containing tin atoms, it can contribute to improving sensitivity while maintaining the LWR of the upper resist film. Furthermore, after high-temperature baking, the alkyl ligands are dissociated and form SnO2 through crosslinking with surrounding chains via oxo bonds, resulting in a composition for forming a metal-containing film with excellent dry etching resistance, and have completed the present invention.

[0046] That is, the present invention relates to a compound for forming a metal-containing film, which is used in a composition for forming a metal-containing film, and the compound is represented by the following general formula (M): [ka] (In general formula (M), T is a group represented by the following general formula (1) or a group represented by the following general formula (1'), at least one is a group represented by the following general formula (1), and one or more of them may be used in combination. Q is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted Carbon number cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated organic 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, a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, or a combination thereof. m and n are arbitrary integers, and satisfy the relationship m + n = 4, m ≥ 1, and n ≥ 2.)

Chemical formula

Chemical formula

[0047] Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto.

[0048] <Compound for forming a metal-containing film> The compound for forming a metal-containing film of the present invention is a compound for forming a metal-containing film, characterized in that it is represented by the following general formula (M).

Chemical formula

[0049] In the general formula (M), T is a group represented by the general formula (1) or a group represented by the general formula (1'), and at least one of T is above Q is a group represented by the general formula (1), and one or more of these groups can be used in combination. Q is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted Carbon numberThe alkyl group may be a cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated organic 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, a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, or a combination thereof, with an unsubstituted alkyl group having 1 to 20 carbon atoms being more preferred, and an n-butyl group being particularly preferred in terms of ease of obtaining the raw material.

[0050] In the above general formula (M), n and m are preferably either n=3 and m=1 or n=2 and m=2 from the viewpoint of the safety and thermosetting properties of the compound, and more preferably n=2 and m=2 from the viewpoint of ease of obtaining raw materials.

[0051] In the general formula (1), X represents a divalent organic group having 1 to 31 carbon atoms, specifically 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, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms. W represents a group represented by the general formulas (W-1) to (W-4), and in (W-1) and (W-3), R1 is preferably a methyl group from the viewpoint of thermal fluidity, and a hydrogen atom from the viewpoint of curability. Furthermore, in (W-3) and (W-4), R2 preferably has the above-described structure other than a hydrogen atom from the viewpoint of thermal fluidity.

[0052] In the above general formula (1), preferred structures of X include, but are not limited to, the structures shown below. [ka] (* represents the bond to the carbon atom of the carbonyl group.)

[0053] In the above general formulae (W-1) to (W-4), preferred structures of R2 include, but are not limited to, the structures shown below. [ka] (* indicates the bond to the nitrogen atom.)

[0054] A metal-containing film-forming compound having such a structure contains an organic group represented by the general formula (1) above, and therefore has excellent solvent solubility and heat resistance. Furthermore, since the compound contains any of the structures represented by the general formulas (W-1) to (W-4) above at its terminal, it has a high crosslinking group density, can reduce rapid volume shrinkage during baking, and has good thermal fluidity, making it possible to provide a resist material with excellent filling / planarization properties.

[0055] Furthermore, compounds having a structure represented by the above general formula (M) can be synthesized by condensing tin oxide or tin chloride or the like with a carboxylic acid composed of X and W, as shown in the following formula. In this case, multiple carboxylic acid components with different X and W can also be used simultaneously. In the following formula, n and m are as explained in the above general formula (M). [ka]

[0056] Furthermore, as shown in the following formula, a carboxylic acid other than the carboxylic acid composed of X and W can be used in combination, and for example, carboxylic acid components (organic groups represented by the above general formula (1')) having terminal groups or functional groups different from the organic group represented by the above general formula (1) can be used and combined in any ratio to suit the required performance such as film-forming ability, solvent solubility, etc. In the following formula, R is an optional substituent, n and m are as explained in the above general formula (M), and m1 and m2 are optional integers satisfying m1≧1, m1+m2≧2, and m1+m2+m=4. [ka]

[0057] Specific examples of the carboxylic acid to be mixed include those listed below. The carboxylic acid to be added can be selected appropriately depending on the purpose, such as a hydroxyl group-containing carboxylic acid to impart adhesion, or a carboxylic acid containing a long-chain alkyl to improve thermal fluidity. Furthermore, mixing can suppress crystallinity, thereby improving solvent solubility and thermal fluidity. On the other hand, from the perspective of preventing a decrease in thermosetting properties due to a decrease in crosslinking group density, the charging ratio of the carboxylic acid composed of X and W is preferably 50 mol % or more of the total carboxylic acids, and more preferably 70 mol % or more. [ka]

[0058] [ka]

[0059] [ka] (* indicates the bond to the tin atom.)

[0060] When a metal-containing film is formed using the compound for forming a metal-containing film of the present invention, the organic group bonded to the Sn atom via a C atom is dissociated during baking to generate radicals. The radicals thus generated form -Sn-O-Sn- bonds, initiating a condensation polymerization reaction, thereby promoting curing of the metal-containing film. On the other hand, since the organic group is dissociated simultaneously with the reaction, significant film shrinkage occurs during baking. However, since the compound has at least one organic group represented by the general formula (1) above, which includes a crosslinking group having a structure represented by (W-1) to (W-4) at its terminal, thermal decomposition can be mitigated. Furthermore, the compound has excellent thermal fluidity, allowing for the provision of a resist material with excellent embedding properties.

[0061] In the general formula (1), X is preferably an unsaturated hydrocarbon group having 2 to 20 carbon atoms.

[0062] A metal-containing film-forming compound having such a structure can further improve the thermosetting properties.

[0063] In addition, in the above general formula (1), X is preferably a group represented by the following general formula (2). [ka] (In general formula (2), R a , and R b is a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and R c is a hydrogen atom or a monovalent organic group having 1 to 17 carbon atoms, and R a and R b The total number of carbon atoms is 0 to 18, and R a and R b may be bonded to form a cyclic substituent, and *1 and *2 each represent the bonding site with the carbonyl group, and *1 and *2 may be reversed.)

[0064] Compounds containing the above general formula (2) are synthesized by condensing tin oxide or tin chloride with a carboxylic acid, as shown in the reaction formula below. The carboxylic acid used can be synthesized by ring-opening an acid anhydride. In the formula below, n and m are as explained in the above general formula (M), and n1 and n2 are arbitrary integers, satisfying n1 + n2 ≥ 2 and n1 + n2 + m = 4. In this case, ring-opening an asymmetric carboxylic anhydride results in a mixture of two types, resulting in the bonding structure described above. The presence of such isomers can suppress crystallinity and is expected to improve solvent solubility and thermal fluidity. [ka] [ka]

[0065] In the above general formula (2), R a , and R b is a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and R cis a hydrogen atom or a monovalent organic group having 1 to 17 carbon atoms, and R a and R b The total number of carbon atoms is 0 to 18, 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 sublimates.

[0066] A metal-containing film-forming compound having such a structure can achieve both thermal fluidity and thermosetting properties, and when used in a metal-containing film-forming composition, it is possible to provide a resist material that maintains planarization properties / filling properties.

[0067] The ratio Mw / Mn (i.e., dispersity) of the weight average molecular weight Mw to the number average molecular weight Mn in terms of polystyrene as determined by gel permeation chromatography of the metal-containing film-forming compound is preferably within the range of 1.00≦Mw / Mn≦1.50, and more preferably 1.00≦Mw / Mn≦1.40. By definition, a monomolecular compound has an Mw / Mn of 1.00, but due to the separability of GPC, the measured value may exceed 1.00. Generally, polymers having repeating units have a very difficult Mw / Mn value approaching 1.00 unless a special polymerization method is used, and have an Mw distribution, resulting in an Mw / Mn value exceeding 1. In the present invention, 1.00≦Mw / Mn≦1.50 is defined as an index of monomolecularity to distinguish between monomolecular compounds and polymers.

[0068] A compound having a dispersity within such a range will have even better thermal fluidity for the metal-containing film-forming compound, and therefore when incorporated into a metal-containing film-forming composition, it will not only be possible to satisfactorily fill the microstructures formed on the substrate, but will also be possible to form a resist film that flattens the entire substrate.

[0069] <Metal-containing film forming composition> The present invention also provides a metal-containing film-forming composition used in semiconductor manufacturing, which is characterized by containing the above-described (A) metal-containing film-forming compound and (B) organic solvent.

[0070] Since such a composition for forming a metal-containing film contains an organotin compound that exhibits both high thermal fluidity and high thermosetting properties, it is possible to provide a resist material that has excellent dry etching resistance compared to conventional resist underlayer film materials and also has high filling / planarization properties. The composition for forming a metal-containing film of the present invention is particularly suitable as a resist underlayer film material.

[0071] Hereinafter, components contained in the metal-containing film-forming composition of the present invention other than the (A) metal-containing film-forming compound will be described.

[0072] <(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 the above-mentioned (A) metal-containing film-forming compound, and, if contained, the later-described (C) crosslinking agent, (E) surfactant, (F) flow promoter, (G) acid generator, and other additives.

[0073] Specifically, the organic solvents described in paragraphs

[0091] and

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

[0074] The amount of the organic solvent (B) to be blended is preferably 200 to 10,000 parts by mass per 100 parts by mass of the compound (A) for forming a metal-containing film. mass parts, more preferably 250 to 5,000 mass The range is as follows:

[0075] The composition may contain one or more of the above-mentioned (A) metal-containing film-forming compounds and (B) organic solvents, and may also contain additives such as (C) crosslinking agents, (E) surfactants, (F) flow promoters, and (G) acid generators, as needed. Hereinafter, components contained in the composition for forming a metal-containing film of the present invention other than (A) the compound for forming a metal-containing film and (B) the organic solvent will be described.

[0076] <(B1) High-boiling point solvent> In the metal-containing film-forming composition of the present invention, the (B) organic solvent may be used as a mixture of one or more organic solvents having a boiling point of less than 180° C. and one or more organic solvents ((B1) high-boiling-point solvents) having a boiling point of 180° C. or higher. That is, the (B) organic solvent preferably contains one or more organic solvents having a boiling point of 180° C. or higher as the (B1) high-boiling-point solvent.

[0077] The (B1) high-boiling point solvent is not particularly limited as long as it can dissolve each component of the metal-containing film-forming composition of the present invention, and may be any of hydrocarbons, alcohols, ketones, esters, ethers, chlorinated solvents, etc., but specific examples include 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2-ethyl-1,3-Hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, glycerin, n-nonyl acetate, monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol-n-butyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono-n-propyl ether, tripropylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triacetin, propylene glycol diacetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,Examples of the diester include 6-hexanediol diacetate, triethylene glycol diacetate, γ-butyrolactone, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, dihexyl malonate, diethyl succinate, dipropyl succinate, dibutyl succinate, dihexyl succinate, dimethyl adipate, diethyl adipate, and dibutyl adipate, and these may be used alone or in combination.

[0078] The (B1) high-boiling-point solvent may be appropriately selected from, for example, those listed above, depending on the temperature at which the metal-containing film-forming composition of the present invention is heat-treated. The (B1) high-boiling-point solvent preferably has a boiling point of 180°C to 300°C, and more preferably 200°C to 300°C. Such a boiling point is unlikely to cause excessively rapid evaporation during baking (heat treatment), thereby ensuring sufficient thermal fluidity during film formation and enabling the formation of a resist film with excellent filling / planarization properties. Furthermore, such a boiling point is unlikely to cause the solvent to remain in the film after baking without volatilizing, thereby eliminating the risk of adversely affecting film properties such as etching resistance.

[0079] When a (B1) high-boiling point solvent is used, the blending amount is preferably 1 to 30 parts by mass per 100 parts by mass of the organic solvent having a boiling point of less than 180° C. This blending amount is preferable because it can impart sufficient thermal fluidity during baking and does not remain in the film, leading to deterioration of film properties such as etching resistance.

[0080] [(C) Crosslinking agent] The metal-containing film-forming composition of the present invention may also contain a (C) crosslinking agent to enhance the curability of the metal-containing film-forming compound and further suppress intermixing with the resist upper layer film. The crosslinking agent is not particularly limited, and a wide variety of known crosslinking agents can be used. Examples include melamine-based crosslinking agents, acrylate-based crosslinking agents, glycoluril-based crosslinking agents, benzoguanamine-based crosslinking agents, urea-based crosslinking agents, β-hydroxyalkylamide-based crosslinking agents, isocyanurate-based crosslinking agents, aziridine-based crosslinking agents, oxazoline-based crosslinking agents, epoxy-based crosslinking agents, and phenol-based crosslinking agents (e.g., methylol or alkoxymethyl-type crosslinking agents of polynuclear phenols). The content of the (C) crosslinking agent is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, per 100 parts by mass of the (A) metal-containing film-forming compound.

[0081] Specific examples of the melamine-based crosslinking agent include hexamethoxymethylated melamine, hexabutoxymethylated melamine, alkoxy- and / or hydroxy-substituted products thereof, and partial self-condensates thereof. A specific example of the acrylate crosslinking agent is dipentaerythritol hexaacrylate. Specific examples of glycoluril crosslinking agents include tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril, alkoxy and / or hydroxy substituted products thereof, and partial self-condensates thereof. Specific examples of benzoguanamine-based crosslinking agents include tetramethoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, alkoxy- and / or hydroxy-substituted products thereof, and partial self-condensates thereof. Specific examples of urea-based crosslinking agents include dimethoxymethylated dimethoxyethylene urea, its alkoxy and / or hydroxy substituted derivatives, and partial self-condensates thereof. A specific example of the β-hydroxyalkylamide crosslinking agent is N,N,N',N'-tetra(2-hydroxyethyl)adipamide. Specific examples of the isocyanurate crosslinking agent include triglycidyl isocyanurate and triallyl isocyanurate. Specific examples of the aziridine crosslinking agent include 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane and 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate]. Specific examples of oxazoline crosslinking agents include 2,2'-isopropylidenebis(4-benzyl-2-oxazoline) and 2,2'-isopropylidenebis(4-phenyl-2-oxazoline). 、2 Examples include 2'-methylenebis-4,5-diphenyl-2-oxazoline, 2,2'-methylenebis-4-phenyl-2-oxazoline, 2,2'-methylenebis-4-tertbutyl-2-oxazoline, 2,2'-bis(2-oxazoline), 1,3-phenylenebis(2-oxazoline), 1,4-phenylenebis(2-oxazoline), and 2-isopropenyloxazoline copolymer. Specific examples of epoxy-based crosslinking agents include diglycidyl ether, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, poly(glycidyl methacrylate), trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, and pentaerythritol tetraglycidyl ether.

[0082] Specific examples of polynuclear phenol-based crosslinking agents include compounds represented by the following general formula (XL-1). [ka] (In general formula (XL-1), L is a single bond or a q-valent hydrocarbon group having 1 to 20 carbon atoms, R3 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and q is an integer of 1 to 5.)

[0083] L is a single bond or a q-valent hydrocarbon group having 1 to 20 carbon atoms. q is an integer of 1 to 5, and more preferably 2 or 3. Specific examples of L include groups obtained by removing q hydrogen atoms from methane, ethane, propane, butane, isobutane, pentane, cyclopentane, hexane, cyclohexane, methylpentane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, benzene, toluene, xylene, ethylbenzene, ethylisopropylbenzene, diisopropylbenzene, methylnaphthalene, ethylnaphthalene, and eicosane. R3 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 methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, ethylhexyl, decyl, and eicosanyl groups, with a hydrogen atom or a methyl group being preferred.

[0084] Specific examples of compounds represented by the general formula (XL-1) include the following compounds. Among these, hexamethoxymethylated triphenolmethane, triphenolethane, 1,1,1-tris(4-hydroxyphenyl)ethane, and tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene are preferred from the viewpoint of improving the curability and film thickness uniformity of the metal-containing film. R3 is the same as above. [ka]

[0085] [ka]

[0086] <(E) Surfactant> To improve the coating properties in spin coating, a surfactant (E) can be added to the metal-containing film-forming composition of the present invention. For example, surfactants described in paragraphs

[0142] to

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

[0087] <(F) Flow promoter> The metal-containing film-forming composition of the present invention can also be blended with other compounds or polymers. (F) Flowability 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 on substrates with uneven surfaces. Furthermore, (F) Flowability promoter is preferably a material with a high carbon atom density and high etching resistance.

[0088] 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, methyl 3-hydroxynaphthalene-2-carboxylate, indene, hydroxyindene, benzofuran, hydroxyanthracene, acenaphthylene, and biphenyl Examples of the resins include novolak resins such as 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 thereof described in JP 2006-293298 A, novolac resins of adamantanephenol compounds described in JP 2006-285095 A, bisnaphthol compounds and novolac resins thereof described in JP 2010-122656 A, fluorene compounds described in JP 2017-119671 A, 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, per 100 parts by mass of the (A) metal-containing film-forming compound of the present invention.

[0089] Furthermore, in the metal-containing film-forming composition of the present invention, additives for imparting filling / planarization properties are preferably used, such as liquid additives having a polyethylene glycol or polypropylene glycol structure, or thermally decomposable polymers having a weight loss rate of 40% by mass or more between 30° C. and 250° C. and a weight-average molecular weight of 300 to 200,000. These thermally decomposable polymers preferably contain repeating units having an acetal structure represented by the following general formulas (DP1) and (DP1a):

[0090] [ka] (In general formula (DP1), R4 represents a hydrogen atom or an optionally substituted saturated or unsaturated monovalent organic group having 1 to 30 carbon atoms, and Y represents a saturated or unsaturated divalent organic group having 2 to 30 carbon atoms.)

[0091] [ka] (In general formula (DP1a), R 4a is an alkyl group having 1 to 4 carbon atoms, and Y a represents 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.

[0092] <(G) Acid Generator> In the metal-containing film-forming composition of the present invention, an acid generator can be added to further accelerate the curing reaction of the (A) metal-containing film-forming compound. Acid generators include those that generate acid upon thermal decomposition and those that generate acid upon light irradiation, and either can be added. Specifically, materials described in paragraphs

[0061] to

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

[0093] 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 added is preferably 0.05 to 50 parts by mass relative to 100 parts by mass of the (A) compound for forming a metal-containing film. mass parts, more preferably 0.1 to 10 mass It is a department.

[0094] <Method for forming resist underlayer film and filling film> The present invention provides a method for forming a filling film that functions as a resist underlayer film of a multilayer resist film used in lithography or a planarizing film for semiconductor manufacturing, using the above-mentioned metal-containing film-forming composition.

[0095] In the method for forming a resist underlayer film using the metal-containing film-forming composition of the present invention, the metal-containing film-forming composition is coated onto a substrate to be processed by spin coating or the like. By using spin coating or the like, excellent embedding properties can be obtained. After spin coating, the solvent is evaporated, and baking (heat treatment) is performed to promote crosslinking reactions and prevent mixing with the resist top layer film or resist intermediate film. Baking is preferably performed at 100°C or higher and 600°C or lower for 10 to 600 seconds, more preferably 200°C or higher and 500°C or lower for 10 to 300 seconds. Considering the effects on device damage and wafer deformation, the upper limit of the heating temperature in lithography wafer processing is preferably 600°C or lower, more preferably 500°C or lower.

[0096] Furthermore, in a method for forming a resist underlayer film using the metal-containing film-forming composition of the present invention, the metal-containing film-forming composition of the present invention can be coated on a substrate to be processed by a spin coating method or the like, as described above, and the metal-containing film-forming composition can be baked and cured in an atmosphere with an oxygen concentration of 0.1% by volume or more and 21% by volume or less, thereby forming a metal-containing film as a resist underlayer film.

[0097] By baking the metal-containing film-forming composition of the present invention in such an oxygen atmosphere, a sufficiently cured film can be obtained. Although air can be used as the atmosphere during baking, it is preferable to seal in an inert gas such as N2, Ar, or He to reduce the oxygen content and prevent oxidation of the metal-containing film. To prevent oxidation, the oxygen concentration must be controlled, preferably to 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 prevents increased absorption and reduced etching resistance.

[0098] The filling film formation method can be the same as the resist underlayer film formation method described above.

[0099] <Pattern Forming Method Using Metal-Containing Film-Forming Composition> Further, in the present invention, there is provided a method for forming a pattern by a two-layer resist process using the above-mentioned metal-containing film-forming composition, which is a method for forming a pattern on a substrate to be processed, comprising the steps of: (I-1) a step of applying the above-described composition for forming a metal-containing film onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (I-2) forming a resist top layer film on the metal-containing film using a photoresist material; (I-3) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a pattern on the resist upper layer film; (I-4) a step of transferring the pattern to the metal-containing film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; and (I-5) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. The present invention provides a pattern forming method comprising the steps of:

[0100] The resist top layer film in the two-layer resist process exhibits etching resistance against chlorine-based gases, and therefore, in the two-layer resist process, dry etching of the metal-containing film using the resist top layer film as a mask is preferably performed using an etching gas mainly containing a chlorine-based gas.

[0101] Further, in the present invention, a pattern formation method by a three-layer resist process using such a metal-containing film-forming composition is a method for forming a pattern on a substrate to be processed, comprising the steps of: (II-1) A step of applying the above-described composition for forming a metal-containing film onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (II-2) forming a silicon-containing resist intermediate film on the metal-containing film; (II-3) forming a resist upper layer film on the silicon-containing resist intermediate film using a photoresist material; (II-4) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a pattern on the resist upper layer film; (II-5) a step of transferring the pattern to the silicon-containing resist intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (II-6) a step of transferring a pattern to the metal-containing film by dry etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; and (II-7) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. The present invention provides a pattern forming method comprising the steps of:

[0102] A pattern formation method using a three-layer resist process will be described with reference to Figure 1. In the present invention, the pattern formation method using such a three-layer resist process using a metal-containing film-forming composition involves forming a metal-containing film 3 on a processable layer 2 on a processable substrate 1 using the metal-containing film-forming composition, forming a silicon-containing resist intermediate film 4 on the metal-containing film using a silicon-containing resist intermediate film material, and forming a resist upper layer film 5 on the silicon-containing resist intermediate film using a photoresist material, as shown in Figure 1(A). Next, as shown in FIG. 1(B), the exposed portion 6 of the resist top layer film is pattern-exposed, and then developed with a developer as shown in FIG. 1(C) to form a resist top layer film pattern 5a on the resist top layer film; as shown in FIG. 1(D), using the patterned resist top layer film as a mask, a silicon-containing resist intermediate film pattern 4a is transferred to the silicon-containing resist intermediate film by dry etching; as shown in FIG. 1(E), using the patterned silicon-containing resist intermediate film as a mask, a metal-containing film pattern 3a is transferred to the metal-containing film by dry etching; and as shown in FIG. 1(F), a pattern forming method is provided in which the processable layer on the processable substrate is processed using the patterned metal-containing film as a mask, thereby forming a pattern 2a on the processable substrate 1.

[0103] The silicon-containing resist intermediate film in the three-layer resist process exhibits etching resistance to chlorine-based gases and hydrogen-based gases. Therefore, in the three-layer resist process, the dry etching of the metal-containing film using the silicon-containing resist intermediate film as a mask is preferably performed using an etching gas mainly containing a chlorine-based gas or a hydrogen-based gas.

[0104] Polysiloxane-based interlayers are also preferred as the silicon-containing resist interlayer in the three-layer resist process. By providing the silicon-containing resist interlayer with anti-reflection properties, reflection can be reduced. For 193 nm exposure, in particular, using an organic film containing many aromatic groups and exhibiting high etching selectivity with the substrate results in a high k value and high substrate reflection. However, by providing the silicon-containing resist interlayer with an absorption that results in an appropriate k value, reflection can be reduced, reducing substrate reflection to 0.5% or less. For silicon-containing resist interlayers with anti-reflection properties, anthracene is preferred for 248 nm and 157 nm exposure, while for 193 nm exposure, polysiloxanes with pendant light-absorbing groups containing phenyl groups or silicon-silicon bonds and crosslinked by acid or heat are preferred.

[0105] In addition, in the present invention, a pattern formation method by a four-layer resist process using such a metal-containing film-forming composition is provided, forming a metal-containing film on a substrate to be processed using the composition for forming a metal-containing film; forming a silicon-containing resist intermediate film on the metal-containing film using a silicon-containing resist intermediate film material; forming an organic antireflective coating (BARC) or an adhesion film on the silicon-containing resist intermediate film; forming a resist top layer film on the BARC or the adhesion film using a photoresist material; the resist upper layer film is pattern-exposed and then developed with a developer to form a pattern on the resist upper layer film; Using the resist upper layer film on which the pattern has been formed as a mask, the pattern is transferred to the BARC or the adhesion film and the silicon-containing resist intermediate film by dry etching; using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask, transferring the pattern to the metal-containing film by dry etching; The present invention provides a pattern forming method, comprising the 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.

[0106] Alternatively, an inorganic hard mask may be formed instead of the silicon-containing resist underlayer film. In this case, at least forming a metal-containing film on a workpiece (substrate) using the composition for forming a metal-containing film of the present invention; forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the metal-containing film; forming a resist upper layer film on the inorganic hard mask intermediate film using a photoresist composition, and forming a circuit pattern on the resist upper layer film; transferring a pattern to the inorganic hard mask intermediate film using the resist upper layer film on which the pattern has been formed as a mask; transferring a pattern to the metal-containing film using the patterned inorganic hard mask intermediate film as a mask; Furthermore, by transferring the pattern onto the workpiece using the metal-containing film on which the pattern has been formed as a mask, a semiconductor device circuit pattern can be formed on the substrate.

[0107] In the present invention, a pattern formation method by a four-layer resist process using such a metal-containing film-forming composition is a method for forming a pattern on a substrate to be processed, which includes the steps of: (III-1) A step of applying the above-described composition for forming a metal-containing film onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (III-2) The above Contains metal forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the film; (III-3) forming an organic thin film on the inorganic hard mask intermediate film; (III-4) forming a resist top layer film on the organic thin film using a photoresist material; (III-5) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a pattern on the resist upper layer film; (III-6) a step of transferring the pattern to the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (III-7) transferring a pattern to the metal-containing film by dry etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; and (III-8) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. The present invention provides a pattern forming method comprising the steps of:

[0108] As described above, when forming an inorganic hard mask intermediate film on a metal-containing film, a silicon oxide film, a silicon nitride film, or a silicon oxynitride film (SiON film) can be formed by a CVD method, an ALD method, or the like. For example, methods for forming a silicon nitride film are described in JP 2002-334869 A and WO 2004 / 066377 A. The thickness of the inorganic hard mask intermediate film is preferably 5 to 200 nm, more preferably 10 to 100 nm. Furthermore, a SiON film, which has a high anti-reflective coating effect, is most preferably used as the inorganic hard mask intermediate film. Since the substrate temperature during SiON film formation is 300 to 500°C, the metal-containing film must be able to withstand temperatures of 300 to 500°C. The metal-containing film-forming composition used in the present invention has high heat resistance and can withstand high temperatures of 300 to 500°C, making it possible to combine an inorganic hard mask intermediate film formed by a CVD method or an ALD method with a metal-containing film formed by a spin-coating method.

[0109] As described above, a photoresist film can be formed as a resist top layer on the inorganic hard mask intermediate film. Alternatively, an organic antireflective coating (BARC) or adhesion film can be formed on the inorganic hard mask intermediate film by spin coating, and then a photoresist film can be formed on top of that. In particular, when a SiON film is used as the inorganic hard mask intermediate film, the two-layer antireflective coating consisting of the SiON film and the BARC can suppress reflection even in immersion lithography with a high NA exceeding 1.0. Another advantage of forming a BARC is that it reduces the footing of the photoresist pattern directly above the SiON film.

[0110] Additionally, the present invention provides a pattern formation method by a multilayer resist process using such a metal-containing film-forming composition, which is a method for forming a pattern on a substrate to be processed, comprising the steps of: (IV-1) forming a resist underlayer film on a substrate to be processed; (IV-2) a step of applying the above-described composition for forming a metal-containing film 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 then 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 it with a developer to form a pattern on the resist upper layer film; (IV-5) a step of transferring a pattern to the organic adhesion film and the metal-containing film, or to 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) 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. By adopting the pattern forming method having the above, a semiconductor device circuit pattern can be formed on a substrate.

[0111] As described above, a photoresist film may be formed on the metal-containing film as a resist upper layer film, or an organic adhesive film may be formed on the metal-containing film by spin coating, and a photoresist film may be formed thereon.

[0112] As described above, when forming a resist underlayer film on a substrate to be processed, the resist underlayer film can be formed by a method using a coating-type resist underlayer film material, a CVD method, an ALD method, or the like. Coating-type resist underlayer film materials include those described in JP 2012-001687 A, JP 2012-077295 A, JP 2004-264710 A, JP 2005-043471 A, JP 2005-250434 A, JP 2007-293294 A, JP 2008-065303 A, JP 2004-205685 A, JP 2007-171895 A, JP 2009-014816 A, JP 2007-199653 A, JP 2008-274250 A, JP 2010-122656 A, JP 2012 -214720, JP 2014-029435, WO 2012 / 077640, WO 2010 / 147155, WO 2012 / 176767, JP 2005-128509, JP 2006-259249, JP 2006-259482, JP 2006-293298, JP 2007-316282, JP 2012-145897, JP 2017-119671, JP 2019-044022 and the like.

[0113] The resist top layer film in the above multilayer resist process may be either positive or negative, and the same photoresist compositions as those commonly used can be used. 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 top layer film is not particularly limited, but is preferably 30 to 500 nm, and more preferably 50 to 400 nm.

[0114] Examples of exposure light include high energy rays with a wavelength of 300 nm or less, specifically excimer lasers with wavelengths of 248 nm, 193 nm, and 157 nm, soft X-rays with wavelengths of 3 to 20 nm, electron beams, and X-rays.

[0115] The method for forming a pattern on the resist upper layer film is preferably photolithography with a wavelength of 5 nm or more and 300 nm or less, direct writing with an electron beam, nanoimprinting, or a combination thereof.

[0116] In the pattern forming method, the development method is preferably alkaline development or development using an organic solvent.

[0117] Next, etching is performed using the obtained resist pattern as a mask. In the three-layer resist process, etching of the silicon-containing resist intermediate film or inorganic hard mask intermediate film is performed using a fluorocarbon-based gas and the resist upper layer film pattern as a mask. This forms a silicon-containing resist intermediate film pattern or an inorganic hard mask intermediate film pattern.

[0118] Next, the metal-containing film is etched using the silicon-containing resist intermediate film pattern or inorganic hard mask intermediate film pattern as a mask, preferably using an etching gas mainly containing a chlorine-based gas.

[0119] The next etching of the workpiece can also be carried out using standard methods. For example, if the workpiece is made of SiO2, SiN, or a silica-based low-k insulating film, etching is carried out using mainly fluorocarbon gases. When etching the substrate with fluorocarbon gases, the silicon-containing resist intermediate film pattern in the three-layer resist process is removed at the same time as the substrate is processed.

[0120] The metal-containing film obtained using the metal-containing film-forming composition of the present invention is characterized by excellent etching resistance when etching the workpiece.

[0121] The workpiece (substrate) is not particularly limited, and may be a substrate such as Si, α-Si, p-Si, SiO2, SiN, SiON, W, TiN, or Al, or a substrate with a workpiece layer formed thereon. The workpiece layer may be a low-k film or a stopper film thereof, such as Si, SiO2, SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, or Al-Si, and may be formed to a thickness of typically 50 to 10,000 nm, particularly 100 to 5,000 nm. When forming a workpiece layer, the substrate and workpiece layer are made of different materials.

[0122] The pattern formation method using the metal-containing film-forming composition of the present invention preferably uses a substrate to be processed having structures or steps with a height of 30 nm or more. As described above, the metal-containing film-forming composition of the present invention has excellent filling / planarization properties, so that a flat metal-containing film can be formed even if the substrate to be processed has structures or steps (unevenness) with a height of 30 nm or more. The height of the structures or steps on the substrate to be processed is preferably 30 nm or more, more preferably 50 nm or more, and even more preferably 100 nm or more. In the method for processing a stepped substrate having a pattern with the above height, forming a film using the metal-containing film-forming composition of the present invention and performing filling / planarization makes it possible to uniformize the film thickness of the subsequently formed resist intermediate film and resist top layer film, which is highly preferable, as it makes it easier to ensure a depth of exposure margin (DOF) during photolithography.

[0123] <Method for forming a tone-reversal pattern using a composition for forming a metal-containing film> Further, in the present invention, a tone-reversal pattern forming method using such a metal-containing film-forming composition is a method for forming a pattern on a workpiece substrate, the method comprising: (V-1) forming a resist underlayer film on a substrate to be processed; (V-2) forming a resist intermediate film or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film on the resist underlayer film; (V-3) forming a resist upper layer film using a photoresist material on the resist intermediate film or the combination of the inorganic hard mask intermediate film and an organic thin film; (V-4) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a pattern on the resist upper layer film; (V-5) a step of transferring a pattern to the resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film, by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (V-6) a step of transferring a pattern to the resist underlayer film by dry etching using the resist interlayer film or inorganic hard mask interlayer film to which the pattern has been transferred as a mask; (V-7) a step of applying the above-described composition for forming a metal-containing film onto the resist underlayer film on which the pattern has been formed, followed by heat treatment to cover the resist underlayer film with a metal-containing film and filling spaces between the resist underlayer film patterns with the metal-containing film; (V-8) etching back the metal-containing film covering the resist underlayer film on which the pattern has been formed by a chemical stripper or dry etching to expose the upper surface of the resist underlayer film on which the pattern has been formed; (V-9) a step of removing the resist intermediate film or the inorganic hard mask intermediate film remaining on the upper surface of the resist underlayer film by dry etching; (V-10) a step of removing the resist underlayer film on which the pattern is formed and the surface is exposed by dry etching, thereby forming a reverse pattern of the original pattern on the metal-containing film; (V-11) A step of processing the substrate to be processed using the metal-containing film on which the reverse pattern has been formed as a mask to form a reverse pattern on the substrate to be processed. The present invention provides a method for forming a tone-reversal pattern, comprising:

[0124] A tone-reversal pattern formation method using a metal-containing film-forming composition will be described with reference to Figure 2. In the tone-reversal pattern formation method using such a metal-containing film-forming composition, as shown in Figure 2(G), a resist underlayer film 7 is formed on a processable layer 2 on a processable substrate 1, a resist intermediate film 4 or a combination of an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film is formed on the resist underlayer film 7, and a resist upper layer film 5 is formed on the resist intermediate film 4 or the combination of the inorganic hard mask intermediate film and the organic thin film using a photoresist material.Subsequently, as shown in FIG. 2(H), the exposed portion 6 of the resist upper layer film is pattern-exposed, and then developed with a developer as shown in FIG. 2(I), to form a resist upper layer film pattern 5a on the resist upper layer film. As shown in FIG. 2(J), using the resist upper layer film on which the pattern has been formed as a mask, a resist intermediate film pattern 4a or an inorganic hard mask intermediate film pattern is transferred to the resist intermediate film, or the organic thin film and the inorganic hard mask intermediate film, by dry etching. As shown in FIG. 2(K), using the resist intermediate film or inorganic hard mask intermediate film on which the pattern has been transferred as a mask, a resist underlayer film pattern 7a is transferred to the resist underlayer film by dry etching. As shown in FIG. 2(L), a metal-containing film 8 is coated on the resist underlayer film on which the pattern has been formed using the metal-containing film-forming composition, to form the resist underlayer film pattern 7a. and forming a reversed pattern in the metal-containing film by etching back the metal-containing film covering the resist underlayer film with a chemical stripper or dry etching, as shown in FIG. 2(M), to form a reversed metal-containing film pattern 8a, exposing the top surface of the resist underlayer film with the pattern formed thereon. Then, removing the resist interlayer film or hard mask interlayer film remaining on the top surface of the resist underlayer film pattern 7a by dry etching, as shown in FIG. 2(N), removing the exposed surface of the resist underlayer film with the pattern formed thereon by dry etching, as shown in FIG. 2(O), to form a reversed pattern of the original pattern in the metal-containing film. Then, processing the workpiece using the metal-containing film with the reversed pattern formed thereon as a mask, as shown in FIG. 2(P), to form a reversed pattern 2b in the workpiece layer.

[0125] As described above, when forming a resist underlayer film on a substrate to be processed, the resist underlayer film can be formed by a method using a coating-type resist underlayer film material, a CVD method, an ALD method, etc. Examples of coating-type resist underlayer film materials include the same resins and compositions as those described above.

[0126] In the tone reversal pattern formation method, after the obtained resist underlayer film pattern is coated with a metal-containing film-forming composition, the metal-containing film is preferably removed using a dry etching gas mainly containing a chlorine-based gas to expose the upper surface of the resist underlayer film pattern. Then, the resist intermediate film or inorganic hard mask intermediate film remaining on the resist underlayer film is removed by dry etching with a fluorocarbon-based gas, and the exposed surface of the resist underlayer film pattern is removed by dry etching with an oxygen-based gas to form the metal-containing film pattern.

[0127] In the tone reversal patterning method, the resist underlayer film pattern preferably has structures or steps with a height of 30 nm or more. As described above, the metal-containing film-forming composition of the present invention has excellent filling / planarization properties, making it possible to form a flat metal-containing film even if the film to be processed has structures or steps (unevenness) with a height of 30 nm or more. The height of the structures or steps in the resist underlayer film pattern is preferably 30 nm or more, more preferably 50 nm or more, and even more preferably 100 nm or more. In a method for reversing a resist underlayer film pattern having a pattern with the above height, forming a film using the metal-containing film-forming composition of the present invention and performing filling / planarization enables high-precision pattern reversal / transfer, which is highly preferred. Compared to resist underlayer films made using conventional coating-type resist underlayer film materials, the metal-containing film-forming composition has superior dry etching resistance using fluorocarbon-based gases. Therefore, by reversing the resist underlayer film pattern with the metal-containing film-forming composition, a desired resist pattern can be formed on the film to be processed with high precision. [Example]

[0128] The present invention will be described in more detail below with reference to Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples, but is not limited thereto. Regarding 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 calculated.

[0129] [Synthesis example] In the following synthesis examples and comparative synthesis examples, raw materials group G: (G1) to (G13) shown below were used. Raw material group G: (G1) to (G13) are shown below. [ka]

[0130] [Synthesis Example 1] Synthesis of metal-containing film-forming compound (A-1) 5.0 g of dibutyltin oxide, 8.5 g of carboxylic acid (G1), and 100 g of toluene were added, and the mixture was refluxed for 7 hours while removing water. After the reaction, the solvent was removed under reduced pressure to obtain compound (A-1). (A-1): Mw = 392, Mw / Mn = 1.03 [ka]

[0131] [Synthesis Examples 2 to 10, Comparative Synthesis Examples 1 to 3] Synthesis of metal-containing film-forming compounds (A-2) to (A-10) and comparative compounds (R-1) to (R-3) Compounds (A-2) to (A-10) for forming metal-containing films and comparative compounds (R-1) to (R-3) shown in Tables 1 to 3 were obtained under the same reaction conditions as in Synthesis Example 1, except that Compound Group G and dibutyltin oxide, di-tert-butyltin oxide, dioctyltin oxide, or dibenzyltin oxide were used in the amounts shown in Tables 1 to 3. The weight-average molecular weight (Mw) and dispersity (Mw / Mn) of these compounds were determined. The results are shown in Table 4. [Table 1]

[0132] [Table 2]

[0133] [Table 3]

[0134] [Table 4]

[0135] [Comparative Synthesis Example 4] Synthesis of Comparative Compound (R-4) 8.0 g of butyltin trichloride was stirred at room temperature, and 10 g of acrylic acid was added dropwise. After the dropwise addition, the temperature was raised to 80°C and the mixture was stirred for 7 hours. After the reaction was completed, the acrylic acid was removed under reduced pressure to obtain (R-4). (R-4): Mw = 51, Mw / Mn = 1.14 [ka]

[0136] [Comparative Synthesis Example 5] Synthesis of Comparative Compound (R-5) As a compound containing 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 in 500 g of IPA was added dropwise to 284 g of titanium tetraisopropoxide (Tokyo Chemical Industry Co., Ltd.) in 500 g of IPA over 2 hours while stirring. 120 g of 2-methyl-2,4-pentanediol was added to the resulting solution and stirred at room temperature for 30 minutes. This solution was concentrated under reduced pressure at 30°C and then heated to 60°C and continued to be heated under reduced pressure until no more distillate was produced. When no more distillate was observed, 1,200 g of PGMEA was added and the mixture was heated under reduced pressure at 40°C until no more IPA was produced, yielding 1,000 g of a PGMEA solution of titanium-containing compound (R-5) (compound concentration: 20% by mass). The molecular weight of this compound measured in terms of polystyrene was found to be Mw = 1,100.

[0137] [Comparative Synthesis Example 6] Synthesis of Comparative Resin (R-6) Under a nitrogen atmosphere, 160.2 g of 1,5-dihydroxynaphthalene, 56.8 g of formaldehyde, and 300 g of PGME (propylene glycol monomethyl ether) were added and homogenized at an internal temperature of 100 °C. A premixed mixture of 8.0 g of paratoluenesulfonic acid monohydrate and 8.0 g of PGME was then slowly added dropwise, and the reaction was carried out at an internal temperature of 80 °C for 8 hours. After the reaction was completed, the mixture was cooled to room temperature, 2,000 ml of MIBK was added, and the mixture was washed six times with 500 ml of purified water. The organic layer was evaporated to dryness under reduced pressure. 300 g of THF was added to the residue to form a homogenous solution, which was then crystallized in 2,000 g of hexane. The precipitated crystals were separated by filtration, washed twice with 500 g of hexane, and then recovered. The recovered crystals were dried in vacuo at 70 °C to obtain resin (R-6). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (R-6): Mw = 3,300, Mw / Mn = 2.54 [ka]

[0138] [Preparation of Metal-Containing Film-Forming Composition (UDL-1)] The metal-containing film-forming compound (A-1) was dissolved in a mixed solvent (solvent) of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (CyHO) containing 0.5 mass% of surfactant FC-4430 (manufactured by Sumitomo 3M Limited) in the proportions shown in Table 5, and the solution was filtered through a 0.02 μm membrane filter to prepare a metal-containing film-forming composition (UDL-1).

[0139] [Preparation of Metal-Containing Film-Forming Compositions (UDL-2 to 13) 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 5. In Table 5, "-" indicates that the corresponding component was not used. The crosslinking agent used was the formula (C-1) below, the acid generator (TAG) used was the formula (G-1) below, the high-boiling point solvent (B-1) used was 1,6-diacetoxyhexane (boiling point 260°C), and the flowability promoter polymer (F-1) was used.

[0140] [Crosslinking agent] The crosslinking agent (C-1) used in the metal-containing film-forming composition is shown below. [ka]

[0141] [Acid generator] The acid generator (G-1) used in the metal-containing film-forming composition is shown below. [ka]

[0142] [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 and the mixture was kept at an internal temperature of 50°C to form a uniform dispersion. 11.9 g of propargyl bromide was slowly added, and the reaction was carried out at an internal temperature of 50°C for 24 hours. 300 ml of methyl isobutyl ketone and 300 g of pure water were added to the reaction mixture to dissolve the precipitated salt, and the separated aqueous layer was then removed. The organic layer was further washed six times with 100 g of 3% aqueous nitric acid solution and 100 g of pure water, and then evaporated to dryness under reduced pressure to obtain polymer (F-1) for use as a fluidity promoter. The weight average molecular weight (Mw) and dispersity (Mw / Mn) were determined by GPC, and the following results were obtained. (F-1): Mw = 8,500, Mw / Mn = 3.46 [ka]

[0143] [Table 5]

[0144] [Evaluation of Heat Resistance and Solvent Resistance (Examples 1-1 to 1-13, Comparative Examples 1-1 to 1-5)] The metal-containing film-forming compositions (UDL-1 to 13, Comparative Examples UDL-1 to 5) prepared above were applied to silicon substrates and baked at 100°C for 60 seconds, after which the film thickness (a [nm]) was measured. Subsequently, after baking for 60 seconds at each baking temperature shown in Table 6, the film thickness (b [nm]) was measured, and the difference in film thickness before and after the additional baking treatment (remaining film ratio: (b / a) × 100) was calculated. Furthermore, PGMEA solvent was dispensed onto the film, left for 30 seconds, spun dry, and baked at 100°C for 60 seconds to evaporate the PGMEA. 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 6 below. [Table 6]

[0145] As shown in Table 6, the metal-containing film-forming compositions of the present invention (Examples 1-1 to 1-13) had a residual film ratio ((b / a) x 100) of 45% or more after high-temperature additional baking. This indicates that films with fewer sublimates can be formed, even compared to Comparative Example 1-3, which used a similar metal-containing film-forming composition, and that these compositions have the high-temperature bake resistance required for resist underlayer films. Furthermore, the films that underwent high-temperature additional baking had a residual film ratio ((c / b) x 100) of 99% or more after a PGMEA rinse treatment, indicating that crosslinking reactions occurred and sufficient solvent resistance was achieved. These results are thought to be due to the compounds of the present invention containing groups represented by the above general formulas (W-1) to (W-4), which have a high crosslinking group density and therefore have excellent thermosetting properties. In particular, Examples 1-2 to 1-4 and 1-7, which contain compounds (UDL-2 to 7) in which W is a group represented by general formula (W-1) or (W-2) and X is a group represented by general formula (2) in the general formula (1), exhibited a residual film ratio ((b / a) × 100) of 50% or more and a residual film ratio ((c / b) × 100) of 100%. It was also found that compounds (UDL-9 to 10) containing other types of carboxylic acids exhibited comparable solvent resistance. On the other hand, Comparative Example UDL-1, lacking a crosslinking group, exhibited insufficient heat resistance, with a residual film ratio ((b / a) × 100) of 5% or less after high-temperature additional baking. Furthermore, Comparative Examples UDL-2 and UDL-4, which have terminal crosslinking groups different from those of the present invention, also exhibited insufficient heat resistance, with a residual film ratio of 5 nm or less after high-temperature baking. Comparative Example 1-5, which used a titanium compound reported in [Synthesis Example A-II] of Japanese Patent No. 6189758 as a compound containing 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 the high-temperature additional bake treatment was large, and it was found that the volume shrinkage due to high-temperature bake was larger than that of the compound for forming a metal-containing film of the present invention.

[0146] [Evaluation of Filling Characteristics (Examples 2-1 to 2-13, Comparative Examples 2-1 to 2-3)] Each of the metal-containing film-forming compositions (UDL-1 to 13 and comparative examples UDL-3, 5, and 6) was applied to a SiO2 wafer substrate with a dense line and space pattern (line width: 40 nm, line depth: 120 nm, center-to-center distance: 80 nm) and heated using a hot plate at the temperature shown in Table 7 for 60 seconds to form a 100-nm-thick metal-containing film. The substrate used was a base substrate 9 (SiO2 wafer substrate) with a dense line and space pattern as shown in Figure 3(Q) (overhead view) and (R) (cross-sectional view). The cross-sectional shape of each wafer substrate was observed using a Hitachi S-4700 electron microscope to confirm the presence of voids (air gaps) within the metal-containing film filling the gaps between the lines. The results are shown in Table 7. When a metal-containing film-forming composition with poor filling properties was used, it was unable to successfully fill the uneven substrate in this evaluation. When a metal-containing film-forming composition with good filling properties is used, in this evaluation, the metal-containing film 10 can fill without gaps between the lines of the base substrate 9 having a dense line and space pattern, as shown in Figure 3(S). ◯ indicates that filling is possible without large voids, △ indicates that voids are visible, and × indicates that filling is not possible. [Table 7]

[0147] As shown in Table 7, in Examples 2-1 to 2-13, which used the metal-containing film-forming compositions of the present invention (UDL-1 to 13), and in Comparative Example 2-1, which used a similar metal-containing film-forming composition (Comparative Example UDL-3), it was possible to fill dense line and space patterns without generating voids, confirming their excellent filling properties. On the other hand, in Comparative Example 2-2, which used the titanium compound reported in [Synthesis Example A-II] of Japanese Patent No. 6189758, voids were observed at the bottom of the pattern. As observed in the solvent resistance evaluation above, it is presumed that the voids were generated due to the large volume shrinkage caused by high-temperature baking. In Comparative Example 2-3, which used Comparative Example UDL-6, it was possible to fill dense line and space patterns without generating voids.

[0148] [Evaluation of Planarization Characteristics (Examples 3-1 to 3-13, Comparative Examples 3-1 to 3-3)] 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 area and the non-line pattern area of ​​the filling film 12 was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd. The results are shown in Table 8. In this evaluation, the smaller the step, the better the planarization property. [Table 8]

[0149] As shown in Table 8, Examples 3-1 to 3-13, which used the metal-containing film-forming compositions (UDL-1 to 13) of the present invention, demonstrated superior planarization characteristics, with smaller film step heights between patterned and non-patterned portions, compared with Comparative Example 3-2, which used Comparative Example UDL-5, an organic resist underlayer film material, and Comparative Example 3-3, which used Comparative Example UDL-6 containing resin (R-6). It can be seen that the inclusion of the structure of general formula (1) improves thermal fluidity and exhibits superior planarization characteristics. In particular, Example 3-10, which used the metal-containing film-forming composition (UDL-10) containing A-10, synthesized by mixing another type of carboxylic acid with a long alkyl chain, demonstrated even more superior planarization characteristics. Furthermore, Examples 3-11 to 3-12, which used compositions for forming metal-containing films (UDL-11 to 12) containing a high-boiling point solvent (B-1) and a flow promoter (F-1), resulted in significantly improved planarization characteristics compared to Example 3-2, which did not contain these additives, demonstrating that the thermal flow properties of compounds for forming metal-containing films can be further improved by using these additives.

[0150] [Evaluation of Etching Resistance (Examples 4-1 to 4-13, Comparative Examples 4-1 to 4-3)] The metal-containing film-forming compositions (UDL-1 to 13, and comparative examples UDL-3, 5, and 6) were applied to silicon substrates and heated for 60 seconds using a hot plate at the temperatures shown in Table 9 to form metal-containing films with a thickness of 100 nm, and film thickness A was measured. Next, etching was performed using CF4 gas, O2 gas, and Cl2 for the specified number of seconds under the conditions shown below using a ULVAC etching system CE-300I, film thickness B was measured, and the film thickness etched per minute was calculated as the etching rate (nm / min) from the film thickness etched per second (film thickness B - film thickness A). The results are shown in Table 9.

[0151] Dry etching conditions with CF4 gas Pressure: 1Pa Antenna RF power: 100W Bias RF power: 15W CF4 gas flow rate: 15sccm Time: 30sec

[0152] Dry etching conditions with O2 gas Pressure: 1Pa Antenna RF power: 300W Bias RF power: 0W O2 gas flow rate: 25sccm Time: 20sec

[0153] Dry etching conditions using Cl2 gas Pressure: 1Pa Antenna RF power: 320W Bias RF power: 30W Cl2 gas flow rate: 25sccm Time: 10sec

[0154] [Table 9]

[0155] As shown in Table 9, Examples 4-1 to 4-13, which used the metal-containing film-forming compositions (UDL-1 to 13) of the present invention, exhibited superior CF4 etching resistance and O2 etching resistance compared to Comparative Example 4-3, which used Comparative Example UDL-6 containing resin (R-6). Furthermore, while they exhibited superior resistance to etching using CF4 and O2 gases, they also exhibited superior removability when etched using Cl2 gas.

[0156] [Pattern Forming Method (Examples 5-1 to 5-13, Comparative Examples 5-1 to 5-2)] The metal-containing film-forming compositions (UDL-1 to 13 and comparative examples UDL-5 to 6) were each applied to a SiO2 wafer substrate with a trench pattern (trench width 10 μm, trench depth 0.10 μm) and baked in air at 250°C for 60 seconds to form a 100 nm thick metal-containing film. A silicon-containing resist interlayer material (SOG-1) was applied on top of the substrate and baked at 220°C for 60 seconds to form a 30 nm thick resist interlayer. An ArF single-layer resist top layer material was then applied on top of that and baked at 105°C for 60 seconds to form a 100 nm thick photoresist film. An immersion protective film material (TC-1) was applied on top of the photoresist film and baked at 90°C for 60 seconds to form a 50 nm thick protective film.

[0157] The silicon-containing resist interlayer material (SOG-1) was prepared by dissolving a polymer designated as ArF silicon-containing interlayer polymer (SiP1) and a thermal crosslinking catalyst (CAT1) in an organic solvent containing 0.1 mass% of FC-4430 (manufactured by Sumitomo 3M) in the proportions shown in Table 10, and filtering the solution through a fluororesin filter with a pore size of 0.1 μm.

[0158] [Table 10]

[0159] The structural formulae of the ArF silicon-containing intermediate film polymer (SiP1) and thermal crosslinking catalyst (CAT1) used are shown below. [ka]

[0160] 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 surfactant FC-4430 (Sumitomo 3M Limited) in the proportions shown in Table 11, and filtering the solution through a 0.1 μm fluororesin filter.

[0161] [Table 11]

[0162] 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]

[0163] The immersion protective film material (TC-1) was prepared by dissolving the protective film polymer (PP1) in an organic solvent in the proportions shown in Table 12 and filtering the solution through a 0.1 μm fluororesin filter.

[0164] [Table 12]

[0165] The protective film polymer (PP1) used in the immersion protective film material (TC-1) is shown below. [ka]

[0166] The resist was then exposed using an ArF immersion exposure system (Nikon Corporation; NSR-S610C, NA 1.30, σ 0.98 / 0.65, 35-degree dipole s-polarized illumination, 6% halftone phase-shift mask), baked at 100°C for 60 seconds (PEB), and developed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 30 seconds to obtain a 55 nm 1:1 positive line-and-space pattern (resist upper layer film pattern).

[0167] Next, the resist intermediate film was dry-etched using the resist upper layer film pattern as a mask to form a hard mask pattern, the metal-containing film was etched using the resulting hard mask pattern as a mask to form a metal-containing film pattern, and the SiO2 film was etched using the resulting metal-containing film pattern as a mask. The etching conditions are as follows:

[0168] Conditions for transferring the resist upper layer film pattern to the resist intermediate film. Dry etching conditions with CF4 gas Pressure: 1Pa Antenna RF power: 100W Bias RF power: 15W CF4 gas flow rate: 15sccm Time: 60sec

[0169] Conditions for transferring hard mask patterns to metal-containing films. Pressure: 1Pa Antenna RF power: 320W Bias RF power: 30W Cl2 gas flow rate: 25sccm Time (Examples 5-1 to 5-13): 15 seconds Time (Comparative Examples 5-1 and 5-2): 60 seconds

[0170] Transfer conditions for metal-containing film pattern onto SiO2 film. Dry etching conditions with CF4 gas Pressure: 1Pa Antenna RF power: 100W Bias RF power: 15W CF4 gas flow rate: 15sccm Time: 60sec

[0171] The cross section of the pattern was observed using an electron microscope (S-4700) manufactured by Hitachi, Ltd. The results are shown in Table 13.

[0172] [Table 13]

[0173] As shown in Table 13, the metals of the present invention Contains In Examples 5-1 to 5-13 in which the film-forming compositions (UDL-1 to 13) were used, the resist upper layer film pattern was successfully transferred to the substrate in the end. Contains The film-forming compositions were confirmed to be suitable for microfabrication using a multilayer resist method. On the other hand, Comparative Example 5-1, which used Comparative Example UDL-5, which was confirmed to have insufficient performance in the filling property evaluation and planarization property evaluation, experienced pattern collapse during pattern processing, and ultimately failed to obtain a satisfactory pattern. Furthermore, Comparative Example 5-2, which used Comparative Example UDL-6, which was confirmed to have insufficient performance in the planarization property evaluation and dry etching resistance evaluation, while exhibiting no problems with filling properties, experienced distortion of the pattern shape during pattern processing, and ultimately failed to obtain a satisfactory pattern.

[0174] From the above, the metal of the present invention Contains Since the film-forming compound is an organotin compound that has a high degree of both thermal fluidity and thermosetting properties, a metal-containing film-forming composition using this compound has excellent dry etching resistance compared to conventional resist underlayer film materials, and can provide a resist underlayer film material 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.

[0175] The present specification includes the following aspects. [1]: A compound for forming a metal-containing film, which is used in a composition for forming a metal-containing film, characterized in that the compound is represented by the following general formula (M): [ka] In the general formula (M), T is a group represented by the following general formula (1) or a group represented by the following general formula (1'), at least one of which is a group represented by the following general formula (1), and one or more of these may be used in combination; Q is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted Carbon number a cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aliphatic unsaturated organic group having 2 to 20 carbon atoms and containing one or more double or triple bonds, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms, or a combination thereof, wherein m and n are any integers and satisfy the relationships m+n=4, m≧1, and n≧2. [ka] (In general formula (1), X represents a divalent organic group having 1 to 31 carbon atoms, W represents a group represented by the following general formulas (W-1) to (W-4), * represents a bond to the Sn atom, and in general formula (1'), R represents an optional substituent, * represents a bond to the Sn atom.) [ka] (In general formulas (W-1) and (W-3), R1 represents a hydrogen atom or a methyl group, which may be the same or different; in (W-3) and (W-4), R2 represents a hydrogen atom, a substituted or unsubstituted saturated monovalent organic group having 1 to 20 carbon atoms or an unsaturated monovalent organic group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted arylalkyl group having 7 to 31 carbon atoms; and * represents the bond to the carbonyl.) [2]: The compound for forming a metal-containing film according to the above [1], wherein in the general formula (1), X is an unsaturated hydrocarbon group having 2 to 20 carbon atoms. [3]: The compound for forming a metal-containing film according to the above [2], wherein in the general formula (1), X is a group represented by the following general formula (2): [ka] (In general formula (2), R a , and R b is a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and R c is a hydrogen atom or a monovalent organic group having 1 to 17 carbon atoms, and R a and R b The total number of carbon atoms is 0 to 18, and R a and R b may be bonded to form a cyclic substituent, and *1 and *2 each represent the bonding site with the carbonyl group, and *1 and *2 may be reversed.) [4]: The compound for forming a metal-containing film according to any one of [1] to [3], 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 on a polystyrene basis by gel permeation chromatography, is 1.00≦Mw / Mn≦1.50. [5]: A composition for forming a metal-containing film used in semiconductor manufacturing, characterized in that it contains (A) a compound for forming a metal-containing film according to any one of [1] to [4] above, and (B) an organic solvent. [6]: The metal-containing film-forming composition according to [5] above, characterized in that the composition further contains one or more of (C) a crosslinking agent, (E) a surfactant, (F) a flowability promoter, and (G) an acid generator. [7]: The metal-containing film-forming composition according to [5] or [6], wherein the (B) organic solvent contains one or more organic solvents having a boiling point of 180°C or higher as (B1) high-boiling-point solvents. [8]: A method for forming a pattern on a workpiece substrate, (I-1) A step of applying any one of the compositions for forming a metal-containing film according to [5] to [7] above onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (I-2) forming a resist top layer film on the metal-containing film using a photoresist material; (I-3) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a pattern on the resist upper layer film; (I-4) a step of transferring the pattern to the metal-containing film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; and (I-5) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. A pattern forming method comprising the steps of: [9]: A method for forming a pattern on a workpiece substrate, (II-1) A step of applying any one of the compositions for forming a metal-containing film according to [5] to [7] above onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (II-2) forming a silicon-containing resist intermediate film on the metal-containing film; (II-3) forming a resist upper layer film on the silicon-containing resist intermediate film using a photoresist material; (II-4) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a pattern on the resist upper layer film; (II-5) a step of transferring the pattern to the silicon-containing resist intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (II-6) a step of transferring a pattern to the metal-containing film by dry etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; and (II-7) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. A pattern forming method comprising the steps of:

[10] : A method for forming a pattern on a workpiece substrate, (III-1) A step of applying any one of the compositions for forming a metal-containing film according to [5] to [7] above onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (III-2) The above Contains metal forming an inorganic hard mask intermediate film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the film; (III-3) forming an organic thin film on the inorganic hard mask intermediate film; (III-4) forming a resist top layer film on the organic thin film using a photoresist material; (III-5) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a pattern on the resist upper layer film; (III-6) a step of transferring the pattern to the organic thin film and the inorganic hard mask intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (III-7) transferring a pattern to the metal-containing film by dry etching using the inorganic hard mask intermediate film to which the pattern has been transferred as a mask; and (III-8) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. A pattern forming method comprising the steps of:

[11] : The pattern forming method according to

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

[12] : A method for forming a pattern on a workpiece substrate, (IV-1) forming a resist underlayer film on a substrate to be processed; (IV-2) A step of applying a composition for forming a metal-containing film according to any one of the above [5] to [7] 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 then 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 it with a developer to form a pattern on the resist upper layer film; (IV-5) a step of transferring a pattern to the organic adhesion film and the metal-containing film, or to 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) 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:

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

[0176] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits similar effects is included within the technical scope of the present invention. [Explanation of symbols]

[0177] 1...Substrate to be processed, 2...Layer to be processed, 2a...pattern (pattern formed on the processing layer), 2b...reverse pattern (reverse pattern formed on the processing layer), 3...metal-containing film, 3a...metal-containing film pattern, 4...resist intermediate film, 4a...resist intermediate film pattern, 5...resist upper layer film, 5a...resist upper layer film pattern, 6...exposed portion, 7...resist lower layer film, 7a...resist underlayer film pattern, 8...metal-containing film, 8a...Inverted metal-containing film pattern, 9...Base substrate having dense line and space pattern, 10...Metal-containing film, 11... base substrate having dense line and space pattern; 12... filling film; Delta 12: Step difference between the filling film in the dense line pattern area and the non-line pattern area.

Claims

1. A compound for forming a metal-containing film, which is used in a composition for forming a metal-containing film, characterized in that the compound is represented by the following general formula (M): 【Chemistry 1】 (In general formula (M), T is a group represented by the following general formula (1) or a group represented by the following general formula (1'), at least one of which is a group represented by the following general formula (1), and one or more of these may be used in combination; Q represents an unsubstituted alkyl group having 1 to 20 carbon atoms, an unsubstituted arylalkyl group having 7 to 31 carbon atoms, or a combination thereof; m and n are any integers and satisfy the relationships m+n=4, m≧1, and n≧2.) 【Chemistry 2】 (In general formula (1), X is a group represented by the following general formula (2), W is a group represented by the following general formulas (W-1) to (W-4), * represents a bonding site with the Sn atom, general formula (1') represents any of the groups represented by the following formulas (1'-1) to (1'-3), * represents a bonding site with the Sn atom.) 【Transformation 3】 (In general formula (2), R a and R b are hydrogen atoms or monovalent organic groups having 1 to 18 carbon atoms, R c is a hydrogen atom or a monovalent organic group having 1 to 17 carbon atoms, the total number of carbon atoms of R a and R b is 0 to 18, R a and R b may be bonded to form a cyclic substituent, *1 and *2 each represent a bonding site with a carbonyl group, and *1 and *2 may be reversed.) 【Chemistry 4】 (In general formulas (W-1) and (W-3), R １ represents a hydrogen atom or a methyl group, which may be the same or different from each other, and in (W-3) and (W-4), R ２ represents any group selected from the following formula (R 2W ), and * represents the bond to the carbonyl. 【Transformation 5】 (* indicates the bond to the nitrogen atom.) 【Transformation 6】 (* indicates the bond with the tin atom.) 【Transformation 7】 (* indicates the bond with the tin atom.) 【Transformation 8】 (* indicates the bond with the tin atom.)

2. 2. The compound for forming a metal-containing film according to claim 1, wherein 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, is 1.00≦Mw / Mn≦1.50, as determined by gel permeation chromatography.

3. A composition for forming a metal-containing film used in semiconductor manufacturing, comprising (A) the compound for forming a metal-containing film according to claim 1 or 2, and (B) an organic solvent.

4. 4. The metal-containing film-forming composition according to claim 3, further comprising one or more of (C) a crosslinking agent, (E) a surfactant, (F) a flowability promoter, and (G) an acid generator.

5. 4. The metal-containing film-forming composition according to claim 3, wherein the (B) organic solvent contains one or more organic solvents having a boiling point of 180° C. or higher as (B1) a high-boiling-point solvent.

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

7. A method for forming a pattern on a workpiece substrate, comprising: (II-1) A step of applying the metal-containing film-forming composition according to claim 3 onto a substrate to be processed, followed by heat treatment to form a metal-containing film; (II-2) forming a silicon-containing resist intermediate film on the metal-containing film; (II-3) forming a resist upper layer film on the silicon-containing resist intermediate film using a photoresist material; (II-4) a step of pattern-exposing the resist upper layer film and then developing it with a developer to form a pattern on the resist upper layer film; (II-5) a step of transferring the pattern to the silicon-containing resist intermediate film by dry etching using the resist upper layer film on which the pattern has been formed as a mask; (II-6) A step of transferring a pattern to the metal-containing film by dry etching using the silicon-containing resist intermediate film to which the pattern has been transferred as a mask; and (II-7) A step of processing the substrate to be processed using the metal-containing film on which the pattern has been formed as a mask to form a pattern on the substrate to be processed. A pattern forming method comprising the steps of:

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

9. 9. The pattern formation method according to claim 8, wherein the inorganic hard mask intermediate film is formed by a CVD method or an ALD method.

10. A method for forming a pattern on a workpiece substrate, comprising: (IV-1) A step of forming a resist underlayer film on a substrate to be processed; (IV-2) A step of applying the metal-containing film-forming composition according to claim 3 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 then 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 it with a developer to form a pattern on the resist upper layer film; (IV-5) a step of transferring a pattern to the organic adhesion film and the metal-containing film, or to 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) transferring the 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:

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

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